CN111363086B - Acrylamide copolymer and preparation method and application thereof - Google Patents
Acrylamide copolymer and preparation method and application thereof Download PDFInfo
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- CN111363086B CN111363086B CN201811603184.5A CN201811603184A CN111363086B CN 111363086 B CN111363086 B CN 111363086B CN 201811603184 A CN201811603184 A CN 201811603184A CN 111363086 B CN111363086 B CN 111363086B
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- 229920006322 acrylamide copolymer Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 19
- 239000000084 colloidal system Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical group CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical group [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims 1
- 230000033558 biomineral tissue development Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000001804 emulsifying effect Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- -1 n-octyl group Chemical group 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 has a structure shown in a formula (1), the structural unit B has a structure shown in a formula (2), the structural unit C has a structure shown in a formula (3), and R is C2‑C12Alkyl groups of (a); and based on the total weight of the acrylamide copolymer, the content of the structural unit A is 85-95 wt%, the content of the structural unit B is 0.5-5 wt%, and the content of the structural unit C is 1-10 wt%. The acrylamide copolymer has higher viscosity under the conditions of high temperature and high mineralization degree, can lower the oil-water surface interfacial tension and has better emulsifying property
Description
Technical Field
The invention relates to the field of oilfield chemicals, and in particular 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, and the viscosity of the aqueous solution is greatly reduced under the conditions of high temperature and high salinity, thereby obviously influencing the oil displacement effect.
In the 90 s, with the continuous rise of water content of oil fields, the requirements of adjusting a water absorption profile at the deep part of an oil reservoir, forcing the liquid flow to turn and improving the water injection development recovery ratio are provided, so that a new hot point of deep profile control technology research is formed, an important role is played in the aspects of oil and water stabilization, and novel chemical agents such as strong gel, weak gel, particle gel and the like are correspondingly developed. However, in the case of the extremely high water content stage, the chemical agents cannot achieve the purpose of deep profile control and flooding due to serious flooding of an oil well, complex oil-water relationship and the like, and can only act in a near-distance zone of the implemented well, so that the field implementation period is short and the effect is poor.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide an acrylamide copolymer, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides an acrylamide copolymer comprising a structural unit a, a structural unit B, and a structural unit C, wherein the structural unit a has a structure represented by formula (1), the structural unit B has a structure represented by formula (2), and the structural unit C has a structure represented by formula (3); based on the total weight of the acrylamide copolymer, the content of the structural unit A is 85-95 wt%, the content of the structural unit B is 0.5-5 wt%, and the content of the structural unit C is 1-10 wt%;
wherein R is C2-C12Alkyl group of (1).
In a second aspect, the present invention provides a method for preparing an acrylamide copolymer, the method comprising:
1) under the condition of solution polymerization and in the presence of an initiator, carrying out polymerization reaction on the monomer mixture in water to obtain copolymer colloid; wherein the monomer mixture contains acrylamide, a monomer X and a monomer Y, the monomer X has a structure shown in a formula (4), and the monomer Y has a structure shown in a formula (5); and based on the total amount of the monomer mixture, the using amount of acrylamide is 85-95 wt%, the using amount of the monomer X is 0.5-5 wt%, and the using amount of the monomer Y is 1-10 wt%;
wherein R is C2-C12Alkyl groups of (a);
2) and carrying out hydrolysis reaction on the copolymer colloid to obtain the acrylamide copolymer.
In a third aspect, the present invention provides the use of the acrylamide copolymer according to the first aspect of the present invention and the acrylamide copolymer obtained by the method according to the second aspect of the present invention in a profile control agent.
According to the invention, the monomer X and the monomer Y are simultaneously introduced into a macromolecular chain of polyacrylamide, so that the prepared polyacrylamide copolymer has higher viscosity under the conditions of high temperature (85 ℃) and high mineralization degree (33000mg/L), can reduce the surface tension of oil and water, and has better emulsifying property.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an acrylamide copolymer, which comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A has a structure shown in a formula (1), the structural unit B has a structure shown in a formula (2), and the structural unit C has a structure shown in a formula (3); based on the total weight of the acrylamide copolymer, the content of the structural unit A is 85-95 wt%, the content of the structural unit B is 0.5-5 wt%, and the content of the structural unit C is 1-10 wt%;
wherein R is C2-C12Alkyl group of (1).
