CN107868174B - Acrylamide copolymer and preparation method and application thereof - Google Patents

Acrylamide copolymer and preparation method and application thereof Download PDF

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CN107868174B
CN107868174B CN201610860515.8A CN201610860515A CN107868174B CN 107868174 B CN107868174 B CN 107868174B CN 201610860515 A CN201610860515 A CN 201610860515A CN 107868174 B CN107868174 B CN 107868174B
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张文龙
杜超
方昭
胡晓娜
刘希
伊卓
祝纶宇
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
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    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers

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Abstract

The invention relates to the field of oilfield chemicals, and discloses an acrylamide copolymer and a preparation method and application thereof. The acrylamide copolymer comprises a structural unit A and a structural unit B, wherein the structural unit A is a structural unit shown in a formula I, and the structural unit B is a structural unit shown in a formula II; and the content of the structural unit A is 60-98 wt% and the content of the structural unit B is 2-40 wt% based on the total weight of the acrylamide copolymer. The acrylamide copolymer has good water solubility and thermal thickening effect, and is suitable for being used as a thermal thickener for tertiary oil recovery of high-temperature and high-salinity oil reservoirs.

Description

Acrylamide copolymer and preparation method and application thereof
Technical Field
The invention relates to the field of oilfield chemicals, and particularly relates to an acrylamide copolymer and a preparation method and application thereof.
Background
The polymer flooding technology is an important technology for increasing the recovery rate of petroleum, and the basic principle is that a water-soluble polymer is added into water injection to increase the viscosity of an aqueous solution, reduce the water/oil fluidity ratio, enlarge the swept volume, increase the swept efficiency and reduce the oil saturation of the swept zone, thereby increasing the recovery rate of petroleum. Practice proves that the oil recovery rate can be greatly improved by adopting the polymer for oil displacement, and great economic benefit and social benefit are generated. For many years, the polymers used for polymer flooding were mainly artificially synthesized partially hydrolyzed polyacrylamides. The limitation of the common partially hydrolyzed polyacrylamide is that the temperature resistance and salt tolerance are low, the hydrolysis speed is high under the conditions of high temperature and high salinity, and the viscosity of the aqueous solution is greatly reduced, so that the oil displacement effect is obviously influenced.
In order to develop a polymer oil displacement agent with better performance and capable of meeting the use requirement of high-temperature oil field tertiary oil recovery, Chinese patents CN1317501A, CN1414057A, CN1876751A and the like invent hydrophobic association polymer oil displacement agents with different molecular structures, and the polymers are characterized in that a molecular main chain contains a certain number of hydrophobic molecular chain segments, and in an aqueous solution, the hydrophobic-hydrophobic interaction between the hydrophobic side chains causes physical crosslinking among the polymer molecular chains, thereby improving the viscosity and the anti-shearing performance of the solution. However, the solubility of the hydrophobically associating polymer is reduced when the content of the hydrophobic monomer in the hydrophobically associating polymer is high due to the complex polymerization process; the solubility is better when the content of hydrophobic monomer in the polymer is low, but the difficulty in forming effective hydrophobic association thickening effect is not obvious at lower polymer concentration.
Chinese patent CN200810095791.5 discloses a thermal thickening terpolymer and a preparation method and application thereof. Wherein a thermo-thickening polymer is a polymer in which the viscosity of an aqueous solution increases with increasing temperature over a range of temperatures. The preparation method adopts the copolymerization preparation of the macromonomer, acrylamide and 2-acrylamide-2-methyl-1-propanesulfonic acid, has better thickening performance in tertiary oil recovery of a high-temperature and high-salinity reservoir, but has the defects of difficult synthesis of the macromonomer, complex synthesis steps, obvious thickening at a lower temperature and no contribution to the migration motion of a polymer in a stratum.
Disclosure of Invention
The invention aims to overcome one of the defects in the prior art and provide an acrylamide copolymer with good water solubility and thermal thickening effect, and a preparation method and application thereof.
In order to achieve the above object, according to a first aspect of the present invention, there is provided an acrylamide copolymer comprising a structural unit a and a structural unit B, wherein the structural unit a is a structural unit represented by formula i, and the structural unit B is a structural unit represented by formula ii; based on the total weight of the acrylamide copolymer, the content of the structural unit A is 60-98 wt%, and the content of the structural unit B is 2-40 wt%;
Figure BDA0001122849430000021
in the formula I, R1Is any one of H and C1-C4 alkyl; in the formula II, R2、R3Each independently selected from H and any one of C1-C12 alkyl; r4Any one selected from the group consisting of H, C1-C12 alkyl groups and C6-C12 aryl groups.
