CN107868176B - Acrylamide copolymer and preparation method and application thereof - Google Patents

Acrylamide copolymer and preparation method and application thereof Download PDF

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Publication number
CN107868176B
CN107868176B CN201610862734.XA CN201610862734A CN107868176B CN 107868176 B CN107868176 B CN 107868176B CN 201610862734 A CN201610862734 A CN 201610862734A CN 107868176 B CN107868176 B CN 107868176B
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structural unit
monomer
acrylamide copolymer
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weight
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CN107868176A (en
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张文龙
伊卓
祝纶宇
刘希
杜超
方昭
胡晓娜
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—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

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, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit shown in a formula I, the structural unit B is a structural unit shown in a formula II, and the structural unit C is a structural unit shown in a formula III; and based on the total weight of the acrylamide copolymer, the content of the structural unit A is 43.5-98 wt%, the content of the structural unit B is 0.6-39 wt%, and the content of the structural unit C is 0.6-39 wt%. The acrylamide copolymer has good water solubility and thermal thickening effect, 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, a structural unit B and a structural unit C, wherein the structural unit a is a structural unit represented by formula i, the structural unit B is a structural unit represented by formula ii, and the structural unit C is a structural unit represented by formula iii; based on the total weight of the acrylamide copolymer, the content of the structural unit A is 43.5-98 wt%, the content of the structural unit B is 0.6-39 wt%, and the content of the structural unit C is 0.6-39 wt%;
Figure BDA0001122700780000021
in the formula I, R1Is any one of H and C1-C4 alkyl; in the formula III, 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: carrying out polymerization reaction on a monomer mixture in water in the presence of an initiator under the condition of solution polymerization reaction of olefin, wherein the monomer mixture contains a monomer D with a structure shown in a formula IV, a monomer E with a structure shown in a formula V and a monomer F with a structure shown in a formula VI, and the weight ratio of the monomer D to the monomer E to the monomer F is 1: (0.01-0.65): (0.01 to 0.65),
Figure BDA0001122700780000031
in the formula IV, R1' is any of H and C1-C4 alkyl; in formula VI, 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 and the structural unit C shown in the formula III are introduced simultaneously, so that the acrylamide copolymer has better water solubility and low-temperature stability, and meanwhile, because the introduced structural unit C has a furan structure, the acrylamide copolymer can generate ring-opening hydrolysis reaction at the formation temperature (80-90 ℃), so as to generate new hydroxyl and carboxyl, and the generation of the new hydroxyl and carboxyl improves the hydration radius of the acrylamide copolymer on one hand, and further improves the viscosity of an aqueous solution of the acrylamide copolymer; 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 more than 48mPa.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 a high-temperature high-salt oil reservoir.
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 C, wherein the structural unit A is a structural unit shown in a formula I, the structural unit B is a structural unit shown in a formula II, and the structural unit C is a structural unit shown in a formula III; based on the total weight of the acrylamide copolymer, the content of the structural unit A is 43.5-98 wt%, the content of the structural unit B is 0.6-39 wt%, and the content of the structural unit C is 0.6-39 wt%;
Figure BDA0001122700780000051
in the formula I, R1Is any one of H (hydrogen) and C1-C4 alkyl; in the formula III, R2、R3Each independently selected from H (hydrogen) and any one of C1-C12 alkyl; r4Selected from any one of H (hydrogen), C1-C12 alkyl and C6-C12 aryl.
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, in the structural unit C represented by the formula III, R2Is 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, the structural unit B and the structural unit C and satisfies the above proportional relationship. Preferably, the content of the structural unit A is 65 to 90 wt%, the content of the structural unit B is 4.5 to 20 wt%, and the content of the structural unit C is 4.5 to 20 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: carrying out polymerization reaction on a monomer mixture in water in the presence of an initiator under the condition of solution polymerization reaction of olefin, wherein the monomer mixture contains a monomer D with a structure shown in a formula IV, a monomer E with a structure shown in a formula V and a monomer F with a structure shown in a formula VI, and the weight ratio of the monomer D to the monomer E to the monomer F is 1: (0.01-0.65): (0.01 to 0.65),
Figure BDA0001122700780000061
in the formula IV, R1' is any of H and C1-C4 alkylOne kind of the material is selected; in formula VI, 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 D, the monomer E and the monomer F in the above-mentioned ratio relationship. Preferably, the weight ratio of the monomer D, the monomer E and the monomer F is 1: (0.05-0.27): (0.05-0.27).
