CN109384887B - Polymer with selective water plugging function and preparation method and application thereof - Google Patents
Polymer with selective water plugging function and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
Abstract
The invention relates to the field of research on profile control and water shutoff materials of oil fields and improvement on the productivity of oil wells in high water cut periods, and discloses a polymer with a water shutoff function, which is prepared by carrying out a polymerization reaction on an emulsion containing a monomer A, a monomer B and oil-soluble resin in the presence of an initiator, a chain transfer agent, a cross-linking agent and water, wherein the monomer A is acrylamide; monomer B is of formula (1), wherein R1Is C5-C15 alkyl, R2Is H, C1-C12 alkyl, -COOH, -SO3H、‑SO3K and-SO3Any one of Na, n is an integer of 8-16; the oil-soluble resin is one or more of rosin resin, dammar resin, oil-soluble phenolic resin, petroleum resin, terpene resin and coumarone resin. The polymer prepared by the invention has excellent effects of selectively blocking water but not oil, and has higher scouring resistance times.
Description
Technical Field
The invention relates to the research field of oil field profile control water shutoff materials and improvement of oil well production of oil reservoirs in high water cut periods, in particular to a polymer with a selective water shutoff function, a method for preparing the polymer with the selective water shutoff function, the polymer with the selective water shutoff function prepared by the method, and application of the polymer with the selective water shutoff function as a selective water shutoff agent.
Background
The water plugging process for the oil well is a key technology for optimizing the development result of water injection of the oil and gas field. The water layer and the oil layer in the stratum are mutually interwoven, the heterogeneity is serious, the two reservoirs are difficult to be effectively isolated by the existing construction technology, but oil field enterprises need to stabilize the yield of crude oil and reduce the comprehensive water content of an oil well as far as possible, and therefore higher requirements are provided for the water shutoff agent with high oil/water selectivity. Although the existing water-based, oil-based and polymer gel water-blocking systems have certain selectivity, the water-blocking and oil-blocking systems block water and oil, and indoor physical model experiment results show that the oil-blocking rate of the existing water-blocking agents is more than 35%, the temperature resistance and salt resistance of the systems are poor, and the popularization and application range is small. Although the water-soluble polymer water shutoff agent can preferentially enter the stratum with higher water saturation, part of the water-soluble polymer water shutoff agent can enter an oil layer in the stratum migration, and the water-soluble polymer water shutoff agent is very difficult to discharge because the water shutoff agent does not have the self-plugging removal capability. Although the oil-based cement water shutoff agent can also improve the crude oil recovery efficiency to a greater extent, the oil-based cement water shutoff agent has the great disadvantage that a stratum with higher water saturation is generally plugged, and when the oil-based cement water shutoff agent flows into an oil-water mixed stratum, even if only a small part of stratum water is mixed in an oil layer, the oil-based cement water shutoff agent can react with the stratum water to solidify the cement, which shows that the water shutoff selectivity of the oil-based cement water shutoff agent is also greatly deficient. The polymer gel water shutoff agent enables the oil-water phase permeability to be reduced unevenly by means of the change of the effective movable volume under the action of oil and water, but the oil-water channel physical shutoff can be caused by the treatment mode, so that the seepage capability of a porous medium is reduced, the oil production capability is also reduced while the water production of an oil well is greatly reduced, the liquid production amount is too low due to improper treatment, and the yield of crude oil is reduced.
At present, selective water shutoff agents and deep profile control technologies at home and abroad are improved day by day, and the selective water shutoff materials are developed greatly on the technologies of research development, construction process and the like, but along with the development of oil fields, the characteristics of oil layers and the environment are changed constantly, particularly, the water shutoff materials are adopted for a long time to make the contradiction of oil reservoir development more prominent in the later development period, the practical development experience of the oil fields is summarized according to the characteristics of the selective water shutoff materials, and the technical problem which must be overcome at present by the selective water shutoff agents is provided so as to develop new technologies in a targeted manner to adapt to the special oil fields and improve the water shutoff effect of a selective system.
In summary, most of the selective plugging agents used for water plugging of oil wells at present are gels or jelly generated by water-soluble polymers such as polyacrylamide and derivatives thereof in the stratum to plug the stratum water, or oil-based plugging agents are used for gelling or curing when meeting water to plug water channeling passages, but due to poor selectivity, the oil phase permeability can be greatly reduced while water plugging is carried out, so that low liquid after plugging is caused, and the application of the water plugging technology of the oil wells is restricted.
Therefore, a novel high-selectivity water plugging material is developed, so that water plugging and oil plugging of an oil layer are realized, and the method has important significance for improving the productivity of an oil well in an ultrahigh water cut period.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polymer with a selective water plugging function, a preparation method and application thereof, namely, a certain amount of acrylamide monomers, surface active monomers and oil-soluble resin particles are added into an aqueous solution, the surface active monomers can participate in polymerization and have strong emulsification, a stable emulsion system can be formed after stirring, an initiator, a chain transfer agent and a cross-linking agent are added, a polymer colloid containing embedded resin particles with a network structure is obtained after polymerization, and the polymer colloid is granulated, dried and crushed to obtain a powder type water plugging material. According to the water plugging material with high selectivity, water plugging agents with different mass concentrations can be prepared by adopting field water according to the field requirements of an oil field, and the water plugging agents are injected into an oil reservoir stratum and enter a water phase layer, so that oil-soluble particles in the water plugging material can effectively plug pore passages, further the water phase permeability is reduced, and the water phase plugging effect is enhanced; after entering the oil phase layer, the oil-soluble particles are dissolved in the crude oil without affecting the oil phase permeability, thereby achieving the effect of selectively blocking water and not blocking oil.