According to the second aspect of the present invention, there is also provided a method for preparing an acrylamide copolymer, the method comprising the steps of: polymerizing a monomer mixture in water under the condition of solution polymerization of olefin in the presence of an initiator, wherein the monomer mixture contains a monomer C with a structure shown in a formula III and a monomer D with a structure shown in a formula IV, and the weight ratio of the monomer C to the monomer D is 1: (0.02-0.65),
Figure BDA0001122849430000031
in the formula III, R1' is any of H and C1-C4 alkyl; in the formula IV, R2′、R3' are each independently selected from H and any one of C1 to C12 alkyl groups; r4' is selected from any one of alkyl groups of H, C1 to C12, and aryl or alkylaryl groups of C6 to C12.
According to a third aspect of the present invention, there is also provided an acrylamide copolymer produced by the above-mentioned method of the present invention.
According to a fourth aspect of the present invention, there is also provided a use of the above-mentioned acrylamide copolymer of the present invention as a thermal thickener
According to the acrylamide copolymer provided by the invention, the structural unit B shown in the formula II is introduced to enable the acrylamide copolymer to have better water solubility and low-temperature stability, and meanwhile, because the introduced structural unit B has a furan structure, the acrylamide copolymer can generate ring-opening hydrolysis reaction at the formation temperature (80-90 ℃), new hydroxyl and carboxyl are generated, and the generation of the new hydroxyl and carboxyl improves the hydration radius of the acrylamide copolymer on one hand, so that the viscosity of an aqueous solution of the acrylamide copolymer is further improved; on the other hand, the intermolecular hydroxyl and carboxyl can generate micro-crosslinking reaction at high temperature, so that the viscosity of the acrylamide copolymer aqueous solution is further improved, and the aim of thickening is fulfilled;
under the high-temperature condition of 80-90 ℃, the apparent viscosity of the aqueous solution of the acrylamide copolymer provided by the invention can reach over 49mPa.s, so that the acrylamide copolymer has the advantage of great thickening and can be used as a thermal thickener for tertiary oil recovery of high-temperature and high-salt oil reservoirs.
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.
The invention provides an acrylamide copolymer, which comprises a structural unit A, a structural unit B and a structural unit B, wherein the structural unit A is a structural unit shown in a formula I, and the structural unit B is a structural unit shown in a formula II; based on the total weight of the acrylamide copolymer, the content of the structural unit A is 60-98 wt%, and the content of the structural unit B is 2-40 wt%;
Figure BDA0001122849430000041
in the formula I, R1Is any one of H (hydrogen) and C1-C4 alkyl; in the formula II, R2、R3Each independently selected from H (hydrogen) and any one of C1-C12 alkyl; r4Any one selected from the group consisting of H, C1-C12 alkyl groups and C6-C12 aryl groups.
Wherein the alkyl group having 1-4 carbon atoms may be linear or branched. Examples of the C1-C4 alkyl group may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
Wherein the alkyl group having 1-12 carbon atoms may be linear or branched. Examples of the C1-C12 alkyl group may include, but are 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.
Wherein the aryl group having C6-C12 is a substituted or unsubstituted phenyl group having 6-12 total carbon atoms. Examples of the aryl group of C6 to C12 include, but are not limited to, phenyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl.
Preferably, R in the structural unit A of the formula I1Is H or methyl.
Preferably, the structure of formula IIR in unit B2Is H, R3Selected from H and any one of C1-C6 alkyl, R4Selected from any one of H and C1-C6 alkyl.
The acrylamide copolymer according to the present invention can achieve the object of the present invention to some extent as long as it contains the structural unit a and the structural unit B and satisfies the above proportional relationship. Preferably, the content of the structural unit A is 83.5 to 96.5 wt% and the content of the structural unit B is 3.5 to 16.5 wt% based on the total weight of the acrylamide copolymer.