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 D having the structure shown in formula iv 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 D is acrylamide or methacrylamide.
According to the preparation method, the monomer E with the structure shown in the formula V is 2-hydroxyethyl methacrylate phosphate, the addition of the monomer E in the polymerization reaction is favorable for increasing the water solubility of the prepared acrylamide copolymer, and the synergistic addition of the monomer E and the monomer F in proportion to the acrylamide copolymer is favorable for comprehensively optimizing the water solubility and the high-temperature thickening effect of the acrylamide copolymer.
According to the preparation method of the invention, the monomer F with the structure shown in the formula VI can be abbreviated as α -methylene-gamma-lactone, and R in the formula VI is preferable2' 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 F for the reaction, the increase in the polymer obtained can be further improvedHas thick effect.
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 D added is preferably 150 to 245 parts by weight, more preferably 187.5 to 225 parts by weight, based on 1000 parts by weight of water. According to the conversion of the weight ratio of the monomer D, the monomer E and the monomer F, the monomer E is added in an amount of 2.5-97.5 parts by weight, preferably 12.5-50 parts by weight, and the monomer F is added in an amount of 2.5-97.5 parts by weight, preferably 12.5-50 parts by weight while the monomer D 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 in the monomer D, the monomer E, and the monomer F, and examples thereof 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 0.03%, preferably 0.0015 to 0.01% by weight of the total weight of the 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 0.03 percent of the total weight of the monomer mixture, and preferably 0.0015 to 0.01 percent; 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 ═ 0.80, intrinsic viscosity [ η ]]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-hydroxyethyl methacrylate phosphate: commercially available from japan chemicals;
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 shown in formula I, the structural unit B is a structural unit shown in formula II, the structural unit C is a structural unit shown in formula III,
Figure BDA0001122700780000111
example 1
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the α -methylene-gamma-lactone employed (commercially available from Aladdin reagent, Inc., below) is as follows:
Figure BDA0001122700780000112
the preparation method of the acrylamide copolymer comprises the following steps:
adding 200g of Acrylamide (AM), 25g of 2-hydroxyethyl methacrylate phosphate, 25g of the α -methylene-gamma-lactone and 1000g of deionized water into a beaker at room temperature under stirring, adding sodium hydroxide into the aqueous solution to adjust the pH of the aqueous solution to 7.5 after the raw materials are dissolved, introducing nitrogen into the aqueous solution to remove oxygen for 30min, sealing the beaker to form an inert atmosphere, adding 0.01g of ammonium persulfate and 0.01g of sodium bisulfite into the aqueous solution as redox initiation systems, reacting for 7 hours at constant temperature of 15 ℃ under normal pressure by using frozen brine to obtain a colloidal polymer solution product, granulating the colloidal polymer solution product into copolymer colloidal particles with the size of 4-6 mm, drying for 1 hour at the temperature of 80 ℃, crushing and screening to obtain a 20-80-mesh acrylamide copolymer product P1, and measuring the viscosity average molecular weight of the acrylamide copolymer product P1 to be 1850 x 104Dissolution time 70 min.
The acrylamide copolymer product P1 contains 80 wt% of structural unit A (wherein R is1H), 10% by weight of structural units B and 10% by weight of structural units C (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 procedure of example 1 was repeated to obtain α -methylene-. gamma.lactone compound.
