CN110790859A - Acrylamide copolymer and preparation method and application thereof - Google Patents
Acrylamide copolymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of oilfield flooding, and discloses an acrylamide copolymer and a preparation method and application thereof, wherein the preparation method comprises the following steps: under the condition of solution polymerization reaction, in the presence of an initiator and a surfactant, carrying out polymerization reaction on a monomer mixture consisting of acrylamide, a comonomer with a structure shown in a formula (1) and an active monomer with a structure shown in a formula (2) in water; the initiator comprises an initiator A and an initiator B, the structure of which is shown as the formula (3), and the initiator B is 4-methyl thiosemicarbazide; wherein R is1‑R3And R5Each is selected from hydrogen or C1-C4 alkyl, R4Is C1-C4 alkylene, M is hydrogen, sodium or potassium; r6‑R9Each is C1-C4 alkyl, n is an integer of 1-10, and m is an integer of 2-6. The prepared acrylamide copolymer has ultrahigh molecular weight, high viscosity, excellent solubility, high temperature resistance, high salt resistance and high surface/interface activity.
Description
Technical Field
The invention relates to the technical field of oilfield flooding, and particularly relates to an acrylamide copolymer and a preparation method and application thereof.
Background
In the process of oilfield flooding, due to the existence of stratum heterogeneity, injected water can suddenly enter along a hypertonic layer, so that the water production rate of an oil well is increased year by year. The profile control of water injection well and water shutoff of oil well have become important measures for stable production and yield increase of oil field. However, with the increase of the turns of conventional plugging regulating systems and measures, the saturation of residual oil in a near well zone is obviously reduced, the oil increasing effect is poor, and the heterogeneity of an oil reservoir can be more effectively regulated and improved only by deep plugging regulation, so that the swept volume and the swept coefficient of an injection liquid are improved, and the crude oil recovery rate in a water injection oil recovery stage is improved.
In the future, deep profile control technology has received general attention in the fields of research and application of oil recovery enhancement technology at home and abroad. According to the actual conditions of the oil fields, proper deep profile control agents and corresponding construction processes are screened out, so that the oil fields play an important role in oil stabilization and water control. In addition, the water shutoff and profile control technology has great significance for improving the productivity of the oil well by the water drive oil reservoir in the ultra-high water cut period, and is an important measure for creating and increasing the efficiency of the low-efficiency well under the low oil price. However, in the ultra-high water content stage, due to serious flooding of an oil well and complex oil-water relationship, the deep profile control under an oil reservoir is difficult to achieve by traditional water plugging profile control agents such as pre-crosslinked gel particles, clay gel polymer flocculation systems and the like, so that the field implementation effect is poor. Therefore, the development of the novel active functional polymer for profile control and flooding has important practical significance and wide application prospect for improving the single-well productivity and creating benefit and efficiency at low oil price.
The living functional polymer is mainly obtained by micellar free radical copolymerization of acrylamide and a living functional monomer (such as an acrylamide-type living monomer). The polymer not only has the viscosity increasing property, but also has the solubilizing and emulsifying properties of the micromolecule surfactant, can effectively overcome the separation phenomenon of the polymer/surfactant binary combination flooding in the stratum migration process, and can improve the sweep efficiency and the oil washing efficiency, thereby improving the crude oil recovery ratio. Generally, acrylamide active monomers have the characteristics of moderate reaction activity, high polymer molecular weight and the like in micelle copolymerization, so that the polymer for deep profile control and flooding can be obtained.
In order to further improve the exploitation effect of high-temperature and high-salt deep oil reservoirs, it is still necessary to develop new polymers with higher molecular weight and better temperature and salt resistance and the like and a preparation method thereof in the field.
Disclosure of Invention
The invention aims to provide an acrylamide copolymer and a preparation method and application thereof. The acrylamide copolymer prepared by the method has ultrahigh molecular weight, viscosity increasing property, excellent solubility, temperature resistance and salt resistance and good surface/interface activity, so that the acrylamide copolymer is particularly suitable to be used as a polymer deep profile control agent for high-temperature and high-salt oil reservoirs.