In order to achieve the above object, a first aspect of the present invention provides a polymer having a selective water shutoff function, wherein the polymer is obtained by an emulsion polymerization reaction of a monomer a, a monomer B and an oil-soluble resin in the presence of an initiator, a chain transfer agent, a crosslinking agent and water as a solvent, wherein the monomer a is acrylamide; the monomer B is a surface active monomer, and the structural formula of the surface active monomer is shown as (1); the oil-soluble resin is one or more of rosin resin, dammar resin, oil-soluble phenolic resin, petroleum resin, terpene resin and coumarone resin;
wherein R is1Is C5-C15 alkyl, R2Is H, C1-C12 alkyl, -COOH, -SO3H、-SO3K and-SO3Any one of Na, n is an integer of 8-16;
preferably, R1Is C8-C12 alkyl, R2is-SO3H、-SO3K and-SO3Any one of Na, n is an integer of 8-12.
Preferably, the monomer A is used in an amount of 5-15 parts by weight, the monomer B is used in an amount of 5-15 parts by weight, and the oil-soluble resin is used in an amount of 20-40 parts by weight, based on 100 parts by weight of water;
preferably, the monomer A is used in an amount of 5-10 parts by weight, the monomer B is used in an amount of 5-10 parts by weight, and the oil-soluble resin is used in an amount of 30-40 parts by weight, based on 100 parts by weight of water;
further preferably, the total amount of the monomer A and the monomer B is 10 to 20 parts by weight based on 100 parts by weight of water.
Preferably, the polymer has a wash-out resistance factor of greater than 50 PV.
Preferably, the initiator is a water-soluble initiator which is a persulfate-sulfite oxidation-reduction initiation system; the chain transfer agent is a tetramethylethylenediamine aqueous solution; the cross-linking agent is N, N-methylene bisacrylamide;
preferably, the persulfate is used in an amount of 0.01 to 0.1 wt% and the sulfite is used in an amount of 0.005 to 0.05 wt%, based on the total amount of the monomer A and the monomer B; and
the amount of the chain transfer agent is 0.01-0.1 wt%; the amount of the crosslinking agent is 0.01 to 0.1% by weight.
The invention provides a preparation method of a polymer with selective water plugging function, wherein the preparation method comprises the following steps:
(1) mixing a monomer A, a monomer B and water to form an aqueous solution;
(2) mixing an oil-soluble resin with the aqueous solution to form an emulsion;
(3) carrying out polymerization reaction on the emulsion in the presence of an initiator, a chain transfer agent and a crosslinking agent;
wherein the monomer A is acrylamide; the monomer B is a surface active monomer, and the structural formula of the surface active monomer is shown as (2); the oil-soluble resin is one or more of rosin resin, dammar resin, oil-soluble phenolic resin, petroleum resin, terpene resin and coumarone resin;
wherein R is3Is C5-C15 alkyl, R4Is H, C1-C12 alkyl, -COOH, -SO3H、-SO3K and-SO3Any one of Na, m is an integer of 8-16;
preferably, R3Is C8-C12 alkyl, R4is-SO3H、-SO3K and-SO3Any one of Na, and m is an integer of 8-12.
In the present invention, the source of the oil-soluble resin is not particularly limited, and for example, it can be obtained by a conventional commercially available means. In a preferable case, the particle size of the oil-soluble resin is 3 to 100 μm, preferably 3 to 50 μm, for the purpose of more preferably achieving selective water shutoff.
Preferably, the monomer A is used in an amount of 5-15 parts by weight, the monomer B is used in an amount of 5-15 parts by weight, and the oil-soluble resin is used in an amount of 20-40 parts by weight, based on 100 parts by weight of water; preferably, the monomer A is used in an amount of 5-10 parts by weight, the monomer B is used in an amount of 5-10 parts by weight, and the oil-soluble resin is used in an amount of 30-40 parts by weight, based on 100 parts by weight of water; further preferably, the total amount of the monomer A and the monomer B is 10 to 20 parts by weight based on 100 parts by weight of water.
Preferably, the polymers produced have a wash-out factor of greater than 50 PV.
Preferably, the initiator is a water-soluble initiator which is a persulfate-sulfite oxidation-reduction initiation system; the chain transfer agent is a tetramethylethylenediamine aqueous solution; the cross-linking agent is N, N-methylene bisacrylamide;
preferably, the persulfate is used in an amount of 0.01 to 0.1 wt% and the sulfite is used in an amount of 0.005 to 0.05 wt%, based on the total amount of the monomer A and the monomer B; and
the amount of the chain transfer agent is 0.01-0.1 wt%; the amount of the crosslinking agent is 0.01 to 0.1% by weight.
Preferably, in step (1), the pH value of the aqueous solution is 6-10; and in the step (3), the conditions of the polymerization reaction are as follows: the temperature is 20-40 deg.C, preferably 25-35 deg.C, and the time is 6-8 hr, preferably 7-8 hr.
The third aspect of the invention provides the polymer with the selective water plugging function prepared by the method.
The fourth aspect of the invention provides an application of the polymer with the selective water plugging function as a selective water plugging agent.