The preparation method of the acrylamide copolymer comprises the following steps:
225g of Acrylamide (AM), 50g of 2-hydroxyethyl methacrylate phosphate and 12.5g of the α -methylene-. gamma. -lactone mentioned above and 1000g of deionized water were added to a beaker at room temperature with stirring, after the raw materials had dissolved, sodium hydroxide was added to the aqueous solution to adjust the pH of the aqueous solution to 6.5, then nitrogen was passed through the aqueous solution to remove oxygen for 30min and the beaker was sealed to form an inert atmosphere, then 0.02g of 2,2' -azobis (2-methylpropionamidine) hydrochloride (AIBA) as an initiator was added to the aqueous solution,then reacting for 4 hours under normal pressure and at the constant temperature of 50 ℃ (temperature controlled by water bath) to obtain a colloidal polymer solution product. The gel-like polymer solution product was pelletized by a pelletizer into copolymer pellets of 4 to 6 mm, dried at 80 ℃ for 1 hour, and then sieved by pulverization to obtain an acrylamide copolymer product P2 of 20 to 80 mesh. The viscosity-average molecular weight of the acrylamide copolymer product P2 was found to be 1700X 104Dissolution time 68 min.
The acrylamide copolymer product P2 contains 78.3 wt.% of structural unit A (wherein R is the same as R) based on the total weight of the product, as determined by calculation of the charge1H), 17.4% by weight of structural unit B and 4.3% by weight of structural unit C (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 procedure of example 1 was repeated to obtain α -methylene-. gamma.lactone compound.
The preparation method of the acrylamide copolymer comprises the following steps:
adding 167.5g of Acrylamide (AM), 40g of 2-hydroxyethyl methacrylate phosphate, 50g of the α -methylene-gamma-lactone and 1000g of deionized water into a beaker under stirring at room temperature, adding sodium hydroxide into the aqueous solution to adjust the pH value of the aqueous solution to 7 after the raw materials are dissolved, introducing nitrogen into the aqueous solution to remove oxygen for 30min, sealing the beaker to form an inert atmosphere, adding 0.01g of initiator 2,2' -azobisisobutyramidine dihydrochloride into the aqueous solution, reacting for 5 hours at constant temperature of normal pressure and 45 ℃ in a water bath to obtain a colloidal polymer solution product, granulating the colloidal polymer solution product into 4-6 mm colloidal particle copolymers by a granulator, drying for 1 hour at 80 ℃, crushing and screening to obtain 20-80-mesh acrylamide copolymer product P3, and measuring the viscosity average molecular weight of the acrylamide copolymer product P3 to be 1600 multiplied by 104Dissolution time 78 min.
The acrylamide copolymer product P3 contains 65.1 wt.% of structural unit A (wherein R is determined by calculation based on the total weight of the product1H), 15.5% by weight of structural unit B and 19.4% by weight of structural unit C (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 procedure of example 1 was repeated to obtain α -methylene-. gamma.lactone compound.
The preparation method of the acrylamide copolymer comprises the steps of adopting the same process conditions as example 1, except that the using amount of the Acrylamide (AM) is 225g, the using amount of the 2-hydroxyethyl methacrylate phosphate is 12.5g, and the using amount of the α -methylene-gamma-lactone is 12.5g, so as to prepare an acrylamide copolymer product P4, wherein the viscosity average molecular weight of the acrylamide copolymer product P4 is 1740 x 104Dissolution time 65 min.
The acrylamide copolymer product P4 contains 90 wt% of structural unit A (wherein R is1Is H), 5% by weight of structural units B and 5% by weight of structural units C (where R is2、R3And R4Are all H).
Example 5
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The procedure of example 1 was repeated to obtain α -methylene-. gamma.lactone compound.
The preparation method of the acrylamide copolymer comprises the following steps:
adding 160g of Acrylamide (AM), 20g of 2-hydroxyethyl methacrylate phosphate, 90g of the α -methylene-gamma-lactone and 1000g of deionized water into a beaker at room temperature under stirring, adding sodium hydroxide into the aqueous solution to adjust the pH value of the aqueous solution to 7 after the raw materials are dissolved, introducing nitrogen into the aqueous solution to remove oxygen for 30min, sealing the beaker to form an inert atmosphere, adding 0.05g of initiator 2,2' -azobis (2-methyl propionamidine) hydrochloride (AIBA) into the aqueous solution, and reacting for 6 hours at the constant temperature of 60 ℃ under normal pressure in a water bath at a controlled temperature to obtain a colloidal polymer solution product4-6 mm size copolymer gel particles, dried at 80 ℃ for 1 hour, and then sieved by pulverizing to obtain 20-80 mesh acrylamide copolymer product P5. The viscosity-average molecular weight of this acrylamide copolymer product P5 was measured to be 1250X 104Dissolution time 80 min.