According to a first aspect of the present invention, there is provided a method for preparing an acrylamide copolymer, the method comprising: under the condition of solution polymerization reaction, in the presence of an initiator and a surfactant, carrying out polymerization reaction on a monomer mixture consisting of acrylamide, a comonomer and an active monomer in water, wherein the structure of the comonomer is shown as a formula (1), and the structure of the active monomer is shown as a formula (2); the initiator comprises an initiator A and an initiator B, the structure of the initiator A is shown as a formula (3), and the initiator B is 4-methyl thiosemicarbazide;
wherein R is1-R3And R5Each independently is hydrogen or C1-C4 alkyl, R4Is C1-C4 alkylene, M is hydrogen, sodium or potassium; r6-R9Each independently is a C1-C4 alkyl group, n is an integer from 1 to 10, and m is an integer from 2 to 6.
According to a second aspect of the present invention there is provided an acrylamide copolymer obtainable by the process of the first aspect of the present invention.
According to a third aspect of the present invention, there is provided the use of the acrylamide copolymer according to the second aspect of the present invention as a deep profile control agent.
In the preparation method provided by the invention, the compound initiation system containing the initiator A and the initiator B can be used for smoothly initiating the copolymerization of acrylamide, comonomer and active monomer at normal temperature (20-40 ℃), the polymerization reaction condition is mild, and the acrylamide copolymer with the viscosity-average molecular weight of 2800-3300 ten thousand can be prepared. In addition, the acrylamide copolymer also has the advantages of high surface/interface activity, high dissolution speed, high temperature and high salt resistance and the like. The acrylamide copolymer has excellent tackifying property, and can obtain higher viscosity under lower polymer concentration, so that the acrylamide copolymer can be used in less amount in actual oilfield development, and the oil recovery cost is greatly saved.
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.
According to a first aspect of the present invention, there is provided a method for preparing an acrylamide copolymer, the method comprising: a monomer mixture consisting of acrylamide, comonomer and reactive monomer is polymerized in water in the presence of an initiator and a surfactant under solution polymerization conditions.
In the invention, the structure of the comonomer is shown as a formula (1), and the structure of the active monomer is shown as a formula (2); the initiator comprises an initiator A and an initiator B, the structure of the initiator A is shown as a formula (3), and the initiator B is 4-methyl thiosemicarbazide;
wherein R is1-R3And R5Each independently is hydrogen or C1-C4 alkyl, R4Is C1-C4 alkylene, M is hydrogen, sodium or potassium; r6-R9Each independently is a C1-C4 alkyl group, n is an integer from 1 to 10, and m is an integer from 2 to 6.
In the present invention, examples of the C1-C4 alkyl group may include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl.
In the present invention, the alkylene group may be linear or branched. Examples of the C1-C4 alkylene group may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene. The alkylene group refers to a residue of an alkane which has been deprived of two hydrogen atoms, which may be two hydrogen atoms on the same carbon atom or two hydrogen atoms on different carbon atoms, and which may be linear or branched, for example, the ethylene group may be-CH2CH2-or-CH (CH)3)-。
The inventor of the present invention found in research that when a composite initiation system including the initiator a (main initiator) and the initiator B (auxiliary initiator) is used to initiate polymerization reaction of acrylamide, the comonomer and the active monomer, the micelle can be mildly decomposed to generate free radicals, so that the concentration of the free radicals in the micelle can be always kept at a low and stable concentration, and further, the polymerization of each monomer can be slowly initiated, the whole polymerization reaction can be smoothly carried out, and the polymerization reaction speed can be effectively controlled, thereby not only being beneficial to obtaining acrylamide copolymer with high molecular weight, but also reducing cross-linking between molecular chains and enabling the copolymer to have good solubility.
Preferably, the initiator A is used in an amount of 0.05 to 0.5 wt% and the initiator B is used in an amount of 0.01 to 0.1 wt%, based on the total weight of the monomer mixture.
Preferably, in the formula (3), R6-R9Are each selected from methyl groups or are each selected from ethyl groups, and are each preferably methyl groups.
In the present invention, the initiator A may be obtained commercially, for example, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetramethylpropylenediamine, N, N, N ', N' -tetramethylbutylenediamine, N, N, N ', N' -tetramethylhexamethylenediamine, etc. available from Aladdin reagent.
In the present invention, the comonomer is at least one selected from the compounds represented by formula (1). From the viewpoint of further improving the temperature resistance and salt resistance of the copolymer, it is preferable that R in the comonomer having a structure represented by formula (1)1Is hydrogen, R2And R3Each independently methyl or ethyl, and M is hydrogen or sodium. More preferably, the comonomer is 2-acrylamido-2-methylpropanesulfonic acid.
