CN108017755B - Polymer with water shutoff profile control performance and preparation method and application thereof - Google Patents

Polymer with water shutoff profile control performance and preparation method and application thereof Download PDF

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CN108017755B
CN108017755B CN201610929341.6A CN201610929341A CN108017755B CN 108017755 B CN108017755 B CN 108017755B CN 201610929341 A CN201610929341 A CN 201610929341A CN 108017755 B CN108017755 B CN 108017755B
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祝纶宇
张文龙
杜超
方昭
胡晓娜
刘希
伊卓
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
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    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
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    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
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Abstract

The invention relates to the field of profile control and water shutoff of oil fields, and discloses a polymer with water shutoff and profile control performances, a preparation method and application thereof, wherein the polymer contains a structural unit A, a structural unit B and a structural unit C, the structural unit A is provided by an acrylamide monomer, the structural unit B is provided by a fumaric acid monomer, and the structural unit C is provided by a monomer with a structure shown in a formula (1); based on the weight of the polymer, the content of the structural unit A is 60-98 wt%, the content of the structural unit B is 1-39 wt%, and the content of the structural unit C is 1-39 wt%;
Figure DDA0001137745400000011
in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl.

Description

Polymer with water shutoff profile control performance and preparation method and application thereof
Technical Field
The invention relates to the field of crude oil recovery, in particular to a polymer with water shutoff and profile control performance, a method for preparing the polymer with water shutoff and profile control performance, the polymer with water shutoff and profile control performance prepared by the method, and application of the polymer with water shutoff and profile control performance in water shutoff and profile control and preparation of products for water shutoff and profile control.
Background
More than 80% of onshore petroleum in China is developed by water injection. A reservoir is often made up of multiple reservoirs. Due to the differences in permeability of the various oil layers, the injected water will project along the high permeability layer, causing premature water lock of the well. Water production is therefore a common problem for oilfield wells developed by water flooding. The main measure for solving the problem is profile control and water shutoff. The water content ratio of the oil well can be reduced by the profile control and water shutoff measures, and the oil yield is improved; the thickness of an oil production layer section is increased, the thickness of a high water-bearing layer is reduced, and the produced fluid cutting surface of an oil well is improved; the utilization rate of injected water is improved, and the water injection displacement effect is improved; improve the water absorption profile of the water injection well. Thereby improving the water injection development effect on the whole. The oil field in China generally adopts a water injection development mode, and the water content rising speed is accelerated in the middle and later development periods due to serious stratum heterogeneity and complex reservoir geology. At present, the average water content of oil well production reaches more than 80 percent. Some old oil fields in the eastern region have water contents of over 90 percent. Therefore, profile control and water shutoff are necessary for water and oil reduction.
The chemical water plugging technology in oil fields in China has been applied to fields for 60 years from 50 years. Oil-based cement, lime cream, resin, active thickened oil and the like are developed after water is blocked by cement slurry at first; resin was the main material in the 60 s; water-soluble polymers and gels thereof began to be used in oil fields in the 70 s. From now on, the oil field water shutoff technology has entered a new development stage, and the stifled agent variety increases rapidly, handles the well number increase, and economic benefits also obviously improves.
The existing water shutoff profile control agent mainly has two problems: 1. the water shutoff profile control agent has short action distance and is only effective in the near wellbore area; 2. the gelling reaction activity of the water plugging profile control agent is uncontrollable, so that the near-wellbore area is often blocked; 3. most of the water shutoff profile control agent is a complex agent, namely A, B agent system, chromatographic separation can occur in the stratum migration process, and uncertainty is caused to the construction design of water shutoff profile control measures.
Aiming at the problems of the existing water shutoff profile control agent system, the invention provides a single-dosage delayed self-crosslinking water-soluble polymer which can realize controllable water shutoff profile control in a far well zone.
Disclosure of Invention
The polymer with the water shutoff and profile control performance can realize slow tackifying and gelling in a longer time range, a system does not need to additionally add a delayed crosslinking agent, and the formed self-crosslinking weak gel has high aging retention viscosity and is suitable for deep water shutoff and profile control of a far well zone.