Meanwhile, the invention also provides a preparation method of the acrylamide copolymer, which comprises the following steps: polymerizing a monomer mixture in water under the condition of solution polymerization of olefin in the presence of an initiator, wherein the monomer mixture contains a monomer C with a structure shown in a formula III and a monomer D with a structure shown in a formula IV, and the weight ratio of the monomer C to the monomer D is 1: (0.02-0.65),
Figure BDA0001122849430000051
in the formula III, R1' is any of H and C1-C4 alkyl; in the formula IV, R2′、R3' are each independently selected from H and any one of C1 to C12 alkyl groups; r4' is any one selected from the group consisting of an alkyl group of H, C1 to C12, and an alkyl group of C6 to C12. The alkyl of C1-C4, the alkyl of C1-C12 and the aryl of C6-C12 are the same as those described above, and are not repeated herein.
According to the preparation method of the present invention, the object of the present invention can be achieved to some extent by the acrylamide copolymer prepared by copolymerizing the monomer C and the monomer D in the above-mentioned ratio. Preferably, the weight ratio of the monomer C, the monomer E and the monomer D is 1: (0.036-0.2).
According to the production method of the present invention, it is preferable that the polymerization reaction is a random copolymerization reaction.
According to the preparation method of the present invention, wherein the monomer C having the structure represented by formula iii is an acrylamide-based monomer, examples that can be used include, but are not limited to, one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide; preferably, the monomer C is acrylamide or methacrylamide.
According to the preparation method of the invention, the monomer D with the structure shown in the formula IV can be simply called alpha-methylene-gamma-lactone, and R in the formula IV is preferably selected2' is H, R3' is selected from any one of H and C1-C6 alkyl, R4' is selected from any one of H and C1 to C6 alkyl. By selecting a specific monomer D for the reaction, the thickening effect of the resulting polymer can be further improved.
According to the production process of the present invention, the solution polymerization reaction is carried out in water, and the ratio of the weight of the monomer mixture to the total weight of water and the monomer mixture at the start of the solution polymerization reaction of the olefin is not particularly limited and may be varied within a wide range as long as the monomer mixture can be dissolved in water to facilitate the solution polymerization reaction. The amount of the monomer C added is preferably 80 to 450 parts by weight, more preferably 100 to 260 parts by weight, based on 1000 parts by weight of water. According to the conversion of the weight ratio of the monomer C to the monomer D, 10 to 50 parts by weight, preferably 10 to 20 parts by weight of the monomer D is added while the monomer C is added in an amount of 1000 parts by weight.
According to the preparation method of the present invention, there is no particular requirement for the selection of the initiator as long as it can promote the solution polymerization of the olefin of the monomer C and the monomer D, and examples thereof may include, but are not limited to, azo-based initiators or redox initiators; the conditions of the solution polymerization reaction of the olefin are not particularly required, and the corresponding reaction conditions can be reasonably adjusted according to the applicable conditions of the selected initiator.
Preferably, the initiator is an azo initiator, and the solution polymerization conditions of the olefin include: inert atmosphere, temperature is 40-70 ℃, preferably 45-50 ℃; the time is 2-10 h, preferably 4-6 h; the pH value is 6 to 8, preferably 6.5 to 7.5.
Preferably, the azo initiator is used in an amount of 0.0002 to 0.05%, preferably 0.0018 to 0.018% by weight of the total monomer mixture; examples of the azo-based initiator include, but are not limited to, at least one of 2,2' -azobisisobutyronitrile, 2' -azobisisobutylamidine dihydrochloride, azobisisoheptonitrile, 2' -azobis (2-methylpropionamidine) hydrochloride, 2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride, and 4,4' -azobis (4-cyanovaleric acid).
Preferably, the initiator is a redox initiator, and the solution polymerization conditions of the olefin include: inert atmosphere, temperature of 15-30 ℃, preferably 15-20 ℃; the time is 5-10 h, preferably 6-7 h; the pH value is 6 to 8, preferably 6.5 to 7.5.
Preferably, the total amount of the redox initiator is 0.0002 to 0.05 percent, preferably 0.0018 to 0.018 percent of the total weight of the monomer mixture; the redox initiator comprises an oxidant and a reductant, and the weight ratio of the oxidant to the reductant is (0.1-1): 1; wherein examples of the oxidizing agent include, but are not limited to, at least one of benzoyl peroxide, hydrogen peroxide, t-butyl hydroperoxide, 2, 5-dimethyl-2, 5 bis (hydroperoxy) hexane, ammonium persulfate, sodium persulfate, and potassium persulfate; the inorganic reducing agent is selected from at least one of ferrous sulfate, ferrous ammonium sulfate, cuprous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium bisulfite; examples of the organic reducing agent include, but are not limited to, at least one of N, N-dimethylethanolamine, N-dimethylpiperazine, tetramethylurea, N-dimethylethylenediamine, and N, N' -tetramethylethylenediamine; examples of the oxidizing agent include, but are not limited to, ammonium persulfate or potassium persulfate, and the oxidizing agent is sodium sulfite or sodium bisulfite.