In the present invention, the reactive monomer is at least one selected from the group consisting of compounds represented by formula (2). Preferably, in the reactive monomer having a structure represented by the formula (2), R5Is methyl or ethyl, more preferably methyl, and n is an integer of 1 to 8.
In the present invention, the content of each component in the monomer mixture may be selected with reference to the acrylamide-based copolymer. In the present invention, it is preferable that acrylamide is used in an amount of 35 to 65 wt%, the comonomer is used in an amount of 30 to 60 wt%, and the reactive monomer is used in an amount of 0.1 to 5 wt%, based on the total weight of the monomer mixture, so that the resulting copolymer can simultaneously achieve better solubility and higher molecular weight, and hydrolysis or purification steps conventionally used in the preparation of acrylamide copolymers can be omitted.
More preferably, acrylamide is used in an amount of 35 to 60 wt%, the comonomer is used in an amount of 38 to 60 wt%, and the reactive monomer is used in an amount of 0.1 to 5 wt%, based on the total weight of the monomer mixture.
According to the invention, the amount of the monomer mixture and water used at the start of the polymerization reaction is not particularly limited and may vary within wide limits. Preferably, the mass ratio of the monomer mixture to the amount of water used is 1:1.5 to 5, more preferably 1:2 to 4.
In the present invention, the polymerization reaction is carried out in the presence of a surfactant; the surfactant is used in an amount of 1 to 5 wt% based on the total weight of the monomer mixture.
Preferably, the surfactant is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
According to the present invention, it is preferred that the polymerization reaction is carried out in the presence of a complexing agent and/or other auxiliaries in order to avoid the influence of impurities in the reaction system (for example, derived from water, monomers and initiator) and to increase the solubility of the monomers in water. Based on the total weight of the monomer mixture, the amount of the complexing agent is 0.01-0.1 wt%, and the amount of the other auxiliary agent is 1-10 wt%. The complexing agent may be selected from at least one of disodium ethylenediaminetetraacetate (EDTA-2Na), citric acid, citrate, and polyhydroxyacrylic acid. The other auxiliary agent may be at least one selected from urea, sodium formate, isopropyl alcohol and sodium hypophosphite.
Preferably, the complexing agent is disodium ethylene diamine tetraacetate, and the other auxiliary agent is urea.
In the present invention, the complexing agent and other auxiliaries may be added to the reaction system before the initiator is added.
In the invention, the initiator can initiate the polymerization of the monomer under a relatively mild condition and the temperature does not suddenly rise after the reaction, so the initiator can be added into the reaction system under a normal temperature condition.
In the present invention, the polymerization reaction is generally carried out in the presence of an inert gas comprising at least one of nitrogen or a gas of a group zero element in the periodic table of the elements, which is conventional in the art, preferably nitrogen.
In the present invention, the solution polymerization reaction conditions may include: the temperature is 20-70 deg.C, preferably 25-70 deg.C, the time is 10-14 hr, and the pH is 6-10. The pH is adjusted by adding a base, which may be selected, for example, from sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia, methylamine, ethylamine, ethanolamine and triethanolamine, more preferably sodium hydroxide or sodium carbonate.
In the present invention, in order to further increase the molecular weight of the copolymer, it is preferable that the polymerization reaction comprises two stages which are sequentially performed, and the reaction conditions of the first stage include: the temperature is 25-40 ℃, and the time is 6-8 hours; the reaction conditions of the second stage include: the temperature is 60-70 ℃ and the time is 4-6 hours.
According to the invention, the polymer obtained after said polymerization is generally a gum. To obtain the acrylamide copolymer product, the method may further comprise: and sequentially granulating, drying, crushing and screening the rubber blocks. The specific conditions of the foregoing processes are well known in the art and will not be described herein.
According to one embodiment, the order of addition of the materials is: mixing acrylamide, a comonomer and water to obtain an aqueous solution, adjusting the pH, adding the active monomer, a surfactant, an optional complexing agent and other auxiliaries, stirring and dispersing to obtain a stable micelle, and finally adding an initiator to initiate polymerization.