In order to achieve the above object, the present invention provides, in a first aspect, a polymer having water shutoff and profile control properties, wherein the polymer comprises a structural unit a, a structural unit B, and a structural unit C, wherein the structural unit a is provided by an acrylamide monomer, the structural unit B is provided by a fumaric acid monomer, and the structural unit C is provided by a monomer having a structure represented by formula (1); wherein, based on the weight of the polymer, the content of the structural unit A is 60-98 wt%, the content of the structural unit B is 1-39 wt%, and the content of the structural unit C is 1-39 wt%;
Figure BDA0001137745390000021
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl.
In a second aspect, the present invention provides a method for preparing a polymer with water shutoff and profile control properties, wherein the method comprises: in the presence of an initiator and water as a solvent, and under an inert gas atmosphere, carrying out solution polymerization reaction on a monomer D, a monomer E and a monomer F; wherein the monomer D is an acrylamide monomer, the monomer E is a fumaric acid monomer, and the monomer F is a monomer with a structure shown in a formula (1); wherein the monomers D, E and F are used in amounts such that the prepared polymer contains 60-98 wt% of the structural unit A, 1-39 wt% of the structural unit B and 1-39 wt% of the structural unit C;
Figure BDA0001137745390000031
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl.
In a third aspect, the present invention provides a polymer having water shutoff and profile control properties prepared by the foregoing method.
In a fourth aspect, the invention provides the application of the polymer with water shutoff and profile control performance in water shutoff and profile control of oil fields.
In a fifth aspect, the invention provides the application of the polymer with water shutoff and profile control performance in preparing an oilfield water shutoff and profile control agent.
According to the technical scheme, in the polymer with the structural unit A, the structural unit B and the structural unit C, the structural unit C is hydrolyzed under the formation temperature condition (70-90 ℃) to generate an N-hydroxymethyl propionamide structure and active hydrogen. The resulting product is further subjected to Mannich reaction with structural unit A to form crosslinks. Hydrolysis of structural unit C in the formation is a relatively slow and gradual process. So that the water plugging profile control agent can be conveyed to a far wellbore zone to slowly gel. Therefore, the polymer with water shutoff and profile control performance provided by the invention can realize slow tackifying and gelling in a longer time range, no delayed crosslinking agent is required to be additionally added in a system, the formed self-crosslinking weak gel has high aging retention viscosity, and the polymer is suitable for deep water shutoff and profile control of a far well zone.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
In a first aspect, the invention provides a polymer with water shutoff and profile control performance, wherein the polymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is provided by an acrylamide monomer, the structural unit B is provided by a fumaric acid monomer, and the structural unit C is provided by a monomer with a structure shown in a formula (1); wherein, based on the weight of the polymer, the content of the structural unit A is 60-98 wt%, the content of the structural unit B is 1-39 wt%, and the content of the structural unit C is 1-39 wt%;
Figure BDA0001137745390000041
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl.
In the process of research, the inventor of the invention finds that in the polymer provided by the invention and having the structural unit A, the structural unit B and the structural unit C, the structural unit C is hydrolyzed under the formation temperature condition (70-90 ℃) to generate an N-hydroxymethyl propionamide structure and active hydrogen. The resulting product is further subjected to Mannich reaction with structural unit A to form crosslinks. Hydrolysis of structural unit C in the formation is a relatively slow and gradual process. So that the water plugging profile control agent can be conveyed to a far wellbore zone to slowly gel. Therefore, the polymer with water shutoff profile control performance provided by the invention can realize slow tackifying and gelling in a longer time range, no delayed crosslinking agent is needed to be added in a system, the formed self-crosslinking weak gel has high aging retention viscosity, and the polymer is suitable for deep water shutoff profile control of a far well zone, thereby completing the invention.