According to the invention, oil-soluble polymer particles are introduced into the emulsion of the water-based acrylamide copolymer, in the polymerization process, under the action of a chain transfer agent, chain transfer can be generated to the surfaces of the resin particles, a surface active monomer can participate in polymerization and has a strong emulsification effect, and meanwhile, under the action of a cross-linking agent, cross-linked particles with a network structure are formed, so that the suspension stability of the resin particles and the interaction among the particles are enhanced, and thus the blocking capability of the water blocking agent in a water phase is improved. The existence of the oil-soluble particles can greatly improve the temperature resistance, salt resistance and scouring resistance of the water plugging agent material. In the stratum, when the water shutoff agent is influenced by the environmental temperature and the pressure of a water layer, the water shutoff agent can deform, and a large amount of gathered oil-soluble particle water shutoff agents interact with each other to effectively block the stratum with the rock pore with higher water saturation, so that the water yield of an oil well is greatly reduced. After part of the oil-soluble particle water plugging agent flows into an oil layer, the oil-soluble particle water plugging agent can be dissolved into crude oil due to good oil solubility of the oil-soluble particle water plugging agent and is discharged back to the ground together with underground crude oil, so that the oil/water selectivity of a water plugging material is obviously improved, the effect of plugging water and not plugging oil is achieved, measures are provided for the low-efficiency well exploitation and benefit increase under the low oil price, and technical support is provided for the improvement of the oil well productivity in the extremely high water-containing period.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a polymer with selective water plugging function, wherein the polymer is generated by polymerizing a monomer A, a monomer B and an oil-soluble resin in the presence of an initiator, a chain transfer agent, a cross-linking agent and water as a solvent, wherein the monomer A is acrylamide; the monomer B is a surface active monomer, and the structural formula of the surface active monomer is shown as (1); the oil-soluble resin is one or more of rosin resin, dammar resin, oil-soluble phenolic resin, petroleum resin, terpene resin and coumarone resin;
wherein R is1Is C5-C15 alkyl, R2Is H, C1-C12 alkyl, -COOH, -SO3H、-SO3K and-SO3Any one of Na, n is an integer of 8-16.
Preferably, R1Is C8-C12 alkyl, R2is-SO3H、-SO3K and-SO3Any one of Na, n is an integer of 8-12.
Wherein, according to the present invention, the alkyl group of C5-C15 may be linear or branched, and the alkyl group of C5-C15 may include, but is not limited to: n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl and n-pentadecyl, preferably n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
Wherein, according to the present invention, the alkyl group of C1-C12 may be linear or branched, and the alkyl group of C1-C14 may include, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and n-pentyl.
The alkyl group is a hydrocarbon group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight chain or a branched chain, and the ethyl group may be, for example, CH2CH2-or CH (CH)3)-。
Wherein n is an integer of 8 to 16, and the integer of 8 to 16 includes 8, 9, 10, 11, 12, 13, 14, 15 and 16. Preferably, n is an integer from 8 to 12, and the integer of 812 includes 8, 9, 10, 11, and 12.
Preferably, the oil-soluble resin may be one or more of an oil-soluble phenolic resin, a petroleum resin and a coumarone resin.
In the present invention, the monomer a, the monomer B, and the oil-soluble resin may be obtained commercially or synthesized by a method of the prior art. For example, the monomer a, the monomer B, and the oil-soluble resin used in the examples section of the present invention are all commercially available.
According to the invention, based on 100 parts by weight of water, the monomer A is used in an amount of 5-15 parts by weight, the monomer B is used in an amount of 5-15 parts by weight, and the oil-soluble resin is used in an amount of 20-40 parts by weight; in the present invention, the specific selection and amount of the monomer A, the monomer B and the oil-soluble resin are controlled within the above-mentioned ranges, but it is preferable that the monomer A is used in an amount of 5 to 10 parts by weight, the monomer B is used in an amount of 5 to 10 parts by weight and the oil-soluble resin is used in an amount of 30 to 40 parts by weight based on 100 parts by weight of water.
Further preferably, the total amount of the monomer A and the monomer B is 10 to 20 parts by weight based on 100 parts by weight of water.
Preferably, the polymer has a wash-out resistance factor of greater than 50 PV.
According to the invention, the initiator may be a water-soluble initiator, which may be an oxidation-reduction initiation system consisting of a persulfate oxidizer and a sulfite reducer. In a preferred aspect, the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B, that is, the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B. For example, the oxidizing agent in the redox initiator may be a 0.2 wt% aqueous solution of potassium persulfate and/or a 0.2 wt% aqueous solution of ammonium persulfate; the reducing agent in the redox initiator may be 0.1 wt% aqueous potassium bisulfite solution and/or 0.1 wt% aqueous sodium bisulfite solution.
Further preferably, the persulfate is used in an amount of 0.01 to 0.05% by weight and the sulfite is used in an amount of 0.01 to 0.05% by weight based on the total amount of the monomer A and the monomer B, more preferably.
Preferably, the chain transfer agent may be a 0.1 wt% aqueous solution of tetramethylethylenediamine; and the amount of the chain transfer agent is 0.01 to 0.1 weight percent based on the total amount of the monomer A and the monomer B; more preferably, the chain transfer agent is used in an amount of 0.01 to 0.05 wt%, which is more effective.
Preferably, the crosslinking agent is a 0.1 wt% aqueous solution of N, N-methylenebisacrylamide; and the amount of the cross-linking agent is 0.01 to 0.1 weight percent based on the total amount of the monomer A and the monomer B; preferably, the crosslinking agent is used in an amount of 0.01 to 0.05% by weight, based on the total amount of the monomers A and B.