Preferably, the pH in the solution polymerization conditions of the olefin is adjusted by adding a base and/or an acid, the base may be an inorganic base or an organic amine compound, such as at least one compound selected from the group consisting of sodium hydroxide, potassium hydroxide, aqueous ammonia, methylamine, ethylamine, ethanolamine and triethanolamine, and is preferably sodium hydroxide. The acid is preferably an inorganic acid, and the inorganic acid may be at least one of hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid, and phosphoric acid.
Preferably, the inert atmosphere (also referred to as protective atmosphere) refers to an atmosphere in the presence of an inert gas (protective gas), wherein the inert gas (protective gas) is a gas that does not react with the raw materials and the products, 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 preparation method of the present invention, the inert atmosphere in the solution polymerization reaction conditions of the olefin is optionally realized 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 20-40 min.
According to the preparation method, the acrylamide copolymer obtained after polymerization reaction is granulated, dried, crushed and screened. Wherein the drying step is not particularly required, and conventional methods known in the art can be adopted, for example, the drying method can be a hot air drying method, and the hot air drying temperature can be 40-120 ℃, preferably 70-90 ℃; the time is 0.2 to 4 hours, preferably 0.5 to 2 hours. The steps of granulation, pulverization and screening are not particularly required, and conventional methods known in the art can be adopted, and are not described in detail herein.
Meanwhile, the invention also provides an acrylamide copolymer prepared by the preparation method. The acrylamide copolymer has the same content of structural units as the acrylamide copolymer described above in the present invention, and will not be described herein again.
In addition, the invention also provides an application of the acrylamide copolymer as a thermal thickener. By adopting the acrylamide copolymer provided by the invention as a thickening agent, the effects of stable structure at low temperature (lower than 80 ℃), good water solubility and easy migration and movement in stratum, and obvious thickening at high temperature (higher than 80 ℃), reduction of water/oil flow ratio and improvement of oil recovery ratio can be obtained, and the acrylamide copolymer is suitable for tertiary oil recovery of high-temperature high-salinity oil reservoirs, and the specific application method can be carried out according to the prior art.
Examples
The following examples are intended to illustrate 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.
In the following examples, the performance test of the product was carried out using the following method:
1. viscosity average molecular weight: according to formula Mv＝([η]/K)1\αCalculation was carried out where K ═ 4.5 × 10-3α is 0.80, intrinsic viscosity [. eta. ]]The determination is carried out according to the determination method of the intrinsic viscosity of the polyacrylamide in GB 12005.1-1989;
2. polymer dissolution time: the measurement was carried out according to the method specified in the Petroleum administration for victory enterprises Standard Q/SH 10201572-2006.
The raw materials used in the following examples are illustrated below:
acrylamide: commercially available from bamo biochemical industries, ltd;
2,2' -azobis (2-methylpropionamidine) hydrochloride, 2' -azobisisobutylamidine dihydrochloride, 4' -azobis (4-cyanovaleric acid): commercially available from Aldrich;
ammonium persulfate and sodium bisulfite: commercially available from beijing chemicals.
In the following examples, the structural unit A is a structural unit represented by formula I, and the structural unit B is a structural unit represented by formula II
Figure BDA0001122849430000091
Example 1
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the alpha-methylene-gamma-lactone employed (commercially available from Aladdin reagent, Inc., the same below) is as follows:
Figure BDA0001122849430000101
the preparation method of the acrylamide copolymer comprises the following steps:
adding 180g of Acrylamide (AM), 20g of the alpha-methylene-gamma-lactone and 1000g of deionized water into a beaker at room temperature under stirring; after the raw materials are dissolved, adding sodium hydroxide into the aqueous solution to adjust the pH value of the aqueous solution to 7.5; then introducing nitrogen into the aqueous solution to remove oxygen for 30min, and sealing the beaker to form inert atmosphere; then 0.01g of ammonium persulfate and 0.01g of sodium bisulfite were added to the aqueous solution as a redox initiation system, followed by reaction at constant temperature of 15 ℃ under normal pressure (controlled by chilled brine) for 7 hours to obtain a gel-like polymer solution product. The gel was taken out, granulated into copolymer crumb of 4 to 6 mm by a granulator, dried at 80 ℃ for 1 hour, and then pulverized and sieved to obtain an acrylamide copolymer product P1 of 20 to 80 mesh. The viscosity-average molecular weight of the acrylamide copolymer product P1 was found to be 1700X 104Dissolution time 80 min.