Preferably, the content of the structural unit A is 75 to 90 wt%, the content of the structural unit B is 5 to 20 wt%, and the content of the structural unit C is 4 to 20 wt%, based on the weight of the polymer.
According to the invention, without going to the contrary, the term "alkyl group of C1-C12" may be linear or branched, said alkyl group of C1-C12 comprising, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
"C6 to C12" in the term "substituted or unsubstituted cycloalkyl group of C6 to C12" means the total number of all carbon atoms, and when a substituent is contained in the cycloalkyl group, the substituent is preferably a straight-chain or branched alkyl group or alkylene group of C1 to C4, for example, the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and the alkylene group may include a substructure of the above alkyl group. The substituent may also be a cycloalkyl group of C2, C3, or C4. The main structure of the "substituted or unsubstituted cycloalkyl group having C6-C12" may be, for example, cyclohexyl, cycloheptyl or cyclooctyl.
The term "C6-C12" in "substituted or unsubstituted aryl group of C6-C12" refers to the total number of all carbon atoms, and when a substituent is contained in the aryl group, the substituent is preferably a straight-chain or branched alkyl or alkylene group of C1-C4, for example, the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and the alkylene group may include a substructure of the above alkyl group. The substituent may also be a cycloalkyl group of C2, C3, or C4. The main structure of "substituted or unsubstituted aryl group of C6-C12" may be, for example, phenyl or naphthyl.
According to the invention, it is further preferred that in formula (1), R1、R2、R3Each independently is H, C1-C4 alkyl, C12 alkyl, C6-C10 substituted or unsubstituted aryl; r4Is C1-C4 alkyl, C12 alkyl, C6-C10 substituted or unsubstituted aryl, C6-C8 cycloalkyl.
According to the invention, without going to the contrary, the term "alkyl of C1-C4" may be linear or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl; the term "C6-C10" in "substituted or unsubstituted aryl group of C6-C10" refers to the total number of all carbon atoms, and when a substituent is contained in the aryl group, the substituent is preferably a straight-chain or branched alkyl or alkylene group of C1-C4, for example, the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, and the alkylene group may include a substructure of the above alkyl group. The substituent may also be a cycloalkyl group of C2, C3, or C4. The main structure of "substituted or unsubstituted aryl group of C6-C10" may be, for example, phenyl or naphthyl.
According to the invention, it is further preferred that R1、R2、R3Each independently is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-dodecyl, phenyl, naphthyl, benzyl or ethylphenyl, more preferably methyl, ethyl or isopropyl; r4Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-dodecyl, phenyl, naphthyl, benzyl, ethylphenyl, cyclohexyl, cycloheptyl or cyclooctyl, more preferably methyl, ethyl, isopropylPhenyl, cyclohexyl or cycloheptyl.
According to the invention, the structural units included in the polymers according to the invention are each obtained by opening the corresponding monomer via a carbon-carbon double bond, without going on to the contrary.
In a second aspect, the present invention provides a method for preparing a polymer with water shutoff and profile control properties, wherein the method comprises: in the presence of an initiator and water as a solvent, and under an inert gas atmosphere, carrying out solution polymerization reaction on a monomer D, a monomer E and a monomer F; wherein the monomer D is an acrylamide monomer, the monomer E is a Fumaric Acid (FA) monomer, and the monomer F is a monomer with a structure shown in a formula (1); wherein the monomers D, E and F are used in amounts such that the prepared polymer contains 60-98 wt% of the structural unit A, 1-39 wt% of the structural unit B and 1-39 wt% of the structural unit C;
Figure BDA0001137745390000071
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl.
The monomer F can be obtained commercially or synthesized by methods known in the art. For example, monomers F used in the examples section of this invention are all commercially available. And the polymerization reaction involved in the method for preparing the polymer with the water shutoff profile control performance is carried out in a random copolymerization mode.
In the present invention, the definitions and species of the substituents in the monomer having the structure represented by formula (1) are the same as those described above, and the present invention is not described herein again, and those skilled in the art should not be construed as limiting the technical scope of the present invention.