In the present invention, the term "C" is used2-C12The "alkyl group" of (a) represents an alkyl group having 2 to 12 carbon atoms in total, and may be, for example, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, etc.
The inventor of the invention unexpectedly finds that by introducing the monomer X and the monomer Y into the macromolecular structure of polyacrylamide and controlling the content of each structural unit within the range, the obtained acrylamide copolymer has higher viscosity under the conditions of high temperature (85 ℃) and high mineralization degree (33000mg/L), can reduce the surface tension of oil and water, has better emulsification performance, can adapt to the environment with serious flooding of an oil well and complex relation of oil and water, and realizes the purpose of deep profile control.
In order to further increase the viscosity of the acrylamide copolymer and reduce the surface interfacial tension, it is preferable that the content of the structural unit a is 88 to 95 wt%, the content of the structural unit B is 0.5 to 3 wt%, and the content of the structural unit C is 1 to 9 wt%, based on the total weight of the acrylamide copolymer.
Preferably, the viscosity average molecular weight of the acrylamide copolymer is from 2700 to 3200 ten thousand. More preferably, the acrylamide copolymer has a viscosity average molecular weight of 2800 to 3200 ten thousand.
In a second aspect, the present invention provides a method for preparing an acrylamide copolymer, the method comprising:
1) under the condition of solution polymerization and in the presence of an initiator, carrying out polymerization reaction on the monomer mixture in water to obtain copolymer colloid; wherein the monomer mixture contains acrylamide, a monomer X and a monomer Y, the monomer X has a structure shown in a formula (4), and the monomer Y has a structure shown in a formula (5); and based on the total amount of the monomer mixture, the using amount of acrylamide is 85-95 wt%, the using amount of the monomer X is 0.5-5 wt%, and the using amount of the monomer Y is 1-10 wt%;
wherein R is C2-C12Alkyl groups of (a);
2) and carrying out hydrolysis reaction on the copolymer colloid to obtain the acrylamide copolymer.
In the present invention, both the monomer X and the monomer Y are commercially available.
Preferably, the monomer mixture is 20 to 40 parts by weight with respect to 100 parts by weight of water.
Preferably, acrylamide is used in an amount of 88 to 95 wt%, the monomer X is used in an amount of 0.5 to 3 wt%, and the monomer Y is used in an amount of 1 to 9 wt%, based on the total amount of the monomer mixture.
Preferably, the conditions of the solution polymerization reaction include: the solution polymerization reaction is carried out in an inert atmosphere, the initiator is an oxidation-reduction system initiator, the temperature is 20-40 ℃, the time is 8-10h, and the pH value is 6-10. The inert atmosphere may be provided by nitrogen. The pH adjustment can be carried out by means customary in the art, for example by adding alkaline substances such as sodium hydroxide.
More preferably, the solution polymerization conditions further comprise: in the presence of an emulsifier, a complexing agent, urea and an accelerator. The emulsifying agent and the accelerator are added in the solution polymerization reaction process, so that the thickening property and the emulsifying property of the prepared acrylamide copolymer can be further improved.
Preferably, the redox system initiator is 0.015 to 0.15 parts by weight, the emulsifier is 0.05 to 1 part by weight, the complexing agent is 0.01 to 0.1 part by weight, the urea is 0.5 to 5 parts by weight, and the accelerator is 0.2 to 1 part by weight, relative to 100 parts by weight of the monomer mixture.
In the present invention, the oxidation-reduction system initiator is preferably a persulfate oxidizer and a sulfite reducer. The persulfate oxidizer may be, for example, potassium persulfate, ammonium persulfate, or the like. The sulfite may be, for example, potassium bisulfite, sodium bisulfite, or the like. Preferably, the persulfate oxidizer is 0.01 to 0.1 parts by weight per 100 parts by weight of the monomer mixture; the sulfite reducing agent is 0.005-0.05 weight part.
Preferably, the emulsifier is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
Preferably, the complexing agent is disodium ethylenediaminetetraacetate (EDTA-2 Na).