The acrylamide copolymer product P1 contains 90 wt% of structural unit A (wherein R is1Is H) and 10% by weight of structural units B (where R is2、R3And R4Are all H).
Example 2
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The alpha-methylene-gamma-lactonate employed: the same as in example 1.
The preparation method of the acrylamide copolymer comprises the following steps:
stirring bar at room temperature166g of Acrylamide (AM), 34g of the above α -methylene- γ -lactone, and 1000g of deionized water were added to a beaker; after the raw materials are dissolved, adding sodium hydroxide into the aqueous solution to adjust the pH of the aqueous solution to 6.5; then introducing nitrogen into the aqueous solution to remove oxygen for 30min, and sealing the beaker to form inert atmosphere; then 0.02g of initiator 2,2' -azobis (2-methyl propionamidine) hydrochloride (AIBA) was added to the aqueous solution, followed by reaction at 50 ℃ for 4 hours under normal pressure (temperature controlled by water bath) to obtain a gel-like polymer solution product. The gel was taken out, granulated into copolymer crumb of 4 to 6 mm by a granulator, dried at 80 ℃ for 1 hour, and then pulverized and sieved to obtain an acrylamide copolymer product P2 of 20 to 80 mesh. The viscosity-average molecular weight of this acrylamide copolymer product P2 was found to be 1620X 104Dissolution time 82 min.
The acrylamide copolymer product P2 contains 83 wt% of structural unit A (wherein R is a structural unit of a structural unit A) based on the total weight of the acrylamide copolymer product, determined by calculation according to the charging amount1Is H) and 17% by weight of structural units B (where R is2、R3And R4Are all H).
Example 3
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The alpha-methylene-gamma-lactonate employed: the same as in example 1.
The preparation method of the acrylamide copolymer comprises the following steps:
192g of Acrylamide (AM), 8g of the above-mentioned α -methylene- γ -lactone and 1000g of deionized water were added to a beaker at room temperature with stirring; after the raw materials are dissolved, adding sodium hydroxide into the aqueous solution to adjust the pH value of the aqueous solution to 7; then introducing nitrogen into the aqueous solution to remove oxygen for 30min, and sealing the beaker to form inert atmosphere; 0.015g of initiator 2,2' -azobisisobutylamidine dihydrochloride is added into the aqueous solution and reacted at a constant temperature of 45 ℃ under normal pressure (temperature controlled by a water bath) for 6 hours to obtain a gummy polymer solution product. The gel was taken out, granulated into copolymer crumb of 4 to 6 mm by a granulator, dried at 80 ℃ for 1 hour, and then pulverized and sieved to obtain an acrylamide copolymer product P3 of 20 to 80 mesh. The acrylamide copolymer product was measuredThe product P3 had a viscosity-average molecular weight of 1720X 104Dissolution time 78 min.
The acrylamide copolymer product P3 contains 96 wt% of structural unit A (wherein R is1Is H) and 4% by weight of structural units B (where R is2、R3、R4Are all H).
Example 4
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The alpha-methylene-gamma-lactonate employed: the same as in example 1.
The preparation method of the acrylamide copolymer comprises the following steps:
124g of Acrylamide (AM) and 76g of the above α -methylene- γ -lactone and 1000g of deionized water were added to a beaker at room temperature with stirring; after the raw materials are dissolved, adding sodium hydroxide into the aqueous solution to adjust the pH value of the aqueous solution to 7; then introducing nitrogen into the aqueous solution to remove oxygen for 30min, and sealing the beaker to form inert atmosphere; then 0.05g of initiator 2,2' -azobis (2-methyl propionamidine) hydrochloride (AIBA) was added to the aqueous solution, followed by reaction at a constant temperature of 60 ℃ under normal pressure (temperature controlled by a water bath) for 6 hours to obtain a gel-like polymer solution product. The gel was taken out, granulated into copolymer crumb of 4 to 6 mm by a granulator, dried at 80 ℃ for 1 hour, and then pulverized and sieved to obtain an acrylamide copolymer product P4 of 20 to 80 mesh. The viscosity-average molecular weight of this acrylamide copolymer product P4 was measured to be 1250X 104Dissolution time 95 min.