According to a more specific preferred embodiment, the process for preparing the acrylamide copolymer comprises the steps of:
1) adding acrylamide, comonomer and water into a three-neck flask (also called a polymerization flask hereinafter) to prepare an aqueous solution, adjusting the pH of the aqueous solution to 6-10 by using alkali, and blowing nitrogen for 20-60min to remove oxygen;
2) under the protection of nitrogen, adding the surfactant, the aqueous solution of the complexing agent, the other auxiliary agents and the active monomer into the aqueous solution, placing the aqueous solution in a water bath at 25-40 ℃, and uniformly stirring and dispersing to form stable micelles;
3) adding an initiator A and an initiator B into the reaction system in the step 2) at the temperature of 25-40 ℃ under the protection of nitrogen until the solution is thickened, namely, starting a polymerization reaction, and maintaining the reaction for 6-8 hours; then heating the reaction to 60-70 ℃, and continuing the reaction for 4-6 hours under the protection of nitrogen to obtain a polymer rubber block;
5) and taking out the rubber block, and granulating, drying, crushing and screening the rubber block to obtain an acrylamide copolymer product.
In step 1), the base is preferably sodium hydroxide or sodium carbonate.
In step 2), the aqueous solution of the complexing agent is preferably an aqueous EDTA-2Na solution with a concentration of 0.5-2 wt%.
According to a second aspect of the present invention there is provided an acrylamide copolymer obtainable by the process according to the first aspect of the present invention. The acryloyl copolymer prepared by the method has ultrahigh molecular weight, viscosity increasing property, excellent solubility, temperature resistance, salt resistance and surface/interface activity, so that the acryloyl copolymer can be used as a polymer deep profile control agent for high-temperature and high-salt oil reservoirs. Typically, the acrylamide copolymer has a viscosity average molecular weight of 2800 to 3300 ten thousand.
According to a third aspect of the present invention, the present invention provides the use of the above acrylamide copolymer as a deep profile control agent.
The acrylamide copolymer disclosed by the invention belongs to an ultrahigh molecular weight polymer, has the viscosity increasing property of a water-soluble high molecular polymer, enters the deep part of an oil reservoir under the action of pressure to perform deep profile control, and can effectively reduce the water phase permeability of a large pore passage; in addition, the acrylamide copolymer also has the characteristics of good surface activity, emulsification and compatibilization and the like due to the introduction of the active monomer, and can reduce the surface tension and the interfacial tension between oil and water, thereby increasing the oil washing capability of the active functional polymer in a deep part.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the reagents used are all chemically pure reagents from commercial sources, unless otherwise specified.
The performance test of the product is carried out by adopting the following method:
1. testing the viscosity-average molecular weight of the polymer by using a one-point method by using a Ubbelohde viscometer;
2. the apparent viscosity of the polymer solution was 1500mg/L of the polymer solution prepared with a salt water having a degree of mineralization of 33000mg/L (wherein the calcium and magnesium ions are 800mg/L) and a Brookfield viscometer (using a ULA spindle) at 25 deg.C, 85 deg.C and a shear rate of 7.34s-1Measuring under the condition;
3. surface tension was determined by measuring the surface tension of an aqueous solution (1500mg/L) of the polymer in pure water at a prescribed test temperature (25 ℃) with a DCAT-21 surface tensiometer;
4. the interfacial tension is measured by a TX500C interfacial tension meter at a specified test temperature (80 ℃) to prepare 1500mg/L solution of the polymer by using saline water with the mineralization degree of 33000mg/L (wherein the calcium and magnesium ions are 800mg/L) and the crude oil;
5. the dissolution time of the polymer was tested according to the method specified in Q/SH 10201572-2006.
The concentration of the EDTA-Na aqueous solution was 1 wt%; 2-acrylamido-2-methylpropanesulfonic acid was purchased from xiamen changtian chemical company, ltd; acrylamide was purchased from bio-chemical industries, ltd, Shandong Baomo; the reactive monomers were purchased from Shanghai Allantin Biotechnology Ltd.
Example 1
This example illustrates the acrylamide copolymer and the preparation method thereof according to the present invention.