Preferably, the accelerator is pentamethyldiethylenetriamine.
In the present invention, the hydrolysis reaction can be performed under alkaline conditions, which can be achieved by adding sodium hydroxide, granular alkali, etc., and the amount of the alkaline substance added is not particularly limited, and can be adjusted by those skilled in the art according to the needs of the reaction. Preferably, the conditions of the hydrolysis reaction include: the temperature is 80-90 ℃ and the time is 2-3 h.
Preferably, after the hydrolysis reaction, the reaction product is granulated, dried, pulverized, and sieved to obtain the acrylamide copolymer.
According to a preferred embodiment of the present invention:
the method for preparing the acrylamide copolymer comprises the following steps:
a) adding acrylamide into a reactor to prepare an aqueous solution, adjusting the pH value, then adding a monomer X, a monomer Y, an emulsifier, a complex aqueous solution, urea and an accelerant, and fully stirring to obtain a stable micelle solution;
b) adding an initiator, blowing inert gas to uniformly mix, sealing and carrying out solution polymerization reaction to obtain polymer colloid;
c) taking out the colloid, granulating, adding alkaline substances, uniformly mixing, and performing hydrolysis reaction;
d) and granulating, drying, crushing and screening the hydrolysis reaction product to obtain the acrylamide copolymer.
In a third aspect, the present invention provides the use of the acrylamide copolymer according to the first aspect of the present invention and the acrylamide copolymer prepared by the method according to the second aspect of the present invention in a profile control agent.
The acrylamide copolymer provided by the invention has higher viscosity under the conditions of high temperature (85 ℃) and high mineralization degree (33000mg/L), can reduce the oil-water surface interfacial tension, has better emulsifying property, can be applied to a profile control agent, and realizes deep profile control.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
all starting materials were obtained commercially, except where specifically indicated. Wherein the monomer X shown in the formula (4) and the monomer Y shown in the formula (5) (R is ethyl in Y1, R is n-hexyl in Y2, and R is n-dodecyl in Y3) are both purchased from Shanghai Aladdin Biotechnology GmbH.
The viscosity-average molecular weight was measured by a one-point method using a Ubbelohde viscometer.
Example 1
1) Adding 19g of acrylamide into a heat-preservation polymerization reaction bottle, adding 60g of deionized water to dissolve the acrylamide to prepare an aqueous solution, adding sodium hydroxide to adjust the pH value to 7, sequentially adding 0.1g of monomer X0.1g, 0.9g of monomer Y1(R is ethyl), 0.1g of sodium dodecyl sulfate, 1 weight percent of EDTA-2Na aqueous solution 1g, 0.1g of urea and 40mg of pentamethyldiethylenetriamine, and fully stirring the mixture to obtain a stable micelle solution;
2) introducing nitrogen into the solution at 30 ℃ for removing oxygen for 30 minutes, then adding 3g of 0.2 weight percent potassium persulfate aqueous solution and 3g of 0.1 weight percent sodium bisulfite aqueous solution, initiating reaction, continuously introducing nitrogen for five minutes, stopping the reaction, and carrying out polymerization reaction for 10 hours after sealing to obtain polymer colloid;
3) taking out the colloid, adding 0.45g of sodium hydroxide granular alkali after granulation, uniformly mixing, and carrying out hydrolysis reaction for 2 hours at 90 ℃;
4) taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular acrylamide copolymer P1.
The viscosity average molecular weight of P1 is 3200 ten thousand;
the amount of structural unit A was 95% by weight, the amount of structural unit B was 0.5% by weight and the amount of structural unit C (where R is ethyl) was 4.5% by weight, based on the total weight of the acrylamide copolymer P1.