The acrylamide copolymer product P4 contains 62 wt% of structural unit A (wherein R is1Is H) and 38% by weight of structural units B (where R is2、R3、R4Are all H).
Example 5
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The alpha-methylene-gamma-lactonate employed: the same as in example 1.
Process for the preparation of acrylamide copolymersComprises the following steps: the same process as in example 1 was used, with the difference that: the dosage of Acrylamide (AM) is 196g, and the dosage of alpha-methylene-gamma-lactone is 4 g; the polymerization reaction is carried out for 6 hours under normal pressure and normal temperature to prepare the acrylamide copolymer product P5. The viscosity-average molecular weight of the acrylamide copolymer product P5 was found to be 1700X 104Dissolution time 76 min.
The acrylamide copolymer product P5 contains 98 wt.% of structural units A (wherein R is the same as R) based on the total weight of the product1Is H) and 4% by weight of structural units B (where R is2、R3And R4Are all H).
Example 6
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the adopted alpha-methylene-gamma-lactone is as follows:
Figure BDA0001122849430000131
the preparation method of the acrylamide copolymer comprises the following steps: the same process conditions as in example 1 were used, with the difference that: the same amount of α -methylene- γ -lactone having the structure described above was used in place of the α -methylene- γ -lactone having the structure of example 1 to give acrylamide copolymer product P6. The viscosity-average molecular weight of the acrylamide copolymer product P6 was found to be 1680X 104Dissolution time 84 min.
The acrylamide copolymer product P6 contains 90 wt% of structural unit A (wherein R is1Is H) and 10% by weight of structural units B (where R is2And R4Is H, R3Is methyl).
Example 7
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the adopted alpha-methylene-gamma-lactone is as follows:
Figure BDA0001122849430000132
the preparation method of the acrylamide copolymer comprises the following steps:
170g of Acrylamide (AM) and 30g of the above α -methylene- γ -lactone and 1000g of deionized water were added to a beaker at room temperature with stirring; after the raw materials are dissolved, introducing nitrogen into the aqueous solution to remove oxygen for 30min, and sealing the beaker to form inert atmosphere; then adding sodium hydroxide into the aqueous solution to adjust the pH value of the aqueous solution to 7; then, 0.015g of initiator 2,2' -azobis (2-methyl propionamidine) hydrochloride (AIBA) was added to the aqueous solution, followed by reaction at 50 ℃ for 5 hours under normal pressure (temperature controlled by water bath) to obtain a gel-like polymer solution product. The gel was taken out, granulated into copolymer crumb of 4 to 6 mm by a granulator, dried at 80 ℃ for 1 hour, and then pulverized and sieved to obtain an acrylamide copolymer product P7 of 20 to 80 mesh. The viscosity average molecular weight of the acrylamide copolymer product P7 was found to be 1600X 104Dissolution time 85 min.
The acrylamide copolymer product P7 contains 85 wt.% of structural units A (wherein R is the same as R) based on the total weight of the product1Is H) and 15% by weight of structural units B (where R is2And R3Are all H, R4Is propyl).
Example 8
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the adopted alpha-methylene-gamma-lactone is as follows:
Figure BDA0001122849430000141
the preparation method of the acrylamide copolymer comprises the following steps: the same process conditions as in example 1 were used, with the difference that: the same amount of α -methylene- γ -lactone having the structure described above was used in place of the α -methylene- γ -lactone having the structure of example 1 to give acrylamide copolymer product P8. The viscosity-average molecular weight of the acrylamide copolymer product P8 was found to be 1350X 104Time of dissolution87min。
The acrylamide copolymer product P8 contains 90 wt% of structural unit A (wherein R is1Is H) and 10% by weight of structural units B (where R is2Is methyl, R3Is ethyl, R4Is H).
Example 9
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the adopted alpha-methylene-gamma-lactone is as follows:
Figure BDA0001122849430000151
the preparation method of the acrylamide copolymer comprises the following steps: referring to the preparation method of the acrylamide copolymer in example 1, except for using the same amount of α -methylene- γ -lactone having the aforementioned structure instead of the α -methylene- γ -lactone having the structure in example 1, an acrylamide copolymer product P9 was obtained. The viscosity-average molecular weight of the acrylamide copolymer product P9 was found to be 1200X 104Dissolution time 90 min.