The invention provides a preparation method of a polymer with selective water plugging function, wherein the preparation method comprises the following steps:
(1) mixing a monomer A, a monomer B and water to form an aqueous solution;
(2) mixing an oil-soluble resin with the aqueous solution to form an emulsion;
(3) carrying out polymerization reaction on the emulsion in the presence of an initiator and a chain transfer agent;
wherein the monomer A can be acrylamide; the monomer B can be a surface active monomer, and the structural formula of the surface active monomer is shown as (2); the oil-soluble resin can be one or more of rosin resin, dammar resin, oil-soluble phenolic resin, petroleum resin, terpene resin and coumarone resin;
wherein R is3Is C5-C15 alkyl, R4Is H, C1-C12 alkyl, -COOH, -SO3H、-SO3K and-SO3Any one of Na, and m is an integer of 8-16.
Preferably, R3Is C8-C12 alkyl, R4is-SO3H、-SO3K and-SO3Any one of Na, and m is an integer of 8-12.
Wherein, according to the present invention, the alkyl group of C5-C15 may be linear or branched, and the alkyl group of C5-C15 may include, but is not limited to:
according to the invention, the alkyl group of C5-C15 may be linear or branched, and the alkyl group of C5-C15 may include, but is not limited to: n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl and n-pentadecyl.
Preferably, the C8-C12 alkyl groups are n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
According to the invention, the alkyl group of C1-C12 may be linear or branched, and the alkyl group of C1-C14 may include, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
Preferably, the alkyl group of C1 to C12 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and n-pentyl.
According to the invention, the alkyl radical is formed by the loss of one hydrogen atom from the alkane moleculeThe hydrocarbon group (C) may be linear or branched, and the ethyl group may be CH, for example2CH2-or CH (CH)3)-。
Wherein m is an integer of 8 to 16, and the integer of 8 to 16 includes 8, 9, 10, 11, 12, 13, 14, 15 and 16. Preferably, m is an integer from 8 to 12, and integers from 8 to 12 include 8, 9, 10, 11 and 12.
Preferably, the oil-soluble resin may be one or more of an oil-soluble phenolic resin, a petroleum resin and a coumarone resin.
The polymerization reaction can also be carried out in the presence of a protective gas, which can preferably be nitrogen.
According to the invention, based on 100 parts by weight of water, the monomer A is used in an amount of 5-15 parts by weight, the monomer B is used in an amount of 5-15 parts by weight, and the oil-soluble resin is used in an amount of 20-40 parts by weight; preferably, the monomer A is used in an amount of 5 to 10 parts by weight, the monomer B is used in an amount of 5 to 10 parts by weight, and the oil-soluble resin is used in an amount of 30 to 40 parts by weight, based on 100 parts by weight of water.
Further preferably, the total amount of the monomer A and the monomer B is 10 to 20 parts by weight based on 100 parts by weight of water.
Preferably, the polymers produced have a wash-out factor of greater than 50 PV.
According to the invention, the initiator may be a water-soluble initiator, which may be an oxidation-reduction initiation system consisting of a persulfate oxidizer and a sulfite reducer. In a preferred aspect, the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B, that is, the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B. For example, the oxidizing agent in the redox initiator may be a 0.2 wt% aqueous solution of potassium persulfate and/or a 0.2 wt% aqueous solution of ammonium persulfate; the reducing agent in the redox initiator may be 0.1 wt% aqueous potassium bisulfite solution and/or 0.1 wt% aqueous sodium bisulfite solution.
Preferably, the persulfate is used in an amount of 0.01 to 0.05 wt% and the sulfite is used in an amount of 0.01 to 0.05 wt%, based on the total amount of the monomer A and the monomer B, and the effect is more excellent.
The chain transfer agent may be a 0.1 wt% aqueous solution of tetramethylethylenediamine; and the amount of the chain transfer agent is 0.01 to 0.1 weight percent based on the total amount of the monomer A and the monomer B; preferably, the chain transfer agent is used in an amount of 0.01 to 0.05% by weight based on the total amount of the monomer A and the monomer B, and the effect is more excellent.
Preferably, the crosslinking agent is a 0.1 wt% aqueous solution of N, N-methylenebisacrylamide; and the amount of the cross-linking agent is 0.01 to 0.1 weight percent based on the total amount of the monomer A and the monomer B; preferably, the crosslinking agent is used in an amount of 0.01 to 0.05% by weight, based on the total amount of the monomers A and B.
According to the invention, in step (1), the pH of the aqueous solution is preferably carried out at a pH of from 6 to 10. The pH may be obtained by adding a pH adjuster, which may be various pH adjusters conventional in the art, to the mixed system, for example, at least one of sodium hydroxide, sodium carbonate, potassium carbonate and ammonia water, preferably sodium hydroxide and/or sodium carbonate.
According to the present invention, in step (3), the conditions of the polymerization reaction may include: the temperature is 20-40 deg.C, preferably 25-35 deg.C, and the time is 6-8 hr, preferably 7-8 hr.
In order to obtain the polymer finished product with the selective water plugging function, the method can also comprise the steps of granulating, drying, crushing and screening the obtained polymer colloid to obtain the polymer finished product with the selective water plugging function.
In the present invention, the environmental conditions of the oil field may include: the temperature is 40-130 ℃, preferably 70-110 ℃, and more preferably 95-110 ℃; the degree of mineralization is 100-200,000mg/L, preferably 10,000-100,000mg/L, more preferably 60,000-100,000mg/L, and most preferably 85,000-100,000 mg/L.