The acrylamide copolymer product P5 contains 59.3 wt.% of structural unit A (wherein R is determined by calculation based on the total weight of the product1H), 7.4% by weight of structural unit B and 33.3% by weight of structural unit C (where R is2、R3、R4Are all H).
Example 6
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The procedure of example 1 was repeated to obtain α -methylene-. gamma.lactone compound.
The preparation method of the acrylamide copolymer comprises the steps of adopting the same process method as that of the example 1, and is characterized in that the dosage of the Acrylamide (AM) is 245g, the dosage of the 2-hydroxyethyl methacrylate phosphate is 3.5g, the dosage of the α -methylene-gamma-lactone is 1.5g, the polymerization reaction condition is that the reaction is carried out for 6 hours at normal pressure and normal temperature to prepare an acrylamide copolymer product P6, and the viscosity average molecular weight of the acrylamide copolymer product P6 is 1760 multiplied by 104Dissolution time 62 min.
The acrylamide copolymer product P6 contains 98 wt.% of structural units A (wherein R is the same as R) based on the total weight of the product1H), 1.4% by weight of structural unit B and 0.6% by weight of structural unit C (where R is2、R3And R4Are all H).
Example 7
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the α -methylene-gamma-lactone employed is as follows:
Figure BDA0001122700780000151
process for producing acrylamide copolymerComprises using the same process conditions as in example 1 except that α -methylene- γ -lactone having the structure in example 1 was replaced with the same amount of α -methylene- γ -lactone having the structure described previously to give an acrylamide copolymer product P7. the viscosity-average molecular weight of this acrylamide copolymer product P7 was found to be 1680X 104Dissolution time 72 min.
The acrylamide copolymer product P7 contains 80 wt% of structural unit A (wherein R is1H), 10% by weight of structural units B and 10% by weight of structural units C (where R is2And R4Is H, R3Is methyl).
Example 8
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the α -methylene-gamma-lactone employed is as follows:
Figure BDA0001122700780000161
the preparation method of the acrylamide copolymer comprises the following steps:
adding 187.5g of Acrylamide (AM), 12.5g of 2-hydroxyethyl methacrylate phosphate, 50g of the α -methylene-gamma-lactone and 1000g of deionized water into a beaker under stirring at room temperature, adding sodium hydroxide into the aqueous solution to adjust the pH of the aqueous solution to 7 after the raw materials are dissolved, introducing nitrogen into the aqueous solution to remove oxygen for 30min, sealing the beaker to form an inert atmosphere, adding 0.015g of 2,2' -azobis (2-methyl propionamidine) hydrochloride (AIBA) into the aqueous solution, reacting for 5 hours at normal pressure and a constant temperature of 50 ℃ in a water bath to obtain a colloidal polymer solution product, granulating the colloidal polymer solution product into copolymer colloidal particles with the average molecular weight of 4-6 mm by a granulator, drying for 1 hour at the temperature of 80 ℃, crushing and screening to obtain the acrylamide copolymer product P8 with the molecular weight of 20-80 meshes, and measuring the viscosity average molecular weight of the acrylamide copolymer product P8 to be 1520 multiplied by 104Dissolution time 74 min.
According to the material chargeThe acrylamide copolymer product P8 contains 75 wt.% of structural units A (wherein R is as defined in the specification) based on the total weight of the product1Is H), 5% by weight of structural unit B and 20% by weight of structural unit C (where R is2And R3Are all H, R4Is propyl).