The acrylamide copolymer product P9 contains 90 wt% of structural unit A (wherein R is1Is H) and 10% by weight of structural units B (where R is2And R3Is H, R4Is a phenylethyl group).
Comparative example 1 (refer to the disclosure of Chinese patent CN 200810095791.5)
In a reaction vessel, solvents of dichloromethane 120ml, monomethoxy polyoxyethylene (MPEG2000)0.01mol, cyclohexyl carbodiimide (DCCI)0.012mol, 4-Dimethylaminopyridine (DMAP)0.04mol and methacrylic acid 0.012mol were added, stirring was continued, the stirring rate was controlled at 300rpm, reaction was carried out at room temperature for 12 hours, then the mixture was filtered, and the filtrate was purified 5 times with diethyl ether to obtain a water-soluble macromonomer (B2000).
In a reaction vessel, a monomer (A) (nonionic water-soluble acrylamide) and a monomer (B2000) were added, and the mixture was diluted with redistilled waterTo the desired concentration, the total amount of monomers was 6 wt%. Stirring until each monomer is dissolved, controlling the temperature of the solution at 45 ℃, and enabling the solution to be transparent after the monomers are completely dissolved. Stirring, introducing high-purity nitrogen for 45min, adding water-soluble free radical initiator in the amount of 0.06% (molar ratio) of the monomer, introducing nitrogen for 20 hr to obtain transparent colloidal polymer product, taking out the colloid, granulating with a granulator to obtain copolymer particles of 4-6 mm size, drying at 80 deg.C for 1 hr, pulverizing, and sieving to obtain 20-80 mesh acrylamide copolymer product DP 1. The viscosity average molecular weight of the product DP1 was found to be 860X 104Dissolution time 100 min.
And (3) testing:
the acrylamide copolymer products P1 to P9 and DP1 prepared in the foregoing examples 1 to 9 and comparative example 1 were used as thermal thickeners, and the apparent viscosities of the respective thermal thickeners at different temperatures were measured.
The test method comprises the following steps: firstly, preparing simulated mineral water with the total mineralization degree of 19334mg/L (wherein the total concentration of calcium ions and magnesium ions is 514mg/L) according to a method of enterprise standard Q/SH10201572-2006 of the Shengli Petroleum administration; then, using the simulated mineral water as a solvent, preparing a polymer (acrylamide copolymer products P1-P9 or DP1) solution with the concentration of 3000mg/L, and stirring for 24 hours at room temperature; finally, the apparent viscosities of the polymer solutions at different temperatures were measured using a rotational viscometer of the model DV-III ULTRA, available from Bohler fly (Brookfield) USA, with a constant shear rate of 25s-1The measuring temperature interval is 30-90 ℃, and the heating rate is 2 ℃/min.
And (3) measuring results: as shown in table 1.
Table 1.
Figure BDA0001122849430000171
As can be seen from the data in Table 1, the viscosity of the aqueous solution of the acrylamide copolymer product provided by the invention increases with the temperature, the viscosity remains unchanged at a lower temperature, and the internal alicyclic ring is opened at a temperature higher than 80 ℃, so that the hydration radius and the crosslinking point are increased, and the viscosity is rapidly increased. Therefore, the acrylamide copolymer product provided by the invention has obvious high-temperature thermal thickening property, belongs to a typical thermal thickening polymer, and is particularly suitable for the field of reservoir development with the formation temperature higher than 80 ℃.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail 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 (22)

1. The application of the acrylamide copolymer as the thermal thickener is characterized in that the acrylamide copolymer contains a structural unit A and a structural unit B, wherein the structural unit A is a structural unit shown as a formula I, and the structural unit B is a structural unit shown as a formula II; based on the total weight of the acrylamide copolymer, the content of the structural unit A is 60-98 wt%, and the content of the structural unit B is 2-40 wt%;
Figure FDA0002395018130000011
in the formula I, R1Is any one of H and C1-C4 alkyl;
in the formula II, R2、R3Each independently selected from H and any one of C1-C12 alkyl; r4Any one selected from the group consisting of H, C1-C12 alkyl groups and C6-C12 aryl groups.
2. The use according to claim 1, wherein the amount of the structural unit A is 83.5 to 96.5 wt% and the amount of the structural unit B is 3.5 to 16.5 wt%, based on the total weight of the acrylamide copolymer.