Example 2
1) Adding 18g of acrylamide into a heat-preservation polymerization reaction bottle, adding 60g of deionized water to dissolve the acrylamide to prepare an aqueous solution, adding sodium hydroxide to adjust the pH value to 10, sequentially adding 1g of EDTA-2Na aqueous solution 1g of monomer X0.5g, 1.5g of monomer Y3(R is n-dodecyl), 0.2g of sodium dodecyl sulfate, 1 weight percent of urea, 0.5g of urea and 100mg of pentamethyldiethylenetriamine, and fully stirring the mixture to obtain a stable micelle solution;
2) introducing nitrogen into the solution at 25 ℃ for 30 minutes to drive oxygen, then adding 4g of 0.2 weight percent potassium persulfate aqueous solution and 4g of 0.1 weight percent sodium bisulfite aqueous solution, initiating reaction, continuously introducing nitrogen for five minutes, stopping, and carrying out polymerization reaction for 8 hours after sealing to obtain polymer colloid;
3) taking out the colloid, adding 0.5g of sodium hydroxide granular alkali after granulation, uniformly mixing, and carrying out hydrolysis reaction for 2.5 hours at 85 ℃;
4) taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular acrylamide copolymer P2.
The viscosity average molecular weight of P2 is 2900 ten thousand;
the amount of the structural unit A was 90% by weight, the amount of the structural unit B was 2.5% by weight and the amount of the structural unit C (wherein R is n-dodecyl group) was 7.5% by weight, based on the total weight of the acrylamide copolymer P2.
Example 3
1) Adding 18g of acrylamide into a heat-preservation polymerization reaction bottle, adding 60g of deionized water to dissolve the acrylamide to prepare an aqueous solution, adding sodium hydroxide to adjust the pH value to 7.5, sequentially adding 0.2g of monomer X0.2g, 1.8g of monomer Y1(R is ethyl), 0.1g of sodium dodecyl sulfate, 1g of EDTA-2Na aqueous solution with the weight percent of 1 weight percent, 0.9g of urea and 150mg of pentamethyldiethylenetriamine, and fully stirring the mixture to obtain a stable micelle solution;
2) introducing nitrogen into the solution at 30 ℃ for removing oxygen for 30 minutes, then adding 10g of potassium persulfate aqueous solution with the weight percent of 0.2 and 10g of sodium bisulfite aqueous solution with the weight percent of 0.1 to initiate reaction, continuously introducing nitrogen for five minutes, stopping the reaction, and carrying out polymerization reaction for 9 hours after sealing to obtain polymer colloid;
3) taking out the colloid, adding 0.45g of sodium hydroxide granular alkali after granulation, uniformly mixing, and carrying out hydrolysis reaction for 2 hours at 85 ℃;
4) taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular acrylamide copolymer P3.
The viscosity average molecular weight of P3 is 3000 ten thousand;
the amount of the structural unit A was 90% by weight, the amount of the structural unit B was 1% by weight and the amount of the structural unit C (wherein R is an ethyl group) was 9% by weight, based on the total weight of the acrylamide copolymer P3.
Example 4
1) Adding 17g of acrylamide into a heat-preservation polymerization reaction bottle, adding 60g of deionized water to dissolve the acrylamide to prepare an aqueous solution, adding sodium hydroxide to adjust the pH value to 6, sequentially adding 1g of monomer X1g, 2g of monomer Y2(R is n-hexyl), 0.2g of sodium dodecyl sulfate, 1 weight percent of EDTA-2Na aqueous solution, 1g of urea and 200mg of pentamethyldiethylenetriamine, and fully stirring the mixture to obtain a stable micelle solution;
2) introducing nitrogen into the solution at 20 ℃ for removing oxygen for 30 minutes, then adding 2g of 0.2 weight percent potassium persulfate aqueous solution and 2g of 0.1 weight percent sodium bisulfite aqueous solution, initiating reaction, continuously introducing nitrogen for five minutes, stopping, and carrying out polymerization reaction for 8 hours after sealing to obtain polymer colloid;
3) taking out the colloid, adding 0.4g of sodium hydroxide granular alkali after granulation, uniformly mixing, and carrying out hydrolysis reaction for 3 hours at 80 ℃;
4) taking out the colloidal particles, granulating, drying at 60 ℃ to constant weight, crushing and sieving to obtain the white granular acrylamide copolymer P4.
The viscosity average molecular weight of P4 is 2700 ten thousand;
the acrylamide copolymer P4 was found to contain 85% by weight of structural unit A, 5% by weight of structural unit B and 10% by weight of structural unit C (wherein R is n-hexyl), based on the total weight of the copolymer.