According to a preferred embodiment of the present invention, the preparation method of the polymer with selective water plugging function comprises the following steps:
step 1: adding the monomer A, the monomer B and water into a polymerization reaction bottle (a heat-preservation polymerization bottle) to prepare an aqueous solution, and adjusting the pH value of the aqueous solution to 6-10 by using alkali;
step 2: adding oil-soluble resin into the aqueous solution obtained in the step 1, and uniformly stirring to form emulsion;
and 3, step 3: blowing nitrogen for 5-60min at the temperature of 20-40 ℃, adding an initiator, a chain transfer agent and a cross-linking agent into the emulsion obtained in the step 2, blowing nitrogen to uniformly mix the mixture, and carrying out sealing polymerization for 6-8h to obtain a polymer colloid;
and 4, step 4: and taking out the colloid, and then granulating, drying, crushing and screening to obtain a polymer finished product with the selective water plugging function.
The third aspect of the invention provides the polymer with the selective water plugging function prepared by the method.
The fourth aspect of the invention provides an application of the polymer with the selective water plugging function as a selective water plugging agent.
In the application of the polymer with the selective water plugging function as the selective water plugging agent, a specific application method is well known by the technical personnel in the field.
The invention adopts a polymerization method to synthesize the water-based water plugging material containing oil-soluble polymer particles in a system, namely, acrylamide monomers and surface active monomers are polymerized in a water phase to form a space-network cross-linking structure under the action of a cross-linking agent, the resin particles are embedded to enhance the suspension stability of the resin particles and the interaction among the particles, and the oil/water selectivity of the water plugging agent material is improved through different action mechanisms of the resin particles and oil and water, so that the effect of plugging water without plugging oil is achieved. According to the technical scheme, the oil-soluble resin is selected as suspended particles, and the nonionic surface active monomer is selected as an emulsion polymerizable monomer, so that the temperature resistance and salt resistance of the water plugging agent and the oil/water selectivity are improved.
The present invention will be described in detail below by way of examples.
The oil-soluble phenolic resin is purchased from Jining HuaKai resin Co., Ltd, and has the brand number of 2402;
the petroleum resin is purchased from Jitian chemical industry Co., Ltd, Shenzhen, and the brand is C5C 9;
coumarone resin was purchased from Shandong Xiang Showa New materials Co., Ltd, and was designated 18 #;
the surface active monomer is purchased from a Honda chemical plant in the great Bridgeon market and has the mark of A-10;
the acrylamide raw material is a commercial product produced by Shandong Baomo biochemical industry Co.
In the following examples, the test methods involved are as follows:
the plugging rate is carried out on a rock core flow test device according to the plugging rate test procedure in SY/T5840-2007 bridge plugging material indoor test method for drilling fluid. Specifically, the method comprises the following steps:
and (3) measuring the water plugging rate: loading the artificial core into core holder, saturating with water, and measuring its pore volume PV and water phase permeability (K)w1) Then injecting 1.0PV water shutoff agent, curing for 24h at 90 ℃, and measuring the permeability (K) of the mixture after adding the water shutoff agent by using waterw2)，Kw2And Kw1Ratio (K)w2/Kw1) Namely the water plugging rate.
And (3) measuring the oil plugging rate: loading the artificial core into core holder, saturating with oil, and measuring its pore volume PV and oil phase permeability (K)o1) Then injecting 1.0PV water shutoff agent, curing for 24h at 90 deg.C, and measuring the permeability (K) after adding water shutoff agent with oilo2)，Ko2And Ko1Of (K)o2/Ko1) Namely the oil plugging rate.
And (3) measuring the scouring resistance multiple: after the water plugging rate is measured, water with 50 times of pore volume multiple (PV) is continuously injected into the rock core, the permeability under different PV numbers is recorded, the water plugging rate under different PV numbers is calculated according to the measuring method of the water plugging rate, and the scouring resistance multiple is the maximum PV number of the injected water when the water plugging rate is more than or equal to 80%. Normally, the water blocking rate at 50PV number is measured, and the value is more than or equal to 80 percent, which indicates that the material has excellent flushing resistance.
Wherein the artificial core is obtained by filling quartz sand of 40-60 meshes in a mould.