It should be noted that, in the polymerization reaction in the present invention, the monomers used are almost completely converted into the corresponding structural units contained in the polymer having water-blocking profile control property, and the amount of the monomers used may be in accordance with the content of the corresponding structural units contained in the polymer having water-blocking profile control property.
Preferably, the monomers D, E and F are used in amounts such that the resulting polymer has a content of structural unit A of 75 to 90 wt.%, a content of structural unit B of 5 to 20 wt.% and a content of structural unit C of 4 to 20 wt.%.
According to the invention, monomer D, monomer E and monomer F are brought into an aqueous solution in the presence of water; more preferably, in the aqueous solution, the ratio of the amount of water to the amount of monomers D, E and F is 1000: 150-245: 2.5-97.5: 2.5-97.5; more preferably 1000: 187.5-225: 12.5-50: 12.5-50. Here, the monomer D, the monomer E and the monomer F may be prepared as aqueous solutions, respectively, and mixed in the above ratio when used, or they may be directly added to the aqueous solutions in the above ratio to prepare predetermined mixed monomer solutions.
According to the present invention, the inert atmosphere refers to a gas which does not react with the raw materials and the products in the presence of an inert gas, and may be, for example, at least one of nitrogen gas or a gas of a group zero element (helium, neon, argon, krypton, xenon) in the periodic table of elements, which is conventional in the art; preferably, the inert gas is nitrogen.
According to the process of the invention, the inert atmosphere in the solution polymerization conditions of the olefins is optionally achieved by: continuously introducing inert gas in the process of the solution polymerization reaction of the olefin; or introducing inert gas into the aqueous solution mixed with the monomer mixture for a predetermined time before the solution polymerization of the olefin begins, and then sealing the solution polymerization space; preferably, the predetermined time is 5 to 60min, more preferably 20 to 40 min.
According to the process of the present invention, the solution polymerization is preferably carried out at a pH of from 8 to 10, preferably from 8.5 to 9.5. The pH may be obtained by adding a pH adjuster, which may be various pH adjusters conventional in the art, to the polymerization system, and may be, for example, at least one of sodium hydroxide, sodium carbonate, potassium carbonate, and ammonia, preferably sodium hydroxide and/or sodium carbonate.
Preferably, the solution polymerization reaction time is 5 to 10 hours, preferably 6 to 7 hours.
Preferably, the initiator may be an initiator conventional in the art, for example, may be an azo-type initiator and/or a redox-type initiator; the azo initiator is preferably at least one selected from 2, 2-azo (2- (2-imidazoline-2-yl) propane) dihydrochloride (alias VA-044), 2-azo (2-methyl-N- (2-hydroxyethyl) propionamide (alias VA-086) and 2, 2-azobis (2-methylpropionamidine) hydrochloride (alias V50), and is more preferably 2, 2-azobis (2-methylpropionamidine) hydrochloride, in the redox initiator, the oxidizing agent is preferably potassium persulfate and/or ammonium persulfate, the reducing agent is preferably sodium sulfite and/or sodium bisulfite, and is more preferably ammonium persulfate and the reducing agent is sodium bisulfite.
Preferably, the amount of the initiator may be an amount conventionally used in the art, as long as it can allow sufficient polymerization of the monomer D, the monomer E and the monomer F to form the polymer having water shutoff profile control properties of the present invention. For example, the initiator may be used in an amount of 0.001 to 0.05 parts by weight, preferably 0.005 to 0.02 parts by weight, based on 1000 parts by weight of water in the solution.
In the preparation method of the invention, when the initiator is azo initiator, the polymerization temperature is preferably 40-70 ℃, and more preferably 45-60 ℃; when the initiator is a redox initiator, the polymerization temperature is preferably 15 to 30 ℃, and more preferably 15 to 20 ℃.
According to the invention, the method preferably comprises adjusting the pH of the aqueous solution of monomers D, E and F and then passing in the inert gas, and more preferably, after the initiator has been added, the passage of nitrogen is stopped.