Comparative example 1
The procedure is as in example 1, except that monomer Y1 is replaced by an equal mass of monomer X, giving acrylamide copolymer D1.
Measuring the viscosity average molecular weight of D1 to be 2000 ten thousand;
the amount of the structural unit A was 95% by weight and the structural unit B was 5% by weight, based on the total weight of the acrylamide copolymer D1.
Comparative example 2
The procedure is as in example 1, except that the monomer X is replaced by an equal mass of monomer Y1 to give an acrylamide copolymer D2.
The viscosity average molecular weight of D2 was determined to be 2200 ten thousand;
the amount of the structural unit A was 95% by weight and the structural unit C was 5% by weight, based on the total weight of the acrylamide copolymer D2.
Comparative example 3
The procedure was followed as in example 1, except that 19.6g of acrylamide was used and 0.3g of the monomer Y1 was used, to give an acrylamide copolymer D3.
The viscosity average molecular weight of D3 was determined to be 2200 ten thousand;
the amount of the structural unit A, the structural unit B and the structural unit C was determined by calculation from the charged amounts to be 98% by weight, 0.5% by weight and 1.5% by weight, based on the total weight of the acrylamide copolymer D3.
Comparative example 4
The procedure of example 1 was repeated, except that 16g of acrylamide was used and 2.5g of the monomer X was used, to obtain an acrylamide copolymer D4.
Measuring the viscosity average molecular weight of D4 to be 2000 ten thousand;
the amount of structural unit A was 80% by weight, the amount of structural unit B was 12.5% by weight and the amount of structural unit C was 7.5% by weight, based on the total weight of the acrylamide copolymer D4.
Test example
The acrylamide copolymers obtained in examples and comparative examples were prepared as 0.15 wt% aqueous solutions, respectively, and the apparent viscosity, surface tension and interfacial tension of each aqueous solution were measured, and the test results are shown in table 1.
Wherein the apparent viscosity of the aqueous solution of the acrylamide copolymer is measured by a Brookfield viscometer, the test temperature is 85 ℃, and the mineralization degree is 33000 mg/L;
the surface tension of the acrylamide copolymer aqueous solution under pure water is measured by a DCAT-21 surface tension meter, and the testing temperature is 25 ℃;
the interfacial tension of the aqueous solution of acrylamide copolymer was measured by an interfacial tension meter TX500C, koro, usa, and the test temperature was 80 ℃, and the experimental oil was kerosene.
TABLE 1
| Product numbering | Apparent viscosity (mPa. s) | Surface tension (mN/m) | Interfacial tension (mN/m) |
| P1 | 85.6 | 28.3 | 6×10-2 |
| P2 | 72.5 | 28.4 | 7×10-2 |
| P3 | 77.8 | 28.4 | 8×10-2 |
| P4 | 64.8 | 30.3 | 9×10-2 |
| D1 | 42.1 | 35.2 | 10.6×10-2 |
| D2 | 38.3 | 34.6 | 10.6×10-2 |
| D3 | 46.1 | 35.9 | 11.9×10-2 |
| D4 | 47.9 | 34.6 | 10.1×10-2 |
The results in table 1 show that the acrylamide copolymer provided by the invention has higher apparent viscosity at 85 ℃ and a mineralization degree of 33000mg/L, and shows excellent high-temperature and high-salt resistance; meanwhile, the surface active agent has lower surface tension and interfacial tension and shows excellent surface activity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. An acrylamide copolymer comprising a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A has a structure represented by formula (1), the structural unit B has a structure represented by formula (2), and the structural unit C has a structure represented by formula (3); based on the total weight of the acrylamide copolymer, the content of the structural unit A is 85-95 wt%, the content of the structural unit B is 0.5-5 wt%, and the content of the structural unit C is 1-10 wt%;
wherein R is C2-C12Alkyl group of (1).
2. The acrylamide copolymer according to claim 1, wherein the content of the structural unit a is 88 to 95 wt%, the content of the structural unit B is 0.5 to 3 wt%, and the content of the structural unit C is 1 to 9 wt%, based on the total weight of the acrylamide copolymer.