Example 9
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the α -methylene-gamma-lactone employed is as follows:
Figure BDA0001122700780000162
the process for preparing an acrylamide copolymer, which comprises using the same process conditions as in example 1 except that the α -methylene- γ -lactone having the structure in example 1 was replaced with the same amount of α -methylene- γ -lactone having the structure described previously to give an acrylamide copolymer product P9. the viscosity-average molecular weight of this acrylamide copolymer product P9 was found to be 1350X 104Dissolution time 80 min.
The acrylamide copolymer product P9 contains 80 wt% of structural unit A (wherein R is1H), 10% by weight of structural units B and 10% by weight of structural units C (where R is2Is methyl, R3Is ethyl, R4Is H).
Example 10
For illustrating the acrylamide copolymer and the preparation method thereof according to the present invention.
The structure of the α -methylene-gamma-lactone employed is as follows:
Figure BDA0001122700780000171
the preparation method of the acrylamide copolymer includes the preparation method of the acrylamide copolymer of reference example 1 except that α -methylene-gamma-lactonate having the aforementioned structure is used in the same amount instead of having the real structureα -methylene- γ -lactone of the structure in example 1, to give an acrylamide copolymer product P10 the viscosity average molecular weight of this acrylamide copolymer product P10 was found to be 1200X 104Dissolution time 90 min.
The acrylamide copolymer product P10 contains 80 wt% of structural unit A (wherein R is1H), 10% by weight of structural units B and 10% of structural units C (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 the reaction vessel, monomer (A) (nonionic water-soluble acrylamide) and monomer (B2000) were charged, and diluted with redistilled water to a desired concentration, the total amount of the monomers being 6% by weight. 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 P10 and DP1 prepared in the foregoing examples 1 to 10 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: first, according to victoryPreparing simulated mineral water with the total mineralization degree of 19334mg/L (wherein the total concentration of calcium ions and magnesium ions is 514mg/L) by using a method of petroleum administration enterprise standard Q/SH 10201572-2006; then, using the simulated mineral water as a solvent, preparing a polymer (acrylamide copolymer products P1-P10 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 BDA0001122700780000191
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 (27)

1. An acrylamide copolymer, which is characterized by comprising a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit shown as a formula I, the structural unit B is a structural unit shown as a formula II, and the structural unit C is a structural unit shown as a formula III; based on the total weight of the acrylamide copolymer, the content of the structural unit A is 43.5-98 wt%, the content of the structural unit B is 0.6-39 wt%, and the content of the structural unit C is 0.6-39 wt%;
Figure FDA0002258148310000011
in the formula I, R1Is any one of H and C1-C4 alkyl;
in the formula III, R2Is any one of H and methyl; r3Any one selected from H and C1-C6 alkyl; r4Any one selected from the group consisting of H, C1-C6 alkyl groups and C6-C12 aryl groups.
2. The acrylamide copolymer according to claim 1, wherein the content of the structural unit A is 65 to 90 wt%, the content of the structural unit B is 4.3 to 20 wt%, and the content of the structural unit C is 4.3 to 20 wt%, based on the total weight of the acrylamide copolymer.
3. The acrylamide copolymer according to claim 1, wherein R1Is H or methyl.
4. The acrylamide copolymer according to claim 1, wherein R2Is H, R4Selected from any one of H and C1-C6 alkyl.
5. A method for preparing an acrylamide copolymer, comprising the steps of: carrying out polymerization reaction on a monomer mixture in water in the presence of an initiator under the condition of solution polymerization reaction of olefin, wherein the monomer mixture contains a monomer D with a structure shown in a formula IV, a monomer E with a structure shown in a formula V and a monomer F with a structure shown in a formula VI, and the weight ratio of the monomer D to the monomer E to the monomer F is 1: (0.01-0.65): (0.01 to 0.65),
Figure FDA0002258148310000021
in the formula IV, R1' is any of H and C1-C4 alkyl;
in formula VI, R2' is any one of H and methyl; r3' any one selected from H and C1-C6 alkyl; r4' is any one selected from the group consisting of an alkyl group of H, C1 to C6, and an aryl group of C6 to C12.