In order to obtain the polymer finished product with the water-plugging profile control performance, 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 water-plugging profile control performance.
According to a preferred embodiment of the present invention, the preparation method of the polymer with water shutoff and profile control properties comprises the following steps:
step 1: adding a monomer D, a monomer E and a monomer F into a polymerization reactor to prepare an aqueous solution, adjusting the pH value of the aqueous solution to 8-10 by using alkali, and introducing nitrogen for 5-60min to remove oxygen in the aqueous solution;
step 2: adding an initiator into the aqueous solution obtained in the step 1, uniformly mixing, stopping introducing nitrogen, sealing, and carrying out polymerization reaction for 5-10 hours to obtain a colloidal polymer aqueous solution; wherein, when the initiator is azo initiator, the temperature of the polymerization reaction is 40-70 ℃; when the initiator is redox initiator, the temperature of the polymerization reaction is 15-30 ℃;
and 3, step 3: taking out the colloid, and then granulating, drying, crushing and screening to obtain the polymer finished product with the water plugging and profile control performance. The methods of granulation, drying, pulverization and screening are all well known to those skilled in the art, and are not described in detail herein.
In a third aspect, the present invention provides a polymer having water shutoff and profile control properties prepared by the foregoing method.
In a fourth aspect, the invention provides the application of the polymer with water shutoff profile control performance in water shutoff profile control of oil fields.
In a fifth aspect, the invention provides an application of the polymer with water shutoff and profile control performance in preparing an oilfield water shutoff and profile control agent.
When the polymer with water shutoff and profile control performance is applied to water shutoff and profile control of oil fields and preparation of water shutoff and profile control agents of oil fields, the specific application method is well known by the technical personnel in the field, and the invention is not described in detail herein.
The polymer with water shutoff and profile control performances, the preparation method and the application thereof have the following specific advantages:
1) in the polymer with the structural unit A, the structural unit B and the structural unit C, the structural unit C is hydrolyzed under the formation temperature condition (70-90 ℃) to generate an N-hydroxymethyl propionamide structure and active hydrogen. The resulting product is further subjected to Mannich reaction with structural unit A to form crosslinks. Hydrolysis of structural unit C in the formation is a relatively slow and gradual process. So that the water plugging profile control agent can be conveyed to a far wellbore zone to slowly gel. Therefore, the polymer with water shutoff and profile control performance provided by the invention can realize slow tackifying and gelling in a longer time range, and is suitable for deep water shutoff and profile control of a far well zone.
2) The system does not need to additionally add a delayed crosslinking agent.
The present invention will be described in detail below by way of examples. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
This example illustrates the polymer with water shutoff and profile control properties and the preparation method thereof
(1) 225 parts by mass of Acrylamide (AM), 50 parts by mass of Fumaric Acid (FA), and 12.5 parts by mass of an acrylamidomethyl ester compound represented by the formula (2) were dissolved in 1000 parts by mass of water with stirring, the pH of the solution was adjusted to 9.2 with sodium hydroxide, and the aqueous solution was deoxygenated by introducing nitrogen gas at room temperature for 30 minutes.
Figure BDA0001137745390000111
(2) 0.02 part of initiator 2, 2-azobis (2-methyl propionamidine) hydrochloride (AIBA) is added, nitrogen is stopped from being introduced, and the reaction is carried out for 6 hours under the sealing condition at the constant temperature of 50 ℃ under the normal pressure, thus obtaining a colloidal polymer solution product.
(3) The product was dried, granulated, crushed and sieved to obtain a polymer a1 having water shutoff and profile control properties, wherein the polymer obtained had a structural unit a content of 78 wt%, a structural unit B content of 17 wt%, and a structural unit C content of 5 wt%, and the molecular weight and solid content of the obtained polymer are shown in table 1.