3. The acrylamide copolymer according to claim 1 or 2, wherein the viscosity average molecular weight of the acrylamide copolymer is from 2700 to 3200 ten thousand.
4. The acrylamide copolymer according to claim 1 or 2, wherein the viscosity average molecular weight of the acrylamide copolymer is 2800 to 3200 ten thousand.
5. A method of preparing an acrylamide copolymer, the method comprising:
1) under the condition of solution polymerization and in the presence of an initiator, carrying out polymerization reaction on the monomer mixture in water to obtain copolymer colloid; wherein the monomer mixture contains acrylamide, a monomer X and a monomer Y, the monomer X has a structure shown in a formula (4), and the monomer Y has a structure shown in a formula (5); and based on the total amount of the monomer mixture, the using amount of acrylamide is 85-95 wt%, the using amount of the monomer X is 0.5-5 wt%, and the using amount of the monomer Y is 1-10 wt%;
wherein R is C2-C12Alkyl groups of (a);
2) and carrying out hydrolysis reaction on the copolymer colloid to obtain the acrylamide copolymer.
6. The method of claim 5, wherein the monomer mixture is 20 to 40 parts by weight with respect to 100 parts by weight of water.
7. The process of claim 5 wherein acrylamide is present in an amount of 88 to 95 wt.%, monomer X is present in an amount of 0.5 to 3 wt.%, and monomer Y is present in an amount of 1 to 9 wt.%, based on the total amount of the monomer mixture.
8. The method of claim 5, wherein the conditions of the solution polymerization reaction comprise: the solution polymerization reaction is carried out in an inert atmosphere, the initiator is an oxidation-reduction system initiator, the temperature is 20-40 ℃, the time is 8-10h, and the pH value is 6-10.
9. The method of claim 8, wherein the solution polymerization conditions further comprise: in the presence of an emulsifier, a complexing agent, urea and an accelerator.
10. The method according to claim 9, wherein the oxidation-reduction system initiator is 0.015 to 0.15 parts by weight, the emulsifier is 0.05 to 1 part by weight, the complexing agent is 0.01 to 0.1 part by weight, the urea is 0.5 to 5 parts by weight, and the accelerator is 0.2 to 1 part by weight, relative to 100 parts by weight of the monomer mixture.
11. The method of claim 10, wherein the oxidation-reduction system initiator is a persulfate oxidizer and a sulfite reducer.
12. The method of claim 10, wherein the emulsifier is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
13. The method of claim 10, wherein the complexing agent is disodium ethylenediaminetetraacetic acid.
14. The method of claim 10, wherein the accelerator is pentamethyldiethylenetriamine.
15. The method of any one of claims 5-14, wherein the conditions of the hydrolysis reaction comprise: the temperature is 80-90 ℃ and the time is 2-3 h.
16. Use of the acrylamide copolymer according to any one of claims 1 to 4 and the acrylamide copolymer prepared by the method according to any one of claims 5 to 15 in a profile control agent.
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| CA3124893A CA3124893C (en) | 2018-12-26 | 2019-12-17 | Acrylamide copolymer and preparation method thereof and use thereof |
| EP19901431.7A EP3882284B1 (en) | 2018-12-26 | 2019-12-17 | Acrylamide copolymer and preparation method therefor and use thereof |
| PCT/CN2019/125897 WO2020135149A1 (en) | 2018-12-26 | 2019-12-17 | Acrylamide copolymer and preparation method therefor and use thereof |
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| CN105566565A (en) * | 2015-12-17 | 2016-05-11 | 中国海洋大学 | Hydrophobic association polymer with double bonds on side chains, method for preparing hydrophobic association polymer and application thereof |
| CN106496411A (en) * | 2016-11-04 | 2017-03-15 | 中国海洋大学 | A kind of purposes of the hydrophobic associated polymer with multiple ring structure side chains and preparation method thereof with it |
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| CN105566565A (en) * | 2015-12-17 | 2016-05-11 | 中国海洋大学 | Hydrophobic association polymer with double bonds on side chains, method for preparing hydrophobic association polymer and application thereof |
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