1) Adding 11.8g of acrylamide, 8.0g of 2-acrylamido-2-methylpropanesulfonic acid and 60.0g of deionized water into a polymerization bottle to dissolve the monomers to obtain an aqueous solution of a monomer mixture, adjusting the pH value to 6.0 by using sodium hydroxide, and blowing nitrogen for 30 min;
2) to a polymerization flask were added 0.2g of sodium lauryl sulfate, 0.2g of reactive monomer (R) under nitrogen blanket5Methyl, n ═ 1), 0.2g of urea and 1.0g of EDTA-2Na aqueous solution, and the polymerization flask is placed in a water bath at 25 ℃ to be stirred and dispersed to form stable micelles;
3) under the protection of nitrogen, adding 0.01g of N, N, N ', N' -tetramethylethylenediamine and 0.002g of 4-methylaminothiourea into a polymerization bottle at 25 ℃, initiating the polymerization of the monomer mixture and reacting for 6 hours, then heating to 60 ℃, and continuing the polymerization for 6 hours to obtain a rubber block;
4) the obtained gel block was granulated, dried, crushed and sieved to obtain an acrylamide copolymer product, the properties of which are shown in table 1.
Example 2
This example illustrates the acrylamide copolymer and the preparation method thereof according to the present invention.
1) Adding 7.0g of acrylamide, 12.0g of 2-acrylamido-2-methylpropanesulfonic acid and 60.0g of deionized water into a polymerization bottle to dissolve the monomers to obtain an aqueous solution of a monomer mixture, adjusting the pH value to 7.0 by using sodium hydroxide, and blowing nitrogen for 30 min;
2) to a polymerization flask were added 1.0g of sodium lauryl sulfate, 1.0g of reactive monomer (R) under nitrogen blanket5Methyl, n ═ 1), 0.4g of urea and 1.0g of EDTA-2Na aqueous solution, and the polymerization flask is placed in a water bath at 40 ℃ for stirring and dispersion to form stable micelles;
3) under the protection of nitrogen, adding 0.1g of N, N, N ', N' -tetramethylethylenediamine and 0.02g of 4-methyl thiosemicarbazide into a polymerization bottle at 40 ℃ to initiate the polymerization of the monomer mixture and react for 8 hours, then heating to 60 ℃ and continuing the polymerization for 4 hours to obtain a rubber block;
4) the obtained gel block was granulated, dried, crushed and sieved to obtain an acrylamide copolymer product, the properties of which are shown in table 1.
Example 3
This example illustrates the acrylamide copolymer and the preparation method thereof according to the present invention.
1) Adding 11.8g of acrylamide, 8.0g of 2-acrylamido-2-methylpropanesulfonic acid and 60.0g of deionized water into a polymerization bottle to dissolve the monomers to obtain an aqueous solution of a monomer mixture, adjusting the pH value to 6.0 by using sodium hydroxide, and blowing nitrogen for 30 min;
2) to a polymerization flask were added 0.2g of sodium lauryl sulfate, 0.2g of reactive monomer (R) under nitrogen blanket5Methyl, n ═ 8), 2.0g of urea and 2.0g of EDTA-2Na aqueous solution, and the polymerization flask is placed in a water bath at 25 ℃ to be stirred and dispersed to form stable micelles;
3) under the protection of nitrogen, adding 0.01g of N, N, N ', N' -tetramethyl hexanediamine and 0.002g of 4-methyl thiosemicarbazide into a polymerization bottle at 25 ℃, initiating the polymerization of the monomer mixture and reacting for 6 hours, then heating to 70 ℃, and continuing the polymerization for 4 hours to obtain a rubber block;
4) the obtained gel block was granulated, dried, crushed and sieved to obtain an acrylamide copolymer product, the properties of which are shown in table 1.
Example 4
This example illustrates the acrylamide copolymer and the preparation method thereof according to the present invention.
1) Adding 9.9g of acrylamide, 10.0g of 2-acrylamido-2-methylpropanesulfonic acid and 60.0g of deionized water into a polymerization bottle to dissolve the monomers to obtain an aqueous solution of a monomer mixture, adjusting the pH value to 10.0 by using sodium hydroxide, and blowing nitrogen for 30 min;
2) 0.2g of sodium dodecylbenzenesulfonate, 0.1g of reactive monomer (R) are added to a polymerization flask under nitrogen protection5Methyl, n-4), 2.0g of urea and 2.0g of EDTA-2Na aqueous solution, and placing the polymerization bottle in a water bath at 25 ℃ for stirring and dispersing to form stable micelles;
3) under the protection of nitrogen, a polymerization reaction bottle is placed in a constant-temperature water bath at 25 ℃, 0.04g of N, N, N ', N' -tetramethyl butanediamine and 0.01g of 4-methyl thiosemicarbazide are added into the polymerization bottle, the polymerization of the monomer mixture is initiated and the reaction lasts for 6 hours, and then the temperature is raised to 70 ℃ and the polymerization reaction continues for 4 hours;
4) the obtained gel block was granulated, dried, crushed and sieved to obtain an acrylamide copolymer product, the properties of which are shown in table 1.