Example 2
This example illustrates the polymer with water shutoff and profile control properties and the preparation method thereof
(1) 200 parts by mass of Acrylamide (AM), 25 parts by mass of Fumaric Acid (FA) and 25 parts by mass of an acrylamidomethyl ester compound represented by the formula (3) were dissolved in 1000 parts by mass of water with stirring, the pH of the solution was adjusted to 9 with sodium hydroxide, and the aqueous solution was deoxygenated by introducing nitrogen gas at room temperature for 30 minutes.
Figure BDA0001137745390000112
(2) Adding 0.01 part of ammonium persulfate and 0.01 part of sodium bisulfite as a redox initiation system, stopping introducing nitrogen, and reacting at constant temperature of 20 ℃ under normal pressure in a sealed condition for 7 hours to obtain a colloidal polymer solution product.
(3) The product was dried, granulated, crushed and sieved to obtain a polymer a2 having water shutoff and profile control properties of the present invention, wherein the content of structural unit a was 80 wt%, the content of structural unit B was 10 wt%, the content of structural unit C was 10 wt%, and the molecular weight and solid content of the obtained polymer are shown in table 1.
Example 3
This example illustrates the polymer with water shutoff and profile control properties and the preparation method thereof
(1) 187.5 parts by mass of Acrylamide (AM), 12.5 parts by mass of Fumaric Acid (FA), and 50 parts by mass of an acrylamidomethyl ester compound represented by the formula (4) were dissolved in 1000 parts by mass of water with stirring, the pH of the solution was adjusted to 8.5 with sodium hydroxide, and the aqueous solution was deoxygenated by introducing nitrogen gas at room temperature for 30 minutes.
Figure BDA0001137745390000121
(2) 0.015 part of 2, 2-azobis (2-methyl propionamidine) hydrochloride (AIBA) as an initiator was added thereto, while stopping the introduction of nitrogen gas, and reacted at a constant temperature of 45 ℃ under a normal pressure in a sealed condition for 6 hours to obtain a gel-like polymer solution product.
(3) The product was dried, granulated, crushed and sieved to obtain a polymer a3 having water shutoff and profile control properties of the present invention, wherein the content of structural unit a was 75 wt%, the content of structural unit B was 5 wt%, the content of structural unit C was 20 wt%, and the molecular weight and solid content of the obtained polymer are shown in table 1.
Example 4
This example illustrates the polymer with water shutoff and profile control properties and the preparation method thereof
The preparation of polymer A4 having water-blocking profile-controlling properties was carried out as in example 3, except that the initiator used was 2, 2-azo (2- (2-imidazolin-2-yl) propane) dihydrochloride (VA-044), and the molecular weights and the solids contents of the resulting polymerization were as indicated in Table 1.
Example 5
This example illustrates the polymer with water shutoff and profile control properties and the preparation method thereof
Preparation of a polymer A5 having water-blocking profile-controlling properties was carried out in the same manner as in example 3, except that Acrylamide (AM) was used in an amount of 150 parts by weight, Fumaric Acid (FA) was used in an amount of 97.5 parts by weight, the monomer represented by the formula (4) was used in an amount of 2.5 parts by weight, and the pH of the reaction was 8.0.
The polymer obtained had a content of the structural unit A of 60% by weight, a content of the structural unit B of 39% by weight and a content of the structural unit C of 1% by weight, and the molecular weight and the solid content of the polymer obtained are shown in Table 1.
Example 6
This example illustrates the polymer with water shutoff and profile control properties and the preparation method thereof
The preparation of polymer A6 having water-blocking profile-controlling properties was carried out in accordance with the procedure of example 3, except that the phenyl group in formula (4) was replaced by a cyclohexyl group, and the molecular weight and the solids content of the resulting polymer are shown in Table 1.
Comparative example 1
This comparative example illustrates a reference polymer with water shut-off and profile control properties and a process for its preparation
The preparation of polymer D1 having water-blocking profile-controlling properties was carried out in accordance with the procedure of example 3, except that the monomer represented by formula (4) was not used and the molecular weight and the solid content of the resulting polymerization were as shown in Table 1.