Example 1
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. 50.0g of acrylamide (5 parts by weight of monomer A based on 100 parts by weight of water) and 50.0g of a surface-active monomer (wherein R is3Is n-pentyl, R4H, m is 8) (the amount of the monomer B is 5 parts by weight based on 100 parts by weight of water) is added into 1000mL of water, stirred and fully dissolved, and then the pH value of the aqueous solution is adjusted to 6.0 by alkali (sodium hydroxide) to obtain a stable aqueous solution;
2. weighing 200.0g of oil-soluble phenolic resin (the amount of the oil-soluble phenolic resin is 20 parts by weight based on 100 parts by weight of water) and adding into the solution, and fully stirring to form stable emulsion;
3. adding 0.2 weight percent of potassium persulfate aqueous solution 0.5g, 0.1 weight percent of sodium bisulfite aqueous solution 0.5g (based on 100g of the total amount of the monomer A and the monomer B, the amount of the persulfate is 0.1 weight percent, and the amount of the sulfite is 0.05 weight percent), 0.1g of tetramethylethylenediamine aqueous solution (based on 100g of the total amount of the monomer A and the monomer B, the amount of the chain transfer agent is 0.01 weight percent), and 0.1 weight percent of N, N-methylene bisacrylamide aqueous solution 0.1g (based on 100g of the total amount of the monomer A and the monomer B, the amount of the cross-linking agent is 0.01 weight percent) into the emulsion in the step 2 in sequence, fully stirring and emulsifying, raising the temperature to 20 ℃, and initiating polymerization for 6 hours to obtain a polymer colloid containing resin particles;
4. and granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely DSJ 1.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 100,000mg/L), the water blocking rate of the DSJ1 is 99.2%, the oil blocking rate is 2.5%, and the scouring resistance multiple is more than 50 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 2
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. 50.0g of acrylamide (5 parts by weight of monomer A based on 100 parts by weight of water) and 50.0g of a surface-active monomer (wherein R is3Is n-octyl, R4is-SO3K, m is 10) (the amount of the monomer B is 5 parts by weight based on 100 parts by weight of water) is added into 1000mL of water, stirred and fully dissolved, and then the pH value of the aqueous solution is adjusted to 6.0 by alkali (sodium carbonate) to obtain a stable aqueous solution;
2. weighing 200.0g of oil-soluble phenolic resin (the amount of the oil-soluble phenolic resin is 20 parts by weight based on 100 parts by weight of water) and adding into the solution, and fully stirring to form stable emulsion;
3. adding 0.2 weight percent of potassium persulfate aqueous solution 0.25g, 0.1 weight percent of sodium bisulfite aqueous solution 0.5g (based on the total dosage of 150g of the monomer A and the monomer B, the dosage of the persulfate is 0.033 weight percent, and the dosage of the sulfite is 0.033 weight percent) and tetramethylethylenediamine aqueous solution 0.75g (based on the total dosage of 150g of the monomer A and the monomer B, the dosage of the chain transfer agent is 0.05 weight percent) and 0.1 weight percent of N, N-methylene bisacrylamide aqueous solution 0.75g (based on the total dosage of 150g of the monomer A and the monomer B, the dosage of the cross-linking agent is 0.05 weight percent) into the emulsion in the step 2 in sequence, fully stirring and emulsifying, raising the temperature to 20 ℃, and initiating polymerization for 6 hours to obtain a polymer colloid containing the network structure embedding resin particles;
4. and granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely DSJ 2.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 100,000mg/L), the water blocking rate of the DSJ2 is 99.9%, the oil blocking rate is 2.3%, and the scouring resistance multiple is more than 50 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 3
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. 80.0g of acrylamide (8 parts by weight of monomer A based on 100 parts by weight of water) and 70.0g of a surface-active monomer (wherein R is3Is n-dodecyl, R4is-SO3Na and m are integers of 12) (the amount of the monomer B is 7 parts by weight based on 100 parts by weight of water) is added into 1000mL of water and stirred to be fully dissolved, and then the pH value of the aqueous solution is adjusted to 7.0 by alkali (sodium hydroxide) to obtain a stable aqueous solution;
2. weighing 300.0g of petroleum resin (based on 100 parts by weight of water, the amount of the oil-soluble resin is 40 parts by weight), adding into the solution, and stirring to form stable emulsion;
3. adding 0.2% potassium persulfate aqueous solution 0.5g, 0.1% sodium bisulfite aqueous solution 1.0g (based on 200g of the total amount of the monomer A and the monomer B, the amount of the persulfate is 0.05 wt%, and the amount of the sulfite is 0.05 wt%), tetramethylethylenediamine aqueous solution 2.0g (based on 200g of the total amount of the monomer A and the monomer B, the amount of the chain transfer agent is 0.1 wt%), and 0.1 wt% N, N-methylene bisacrylamide aqueous solution 2.0g (based on 200g of the total amount of the monomer A and the monomer B, the amount of the cross-linking agent is 0.1 wt%) into the emulsion in the step 2 in sequence, stirring and emulsifying, raising the temperature to 25 ℃, and initiating polymerization for 8 hours to obtain a polymer colloid containing the embedding resin particles with a network structure;
4. and granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely DSJ 3.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 100,000mg/L), the water blocking rate of the DSJ3 is 99.9%, the oil blocking rate is 2.0%, and the scouring resistance multiple is more than 50 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 4
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
1. 100.0g of acrylamide (10 parts by weight of monomer A based on 100 parts by weight of water) and 100.0g of a surface-active monomer (wherein R is3Is n-pentadecyl, R4M is methyl, m is 16) (the amount of the monomer B is 10 parts by weight based on 100 parts by weight of water) is added into 1000mL of water, stirred and fully dissolved, and then the pH value of the aqueous solution is adjusted to 8.0 by alkali (sodium carbonate) to obtain a stable aqueous solution;
2. weighing 400.0g of coumarone resin (based on 100 parts by weight of water, the amount of the oil-soluble resin is 40 parts by weight) and adding into the solution, and fully stirring to form stable emulsion;
3. adding 0.2% potassium persulfate aqueous solution 0.1g, 0.1% sodium bisulfite aqueous solution 0.2g (based on 200g of the total amount of the monomer A and the monomer B, the persulfate is 0.01 wt%, the sulfite is 0.01 wt%), tetramethylethylenediamine aqueous solution 1.0g (based on 200g of the total amount of the monomer A and the monomer B, the chain transfer agent is 0.05 wt%) and 0.1 wt% N, N-methylene bisacrylamide aqueous solution 1.0g (based on 200g of the total amount of the monomer A and the monomer B, the cross-linking agent is 0.05 wt%) into the emulsion in the step 2 in sequence, stirring and emulsifying fully, raising the temperature to 25 ℃, and initiating polymerization for 7 hours to obtain a polymer colloid containing the embedding resin particles with a network structure;
4. and granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely DSJ 4.