Comparative example 1
1) Adding 10.0g of acrylamide, 10.0g of 2-acrylamido-2-methylpropanesulfonic acid and 60.0g of deionized water into a polymerization bottle to dissolve the monomers to obtain an aqueous solution of a monomer mixture, adjusting the pH value to 10.0 by using sodium hydroxide, and blowing nitrogen for 30 min;
2) under the protection of nitrogen, 0.2g of sodium dodecyl benzene sulfonate, 2.0g of urea and 2.0g of EDTA-2Na aqueous solution are added into a polymerization bottle, and the polymerization bottle is placed in a water bath at 25 ℃ for stirring and dispersing to form stable micelles;
3) under the protection of nitrogen, adding 0.04g of N, N, N ', N' -tetramethyl butanediamine and 0.01g of 4-methyl thiosemicarbazide into a polymerization bottle at 25 ℃, initiating the polymerization of the monomer mixture and reacting for 6 hours, then heating to 70 ℃, and continuing the polymerization for 4 hours to obtain a rubber block;
4) the obtained gel block was granulated, dried, crushed and sieved to obtain an acrylamide copolymer product, the properties of which are shown in table 1.
Comparative example 2
1) Adding 11.8g of acrylamide, 8.0g of 2-acrylamido-2-methylpropanesulfonic acid and 60.0g of deionized water into a polymerization bottle to dissolve the monomers to obtain an aqueous solution of a monomer mixture, adjusting the pH value to 6.5 by using sodium hydroxide, and blowing nitrogen for 30 min;
2) to a polymerization flask were added 2.0g of sodium lauryl sulfate, 0.2g of reactive monomer (R) under nitrogen blanket5Methyl, n ═ 1), 1.0g of urea and 2.0g of EDTA-2Na aqueous solution, and the polymerization flask is placed in a water bath at 40 ℃ for stirring and dispersion to form stable micelles;
3) under the protection of nitrogen, 3.0g of 0.1 weight percent potassium persulfate aqueous solution and 1.5g of 0.1 weight percent sodium bisulfite aqueous solution are added into a polymerization bottle at 40 ℃ to initiate the polymerization of the monomer mixture and react for 6 hours, and then the temperature is raised to 70 ℃ to continue the polymerization for 6 hours to obtain a rubber block;
4) the obtained gel block was granulated, dried, crushed and sieved to obtain an acrylamide copolymer product, the properties of which are shown in table 1.
Comparative example 3
An acrylamide copolymer was prepared according to the method of example 1, except that 4-methylthiosemicarbazide in the initiator was replaced with equal mass of dithiobiuret, thereby obtaining an acrylamide copolymer product, the properties of which are shown in Table 1.
TABLE 1
It can be seen from the data in Table 1 that acrylamide copolymers of higher molecular weight can be obtained using the composite initiator system of the present invention. Compared with the comparative examples 1 to 3, the composite initiation system disclosed by the invention has the advantages that the acrylamide copolymer obtained by copolymerizing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and an active monomer under the initiation of the composite initiation system disclosed by the invention has a higher molecular weight, and the aqueous solution of the copolymer has a higher apparent viscosity at both low temperature and high temperature under a high mineralization degree, so that the copolymer has better high-temperature resistance and salt resistance, and the surface tension and the interfacial tension of the aqueous solution of the polymer are low, so that the copolymer is suitable for being used as a deep profile control agent of a high-temperature high-salt oil reservoir.
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 (14)
1. A method for preparing an acrylamide copolymer, the method comprising: under the condition of solution polymerization reaction, in the presence of an initiator and a surfactant, carrying out polymerization reaction on a monomer mixture consisting of acrylamide, a comonomer and an active monomer in water, wherein the structure of the comonomer is shown as a formula (1), and the structure of the active monomer is shown as a formula (2); the initiator comprises an initiator A and an initiator B, the structure of the initiator A is shown as a formula (3), and the initiator B is 4-methyl thiosemicarbazide;
wherein R is1-R3And R5Each independently is hydrogen or C1-C4 alkyl, R4Is C1-C4 alkylene, M is hydrogen, sodium or potassium; r6-R9Each independently is a C1-C4 alkyl group, n is an integer from 1 to 10, and m is an integer from 2 to 6.