Comparative example 2
This comparative example illustrates a reference polymer with water shut-off and profile control properties and a process for its preparation
Preparation of polymer D2 having water-blocking profile-controlling properties was carried out in the same manner as in example 3, except that Acrylamide (AM) was used in an amount of 100 parts by weight, Fumaric Acid (FA) was used in an amount of 25 parts by weight, and the monomer represented by the formula (4) was used in an amount of 100 parts by weight.
The polymer obtained had a content of the structural unit A of 44.4% by weight, a content of the structural unit B of 11.2% by weight and a content of the structural unit C of 44.4% by weight, and the molecular weight and the solid content of the polymer obtained were as shown in Table 1.
Comparative example 3
This comparative example illustrates a reference polymer with water shut-off and profile control properties and a process for its preparation
The preparation of polymer D3 having water-blocking profile-controlling properties was carried out in accordance with the procedure of example 3, except that in step (1) no nitrogen gas was fed and the polymerization was carried out without further sealing, the molecular weight and the solids content of the resulting polymerization being shown in Table 1.
Test example
(1) The obtained water shutoff profile control agent product is prepared into 1500mg/L aqueous solution (prepared by using water with the mineralization degree of 10000 mg/L), oxygen is removed, sealing is carried out, and heat aging is carried out at the temperature of 80 ℃. The solution viscosity was measured (test conditions: shear rate 7.34/S) for different aging times and the results are shown in Table 1.
TABLE 1
Figure BDA0001137745390000151
(viscosity units mPas)
(2) The obtained water shutoff profile control agent product is prepared into 1500mg/L aqueous solution (prepared by using water with the mineralization degree of 10000 mg/L), oxygen is removed, sealing is carried out, and heat aging is carried out at the temperature of 90 ℃. The solution viscosity was measured (test conditions: shear rate 7.34/S) for various aging times, and the results are shown in Table 2.
TABLE 2
Figure BDA0001137745390000152
(viscosity units mPas)
Test results show that the single-dosage delayed self-crosslinking water-soluble polymer provided by the invention can realize slow tackifying and gelling in a longer time range. The system does not need to additionally add a delayed crosslinking agent. The formed self-crosslinking weak gel has high aging retention viscosity and is suitable for deep water shutoff profile control of a far well zone. And the above properties of the polymer within the preferred range of the present invention are more excellent.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (17)

1. The application of the polymer in water shutoff and profile control of oil fields, wherein the polymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is provided by an acrylamide monomer, the structural unit B is provided by a fumaric acid monomer, and the structural unit C is provided by a monomer with a structure shown in a formula (1); wherein, based on the weight of the polymer, the content of the structural unit A is 60-98 wt%, the content of the structural unit B is 1-39 wt%, and the content of the structural unit C is 1-39 wt%;
Figure FDA0002317459020000011
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl.
2. The application of the polymer in preparing the oilfield water shutoff profile control agent is disclosed, wherein the polymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is provided by an acrylamide monomer, the structural unit B is provided by a fumaric acid monomer, and the structural unit C is provided by a monomer with a structure shown in a formula (1); wherein, based on the weight of the polymer, the content of the structural unit A is 60-98 wt%, the content of the structural unit B is 1-39 wt%, and the content of the structural unit C is 1-39 wt%;
Figure FDA0002317459020000012
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substituted or unsubstituted aryl.
3. Use according to claim 1 or 2, wherein the structural unit a is present in an amount of 75-90 wt.%, the structural unit B is present in an amount of 5-20 wt.% and the structural unit C is present in an amount of 4-20 wt.%, based on the weight of the polymer.
4. Use according to claim 1 or 2, wherein, in formula (1), R1、R2、R3Each independently is H, C1-C4 alkyl, C12 alkyl, C6-C10 substituted or unsubstituted aryl; r4Is C1-C4 alkyl, C12 alkyl, C6-C10 substituted or unsubstituted aryl.