6. The method of claim 5, wherein the weight ratio of monomer D, monomer E, and monomer F is 1: (0.05-0.27): (0.05-0.27).
7. The method of claim 5, wherein the monomer D is acrylamide or methacrylamide.
8. The method of claim 5 wherein R is in monomer F having the structure of formula VI2' is H, R4' is selected from any one of H and C1 to C6 alkyl.
9. The method according to claim 5, wherein the monomer D is added in an amount of 150 to 245 parts by weight based on 1000 parts by weight of water in the preparation method.
10. The method according to claim 9, wherein the monomer D is added in an amount of 187.5 to 225 parts by weight based on 1000 parts by weight of water in the preparation method.
11. The method according to claim 5, wherein the initiator is an azo-based initiator, and the solution polymerization conditions of the olefin comprise: the temperature of the inert atmosphere is 40-70 ℃, the time is 2-10 h, and the pH value is 6-8.
12. The process of claim 11, wherein the temperature of the solution polymerization of the olefin is from 45 ℃ to 50 ℃.
13. The method according to claim 11, wherein the time for the solution polymerization of the olefin is 4 to 6 hours.
14. The method according to claim 11, wherein the solution polymerization of the olefin has a pH of 6.5 to 7.5.
15. The method of claim 11, wherein the azo initiator is used in an amount of 0.0002 to 0.03% by weight based on the total weight of the monomer mixture.
16. The method of claim 15, wherein the azo initiator is used in an amount of 0.0015 to 0.01% by weight based on the total weight of the monomer mixture.
17. The process according to claim 11, wherein the azo-based initiator is at least one selected from the group consisting 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).
18. The method of claim 5, wherein the initiator is a redox-based initiator, and the solution polymerization conditions of the olefin comprise: the temperature of the inert atmosphere is 15-30 ℃, the time is 5-10 h, and the pH value is 6-8.
19. The process of claim 18, wherein the temperature of the solution polymerization of the olefin is from 15 ℃ to 20 ℃.
20. The method according to claim 18, wherein the time for the solution polymerization of the olefin is 6 to 7 hours.
21. The method according to claim 18, wherein the solution polymerization of the olefin has a pH of 6.5 to 7.5.
22. The method of claim 18, wherein the redox initiator is used in a total amount of 0.0002 to 0.03% by weight of the total 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.
23. the method of claim 22, wherein the redox initiator is used in a total amount of 0.0015 to 0.01% by weight based on the total weight of the monomer mixture.
24. The method of claim 22, 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 reducing agent is at least one selected from ferrous sulfate, ferrous ammonium sulfate, cuprous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite, sodium bisulfite, N, N-dimethylethanolamine, N, N-dimethylpiperazine, tetramethylurea, N, N-dimethylethylenediamine and N, N, N ', N' -tetramethylethylenediamine.
25. The method of claim 22, wherein the oxidizing agent is ammonium persulfate or potassium persulfate and the reducing agent is sodium sulfite or sodium bisulfite.
26. An acrylamide copolymer produced by the method of any one of claims 5 to 25.
27. Use of an acrylamide copolymer as defined in any one of claims 1 to 4 and 26 as a thermal thickener.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1414057A (en) * 2001-10-26 2003-04-30 中国石油天然气股份有限公司 Comb shaped antisalt polymer thickening agent
CN101302267A (en) * 2007-05-11 2008-11-12 中国科学院成都有机化学有限公司 Non-ionic thermal tackifying water-soluble polymers
CN102031101A (en) * 2009-09-25 2011-04-27 中国石油化工股份有限公司 Heat-resistant and salt-resistant polymer thickening agent and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1414057A (en) * 2001-10-26 2003-04-30 中国石油天然气股份有限公司 Comb shaped antisalt polymer thickening agent
CN101302267A (en) * 2007-05-11 2008-11-12 中国科学院成都有机化学有限公司 Non-ionic thermal tackifying water-soluble polymers
CN102031101A (en) * 2009-09-25 2011-04-27 中国石油化工股份有限公司 Heat-resistant and salt-resistant polymer thickening agent and preparation method thereof

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