2. The process according to claim 1, wherein in the formula (3), R is6-R9Are all selected from methyl or are all selected from ethyl, preferably are all methyl.
3. The preparation method according to claim 1 or 2, wherein the initiator a is used in an amount of 0.05 to 0.5 wt% and the initiator B is used in an amount of 0.01 to 0.1 wt%, based on the total weight of the monomer mixture.
4. The process according to claim 1, wherein in the formula (1), R is1Is hydrogen, R2And R3Each independently methyl or ethyl, and M is hydrogen or sodium.
5. The process according to claim 1, wherein in the formula (2), R is5Is methyl or ethyl, preferably methyl; n is an integer of 1 to 8.
6. The method of any one of claims 1, 4 and 5, wherein acrylamide is used in an amount of 35 to 65 wt%, the comonomer is used in an amount of 30 to 60 wt%, and the reactive monomer is used in an amount of 0.1 to 5 wt%, based on the total weight of the monomer mixture.
7. The production method according to any one of claims 1 to 6, wherein the mass ratio of the monomer mixture to the amount of water used is 1:1.5 to 5, preferably 1:2 to 4.
8. The method according to any one of claims 1 to 7, wherein the surfactant is used in an amount of 1 to 5 wt% based on the total weight of the monomer mixture;
preferably, the surfactant is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
9. The production method according to any one of claims 1 to 8, wherein the polymerization reaction is carried out in the presence of a complexing agent and other auxiliaries; based on the total weight of the monomer mixture, the use amount of the complexing agent is 0.01-0.1 wt%, and the use amount of the other auxiliary agents is 1-10 wt%;
the complexing agent is at least one selected from ethylene diamine tetraacetic acid, citric acid, citrate and polyhydroxyacrylic acid, and is preferably ethylene diamine tetraacetic acid disodium;
the other auxiliary agent is at least one selected from urea, sodium formate, isopropanol and sodium hypophosphite, and is preferably urea.
10. The production method according to any one of claims 1 to 9, wherein the polymerization reaction is carried out in the presence of an inert gas, and the solution polymerization reaction conditions include: the temperature is 20-70 deg.C, the time is 10-14 hr, and the pH is 6-10.
11. The production method according to claim 10, wherein the polymerization reaction comprises two stages carried out in sequence, and the reaction conditions of the first stage include: the temperature is 25-40 ℃, and the time is 6-8 hours; the reaction conditions of the second stage include: the temperature is 60-70 ℃ and the time is 4-6 hours.
12. An acrylamide copolymer produced by the method of any one of claims 1 to 11.
13. The acrylamide copolymer according to claim 12, wherein the viscosity average molecular weight of the acrylamide copolymer is 2800 to 3300 ten thousand.
14. Use of the acrylamide copolymer according to claim 12 or 13 as a deep profile control agent.
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|---|---|---|---|---|
| CN113336890A (en) * | 2020-03-02 | 2021-09-03 | 中国石油化工股份有限公司 | Polymer with surface activity function and preparation method and application thereof |
| CN116063619A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Acrylamide copolymer containing hydroxyl-terminated long-chain structure, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100331510A1 (en) * | 2009-05-20 | 2010-12-30 | Basf Se | Hydrophobically associating copolymers |
| CN106317299A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
| CN106543352A (en) * | 2015-09-21 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
-
2018
- 2018-08-01 CN CN201810864090.7A patent/CN110790859B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100331510A1 (en) * | 2009-05-20 | 2010-12-30 | Basf Se | Hydrophobically associating copolymers |
| CN106317299A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Acrylamide copolymer, and preparation method and application thereof |
| CN106543352A (en) * | 2015-09-21 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of hydrophobic associated polymer and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336890A (en) * | 2020-03-02 | 2021-09-03 | 中国石油化工股份有限公司 | Polymer with surface activity function and preparation method and application thereof |
| CN113336890B (en) * | 2020-03-02 | 2022-07-12 | 中国石油化工股份有限公司 | Polymer with surface activity function and preparation method and application thereof |
| CN116063619A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Acrylamide copolymer containing hydroxyl-terminated long-chain structure, and preparation method and application thereof |
| CN116063619B (en) * | 2021-11-01 | 2024-03-26 | 中国石油化工股份有限公司 | Acrylamide copolymer containing hydroxyl-terminated long-chain structure, and preparation method and application thereof |
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