As a result of the test, under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 100,000mg/L), the water blocking rate of the DSJ4 is 99.7%, the oil blocking rate is 1.8%, and the scouring resistance multiple is more than 65 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 5
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in the present examples were different, specifically:
acrylamide was used in an amount of 60g (monomer A was used in an amount of 6 parts by weight based on 100 parts by weight of water), a surface-active monomer (wherein R was3Is n-pentyl, R4M is 8) is 40g (4 parts by weight based on 100 parts by weight of water, monomer B) and the oil-soluble phenol resin is 200g (20 parts by weight based on 100 parts by weight of water).
The rest was the same as in example 1 to obtain a polymer colloid containing resin particles;
and granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely DSJ 5.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 100,000mg/L), the water blocking rate of the DSJ5 is 99.5%, the oil blocking rate is 3.1%, the scouring resistance multiple is more than 60PV, and specifically, the scouring resistance multiple is 60-70 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance on oil/water, and particularly still has better selective plugging rate on oil/water under high temperature and high salt conditions.
Example 6
This example illustrates a polymer having selective water shutoff functionality prepared by the method of the present invention.
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in the present examples were different, specifically:
acrylamide was used in an amount of 50g (monomer A was used in an amount of 5 parts by weight based on 100 parts by weight of water), a surface-active monomer (wherein R was3Is n-pentyl, R4M is 8) is 30g (3 parts by weight of monomer B based on 100 parts by weight of water) and the oil-soluble phenol resin is 300g (30 parts by weight of oil-soluble resin based on 100 parts by weight of water).
The rest was the same as in example 1 to obtain a polymer colloid containing resin particles;
and granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely DSJ 6.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the mineralization degree is 100,000mg/L), the water blocking rate of the DSJ6 is 99.4%, the oil blocking rate is 2.4%, the scouring resistance multiple is more than 80PV, and specifically, the scouring resistance multiple is 80-90 PV.
The water plugging material prepared in the embodiment has excellent selective plugging rate and flushing resistance to oil/water, and particularly still has better selective plugging rate to oil/water under the conditions of high temperature and high salt
Comparative example 1
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in this example were varied, specifically, acrylamide was used in an amount of 160g (16 parts by weight based on 100 parts by weight of water, monomer A was used), the surface active monomer was used in an amount of 60g (6 parts by weight based on 100 parts by weight of water, monomer B was used), and the oil-soluble phenol resin was used in an amount of 100g (10 parts by weight based on 100 parts by weight of water, oil-soluble resin was used).
The rest of the procedure was the same as in example 1, to obtain a polymer colloid containing resin particles.
And granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely D1.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 100,000mg/L), the water blocking rate of the D1 is 83.8 percent, the oil blocking rate is 18.5 percent, and the scouring resistance multiple is 2 PV.
The water plugging material prepared by the comparative example does not have excellent selective plugging rate and flushing resistance on oil/water, and particularly does not have good selective plugging rate on oil/water under high-temperature and high-salt conditions.
Comparative example 2
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: the monomers used in this example were varied, specifically, acrylamide was used in an amount of 200g (monomer A was used in an amount of 20 parts by weight based on 100 parts by weight of water), a surface active monomer was used in an amount of 100g (monomer B was used in an amount of 10 parts by weight based on 100 parts by weight of water), and an oil-soluble phenol resin was used in an amount of 500g (oil-soluble resin was used in an amount of 50 parts by weight based on 100 parts by weight of water).
The rest of the procedure was the same as in example 1, to obtain a polymer colloid containing resin particles.
And granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely D2.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 100,000mg/L), the water blocking rate of the D2 is 82.3%, the oil blocking rate is 20.1%, and the scouring resistance multiple is 3 PV.
The water plugging material prepared by the comparative example does not have excellent selective plugging rate and flushing resistance on oil/water, and particularly does not have good selective plugging rate on oil/water under high-temperature and high-salt conditions.
Comparative example 3
The same method as that of example 1 for preparing a polymer having a selective water shutoff function was employed, except that: no crosslinking agent was added and no polymer colloid containing network structure embedded resin particles was obtained.
And granulating, drying and crushing the polymer colloid to obtain a powder type water plugging material, and preparing the water plugging material into an aqueous solution with the mass concentration of 0.1% by adopting simulated saline with the mineralization degree of 100,000mg/L, namely D3.
And (3) testing results: under the conditions of high temperature (95 ℃) and high salt (the degree of mineralization is 100,000mg/L), the water blocking rate of the D3 is 96.9 percent, the oil blocking rate is 5.5 percent, and the scouring resistance multiple is 10 PV.
It is shown that the water shutoff material prepared in the comparative example has excellent selective shutoff rate and flushing resistance to oil/water and also has a good selective shutoff rate to oil/water under high temperature and high salt conditions, but the effect is not as good as that of examples 1 to 6 because no crosslinking agent is added and no polymer colloid for embedding resin particles in a network structure is formed in the comparative example.