5. Use according to claim 4, wherein R1、R2、R3Each independently is H, methyl, ethyl, propyl, butyl, dodecyl, phenyl, naphthyl, benzyl, or ethylphenyl; r4Is methyl, ethyl, propyl, butyl, dodecyl, phenyl, naphthyl, benzyl, ethylphenyl, cyclohexyl, cycloheptyl or cyclooctyl.
6. Use according to claim 1 or 2, wherein the polymer is prepared by a process comprising: in the presence of an initiator and water as a solvent, and under an inert gas atmosphere, carrying out solution polymerization reaction on a monomer D, a monomer E and a monomer F; wherein the monomer D is an acrylamide monomer, the monomer E is a fumaric acid monomer, and the monomer F is a monomer with a structure shown in a formula (1); wherein the monomers D, E and F are used in amounts such that the prepared polymer contains 60-98 wt% of the structural unit A, 1-39 wt% of the structural unit B and 1-39 wt% of the structural unit C;
Figure FDA0002317459020000021
wherein, in the formula (1), R1、R2、R3Each independently is H, C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl; r4Is C1-C12 alkyl, C6-C12 substituted or unsubstituted cycloalkyl, C6-C12 substitutedA substituted or unsubstituted aryl group.
7. The use according to claim 6, wherein the monomers D, E and F are used in amounts such that a polymer is produced in which the structural unit A is present in an amount of from 75 to 90% by weight, the structural unit B is present in an amount of from 5 to 20% by weight and the structural unit C is present in an amount of from 4 to 20% by weight.
8. Use according to claim 6, wherein, in formula (1), R1、R2、R3Each independently is H, C1-C4 alkyl, C12 alkyl, C6-C10 substituted or unsubstituted aryl; r4Is C1-C4 alkyl, C12 alkyl, C6-C10 substituted or unsubstituted aryl.
9. Use according to claim 8, wherein R1、R2、R3Each independently H, methyl, ethyl, propyl, butyl, dodecyl, phenyl, naphthyl, benzyl or ethylphenyl, R4Is methyl, ethyl, propyl, butyl, dodecyl, phenyl, naphthyl, benzyl, ethylphenyl, cyclohexyl, cycloheptyl or cyclooctyl.
10. Use according to claim 6, wherein the inert gas is nitrogen.
11. Use according to claim 6, wherein the conditions of the solution polymerization reaction comprise: the pH value is 8-10; the temperature is 15-70 deg.C, and the time is 5-10 hr.
12. Use according to claim 6, wherein the initiator comprises an azo-type initiator and/or a redox-type initiator.
13. The use according to claim 12, wherein the azo-type initiator is at least one of 2, 2-azo (2- (2-imidazolin-2-yl) propane) dihydrochloride, 2-azo (2-methyl-N- (2-hydroxyethyl) propionamide), and 2, 2-azobis (2-methylpropionamidine) hydrochloride; in the redox initiator, an oxidant is potassium persulfate and/or ammonium persulfate, and a reducing agent is sodium sulfite and/or sodium bisulfite.
14. Use according to claim 13, wherein the azo-type initiator is 2, 2-azobis (2-methylpropionamidine) hydrochloride.
15. The use according to claim 13, wherein in the redox initiator, the oxidizing agent is ammonium persulfate and the reducing agent is sodium bisulfite.
16. Use according to claim 12, wherein the initiator is an azo-type initiator and the temperature of the solution polymerization reaction is between 40 and 70 ℃;
17. use according to claim 12, wherein the initiator is a redox initiator and the polymerization temperature is from 15 to 30 ℃.
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CN104231164A (en) * 2013-06-20 2014-12-24 中国石油化工股份有限公司 Acrylamide copolymer as well as preparation method and application of acrylamide copolymer
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CN104231164A (en) * 2013-06-20 2014-12-24 中国石油化工股份有限公司 Acrylamide copolymer as well as preparation method and application of acrylamide copolymer
CN104610490A (en) * 2013-11-04 2015-05-13 中国石油化工股份有限公司 Acrylamide copolymer and preparation method and application thereof

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