3. Use according to claim 1, wherein R1Is H or methyl.
4. Use according to claim 1, wherein R2Is H, R3Selected from H and any one of C1-C6 alkyl, R4Selected from any one of H and C1-C6 alkyl.
5. Use according to claim 1, wherein the process for preparing the acrylamide copolymer comprises the following steps: polymerizing a monomer mixture in water under the condition of solution polymerization of olefin in the presence of an initiator, wherein the monomer mixture contains a monomer C with a structure shown in a formula III and a monomer D with a structure shown in a formula IV, and the weight ratio of the monomer C to the monomer D is 1: (0.02-0.65),
Figure FDA0002395018130000021
in the formula III, R1' is any of H and C1-C4 alkyl;
in the formula IV, R2′、R3' are each independently selected from H and any one of C1 to C12 alkyl groups; r4' is any one selected from the group consisting of an alkyl group of H, C1 to C12, and an aryl group of C6 to C12.
6. Use according to claim 5, wherein the weight ratio between said monomer C and said monomer D is 1: (0.036-0.2).
7. Use according to claim 5, wherein the monomer C is acrylamide and/or methacrylamide.
8. Use according to claim 5, wherein the monomer C is acrylamide or methacrylamide.
9. According to the rightThe use according to claim 5, wherein R in the monomer D having the structure of formula IV2' is H, R3' is selected from any one of H and C1-C6 alkyl, R4' is selected from any one of H and C1 to C6 alkyl.
10. The use according to claim 5, wherein the monomer C is added in an amount of 150 to 245 parts by weight based on 1000 parts by weight of water in the preparation process.
11. The use according to claim 10, wherein the monomer C is added in an amount of 187.5 to 225 parts by weight based on 1000 parts by weight of water in the preparation process.
12. Use according to claim 5, wherein the initiator is an azo-based initiator and the solution polymerization conditions of the olefin comprise: inert atmosphere at 40-70 deg.c; the time is 2-10 h; the pH value is 6-8.
13. Use according to claim 12, wherein the solution polymerization conditions of the olefins comprise: inert atmosphere at 45-50 deg.c; the time is 4-6 h; the pH value is 6.5-7.5.
14. The use according to claim 12, wherein the azo initiator is used in an amount of 0.0002 to 0.05% by weight based on the total weight of the monomer mixture.
15. The use according to claim 12, wherein the azo initiator is used in an amount of 0.0018 to 0.018% by weight based on the total weight of the monomer mixture.
16. The use according to claim 12, wherein the azo-based initiator is selected from at least one of 2,2' -azobisisobutyronitrile, 2' -azobisisobutylamidine dihydrochloride, azobisisoheptonitrile, 2' -azobis (2-methylpropionamidine) hydrochloride, 2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride and 4,4' -azobis (4-cyanovaleric acid).
17. Use according to claim 5, wherein the initiator is a redox initiator and the solution polymerization conditions of the olefin comprise: inert atmosphere at 15-30 deg.c; the time is 5-10 h; the pH value is 6-8.
18. Use according to claim 17, wherein the solution polymerization conditions of the olefins comprise: inert atmosphere at 15-20 deg.c; the time is 6-7 h; the pH value is 6.5-7.5.
19. The use according to claim 17, wherein the redox initiator is used in a total amount of 0.0002 to 0.05% by weight of the total weight of the monomer mixture, the redox initiator comprises an oxidizing agent and a reducing agent, and the weight ratio of the oxidizing agent to the reducing agent is (0.1 to 1): 1.
20. the use according to claim 19, wherein the redox initiator is used in a total amount of 0.0018 to 0.018 wt% based on the total weight of the monomer mixture.
21. The use of claim 19, wherein the oxidizing agent is selected from at least one of benzoyl peroxide, hydrogen peroxide, t-butyl hydroperoxide, 2, 5-dimethyl-2, 5 bis (hydroperoxy) hexane, ammonium persulfate, sodium persulfate, and potassium persulfate; the inorganic reducing agent is selected from at least one of ferrous sulfate, ferrous ammonium sulfate, cuprous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium bisulfite; the organic reducing agent is at least one selected from N, N-dimethylethanolamine, N, N-dimethylpiperazine, tetramethylurea, N, N-dimethylethylenediamine and N, N, N ', N' -tetramethylethylenediamine.
22. The use of claim 21, wherein the oxidizing agent is ammonium persulfate or potassium persulfate and the oxidizing agent is sodium sulfite or sodium bisulfite.
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