As can be seen from the above examples and comparative examples, the present invention is a powder-type water plugging material obtained by adding acrylamide monomer, surfactant monomer and oil-soluble resin into an aqueous solution, stirring to form a stable emulsion system, adding initiator, chain transfer agent and cross-linking agent, initiating and polymerizing at 20-40 deg.C to obtain a polymer colloid containing resin particles, and granulating, drying and pulverizing the colloid. According to the field requirements of the oil field, the water plugging agent with different mass concentrations can be prepared by adopting field water; and the amounts of the acrylamide monomer, the surface active monomer and the oil-soluble resin are within the above-defined ranges, the present invention can be accomplished, and has excellent effects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (20)
1. A polymer with selective water plugging function is characterized in that the polymer is prepared by emulsion polymerization reaction of a monomer A, a monomer B and oil-soluble resin in the presence of an initiator, a chain transfer agent, a cross-linking agent and water as a solvent, wherein the monomer A is acrylamide; the monomer B is a surface active monomer, and the structural formula of the surface active monomer is shown as a formula (1); the oil-soluble resin is one or more of rosin resin, dammar resin, oil-soluble phenolic resin, petroleum resin, terpene resin and coumarone resin;
wherein R is1Is C5-C15Alkyl of R2Is H, C1-C12Alkyl group, -COOH, -SO3H、-SO3K and-SO3Any one of Na, n is an integer of 8-16.
2. The polymer of claim 1, wherein R1Is C8-C12Alkyl of R2is-SO3H、-SO3K and-SO3Any one of Na, n is an integer of 8-12.
3. The polymer according to claim 1, wherein the monomer a is used in an amount of 5 to 15 parts by weight, the monomer B is used in an amount of 5 to 15 parts by weight, and the oil-soluble resin is used in an amount of 20 to 40 parts by weight, based on 100 parts by weight of water.
4. The polymer according to claim 3, wherein the monomer A is used in an amount of 5 to 10 parts by weight, the monomer B is used in an amount of 5 to 10 parts by weight, and the oil-soluble resin is used in an amount of 30 to 40 parts by weight, based on 100 parts by weight of water.
5. The polymer according to claim 4, wherein the total amount of the monomer A and the monomer B is 10 to 20 parts by weight based on 100 parts by weight of water.
6. The polymer of claim 2, wherein the polymer has a wash-out factor greater than 50 PV.
7. The polymer of claim 1, wherein the initiator is a water soluble initiator that is a persulfate-sulfite oxidation-reduction initiation system; the chain transfer agent is a tetramethylethylenediamine aqueous solution; the cross-linking agent is N, N-methylene bisacrylamide.
8. The polymer according to claim 7, wherein the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B; and the amount of the chain transfer agent is 0.01-0.1 wt%; the amount of the crosslinking agent is 0.01 to 0.1% by weight.
9. A preparation method of a polymer with selective water plugging function is characterized by comprising the following steps:
(1) mixing a monomer A, a monomer B and water to form an aqueous solution;
(2) mixing an oil-soluble resin with the aqueous solution to form an emulsion;
(3) carrying out polymerization reaction on the emulsion in the presence of an initiator, a chain transfer agent and a crosslinking agent;
wherein the monomer A is acrylamide; the monomer B is a surface active monomer, and the structural formula of the surface active monomer is shown as (2); the oil-soluble resin is one or more of rosin resin, dammar resin, oil-soluble phenolic resin, petroleum resin, terpene resin and coumarone resin;
wherein R is3Is C5-C15Alkyl of R4Is H, C1-C12 alkyl, -COOH, -SO3H、-SO3K and-SO3Any one of Na, and m is an integer of 8-16.
10. The method of claim 9, wherein R3Is C8-C12Alkyl of R4is-SO3H、-SO3K and-SO3Any one of Na, and m is an integer of 8-12.
11. The production method according to claim 9, wherein the monomer a is used in an amount of 5 to 15 parts by weight, the monomer B is used in an amount of 5 to 15 parts by weight, and the oil-soluble resin is used in an amount of 20 to 40 parts by weight, based on 100 parts by weight of water.
12. The production method according to claim 11, wherein the monomer a is used in an amount of 5 to 10 parts by weight, the monomer B is used in an amount of 5 to 10 parts by weight, and the oil-soluble resin is used in an amount of 30 to 40 parts by weight, based on 100 parts by weight of water.
13. The production method according to claim 12, wherein the total amount of the monomer a and the monomer B is 10 to 20 parts by weight based on 100 parts by weight of water.
14. The method of claim 9, wherein the polymer produced has a wash-out factor of greater than 50 PV.
15. The production method according to claim 9, wherein the initiator is a water-soluble initiator which is an oxidation-reduction initiation system of persulfate-sulfite; the chain transfer agent is a tetramethylethylenediamine aqueous solution; the cross-linking agent is N, N-methylene bisacrylamide.
16. The production method according to claim 15, wherein the persulfate is used in an amount of 0.01 to 0.1% by weight and the sulfite is used in an amount of 0.005 to 0.05% by weight, based on the total amount of the monomer A and the monomer B; and the amount of the chain transfer agent is 0.01-0.1 wt%; the amount of the crosslinking agent is 0.01 to 0.1% by weight.
17. The production method according to claim 9, wherein, in the step (1), the pH value of the aqueous solution is 6 to 10; and in step (3), the polymerization conditions include: the temperature is 20-40 ℃ and the time is 6-8 hours.
18. The method of claim 17, wherein the temperature is 25-35 ℃ and the time is 7-8 hours.
19. A polymer having selective water shutoff function prepared by the method of any one of claims 9 to 18.
20. Use of the polymer having a selective water shutoff function according to any one of claims 1 to 8 and 19 as a selective water shutoff agent.
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