CN116731266B - Graphene oxide nanosheets and preparation method thereof - Google Patents
Graphene oxide nanosheets and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 86
- 239000002135 nanosheet Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006073 displacement reaction Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims abstract description 4
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 89
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 47
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 26
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 26
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 18
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 239000003350 kerosene Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002064 nanoplatelet Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000012530 fluid Substances 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 238000011084 recovery Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 230000005661 hydrophobic surface Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000005983 Crescentia cujete Nutrition 0.000 description 2
- 235000009797 Lagenaria vulgaris Nutrition 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- -1 salt ions Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 240000009087 Crescentia cujete Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 244000174681 Michelia champaca Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical group [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of nano-sheet material preparation, and particularly discloses a graphene oxide nano-sheet and a preparation method thereof. The graphene oxide nano sheet provided by the invention comprises a graphene oxide sheet, wherein one surface of the graphene oxide sheet is grafted with CB [ n ], and the other surface of the graphene oxide sheet is grafted with a styrene-methyl methacrylate copolymer. The graphene oxide nano-sheet provided by the invention has good temperature resistance and salt resistance, can be aggregated on an oil-water interface to form an interfacial film with viscoelasticity when being used as a displacement agent, has good interfacial film stability, and can obviously improve the oil displacement efficiency of nano-fluid under low concentration.
Description
Technical Field
The invention relates to the technical field of nano-sheet material preparation, in particular to a graphene oxide nano-sheet and a preparation method thereof.
Background
With the rapid development of economy, the demand of human beings for petroleum energy is becoming more and more evident. At present, it is increasingly difficult to develop a large number of new oil and gas fields, and thus, it is highly desirable to maximize the recovery of petroleum based on existing oil and gas fields. After the secondary oil recovery stage, tertiary oil recovery technology is important for further extracting residual crude oil in the low-permeability oil reservoir, but the problems of degradation, adsorption and the like of the conventional chemical displacement agent in the forward migration process limit the use of the chemical displacement agent. Accordingly, there is an urgent need to provide new displacement agent materials for enhanced oil recovery.
The two sides of the Janus material have hydrophilicity and hydrophobicity respectively, i.e. have different characteristics at the interface of the same material. In various Janus materials, the two-dimensional (2D) Janus nano sheet has special wettability due to the high anisotropic shape and asymmetric chemical property, and the amphiphilic Janus nano fluid can be gathered on an oil-water interface to form a viscoelastic interface film, so that intelligent and efficient oil finding is realized, the oil displacement performance is remarkably improved, and the consumption of an oil displacement agent is reduced. However, the collision between nanofluids and salt ions in the geological environment of high temperature and high salt of the Janus material used at present makes the nanofluids and the salt ions more likely to aggregate and precipitate, so that the oil displacement performance is reduced or even destroyed.
In view of the above, the present invention aims to provide a new two-dimensional (2D) Janus nanoplatelet material, namely a graphene oxide nanoplatelet material, to obtain a displacement agent that is stable under high temperature and high salt environments.
Disclosure of Invention
The invention mainly solves the technical problem of providing a graphene oxide nano sheet and a preparation method of the graphene oxide nano sheet, and the graphene oxide nano sheet provided by the invention can be applied to the tertiary oil recovery field and used as a displacement agent.
In order to solve the technical problems described above, in a first aspect, the present invention provides a graphene oxide nanosheet, including a graphene oxide sheet, one surface of the graphene oxide sheet is grafted with CB [ n ], and the other surface of the graphene oxide sheet is grafted with a styrene-methyl methacrylate copolymer, where the structure of the graphene oxide nanosheet includes: PS-co-PMMA/GO/CB [ n ].
As an embodiment of the present invention, wherein CB [ n ] is CB [6] or CB [7].
In a second aspect, the present invention provides a method for preparing graphene oxide nanoplatelets, comprising the steps of:
(1) Dispersing graphene oxide sheets in NaCl aqueous solution to prepare a dispersion liquid 1;
dissolving azodiisobutyronitrile, methyl methacrylate and styrene in kerosene to prepare a solution 2;
dissolving ceric ammonium nitrate in water to prepare a solution 3;
dissolving CB [ n ] acrylamide in water to prepare solution 4;
(2) Under the protection of nitrogen, firstly adding the solution 2 into the dispersion liquid 1, then adding the solution 3, stirring, then adding the solution 4, then reacting for 10-15 hours at 35-45 ℃, then heating to 70-90 ℃ for continuous reaction for 5-10 hours, collecting solid powder after the reaction is finished, and washing the obtained solid powder to obtain the graphene oxide nanosheets.
As one embodiment of the invention, the content of graphene oxide sheets in the dispersion liquid 1 is 0.8-1.2g/L, and the concentration of NaCl in the NaCl aqueous solution is 10-15 g/L.
As one embodiment of the present invention, in the solution 2, the concentration of azobisisobutyronitrile is 0.015 to 0.030mol/L, the concentration of methyl methacrylate is 1.2 to 2.0mol/L, and the concentration of styrene is 0.2 to 0.7mol/L.
As an embodiment of the present invention, in the solution 2, the molar ratio of the methyl methacrylate and the styrene is (2-9): 1.
as one embodiment of the invention, the concentration of the ceric ammonium nitrate in the solution 3 is 30-35g/L.
As one embodiment of the present invention, the concentration of CB [ n ] acrylamide in said solution 4 is from 6 to 18g/L.
As one embodiment of the present invention, the CB [ n ] acrylamide is CB [6] acrylamide or CB [7] acrylamide.
As one embodiment of the present invention, the dispersion 1, the solution 2, the solution 3, the solution 4 are in a volume ratio (3-4): (1-1.5): (1-1.2): (1-1.2) carrying out a mixing reaction.
As a preferred embodiment of the present invention, the concentration of azobisisobutyronitrile in the solution 2 is 0.018 to 0.025mol/L.
As one embodiment of the present invention, the dispersion 1, the solution 2, the solution 3, the solution 4 are in a volume ratio (3-4): (1-1.2): (1-1.1): 1, carrying out a mixing reaction.
In a third aspect, the present invention provides an application of the graphene oxide nanosheets, or an application of the graphene oxide nanosheets prepared by the preparation method of the present invention as oil recovery displacement agents, and further preferably as tertiary oil recovery displacement agents.
In a fourth aspect, the invention also provides an oil extraction displacement agent, which comprises polyvinylpyrrolidone, poly (2-acrylamide-2-methylpropanesulfonic acid) and the graphene oxide nano-sheets, wherein the graphene oxide nano-sheets, the polyvinylpyrrolidone and the poly (2-acrylamide-2-methylpropanesulfonic acid) are mixed according to a mass ratio of 10:1:1.
The graphene oxide nano sheet is a Janus Graphene Oxide (GO) nano sheet, is prepared by in-situ free radical polymerization, and is prepared by performing asymmetric functionalization on the surface of the graphene oxide sheet (GO) by using hydrophobic polymer polystyrene-co-polymethyl methacrylate and cucurbituril [ n ] urea (CB [ n ]) in Pickering emulsion environment, so as to obtain the graphene oxide nano sheet with one side grafted with CB [ n ] and the other side grafted with styrene-methyl methacrylate copolymer, namely polystyrene-co-polymethyl methacrylate/graphene oxide/cucurbituril Janus nano sheet (PS-co-PMMA/GO/CB [ n ]).
In the preparation process of the graphene oxide nanosheets, in-situ radical copolymerization is carried out on methyl methacrylate and styrene monomer dissolved in an oil phase through azodiisobutyronitrile initiation in the oil phase, and a hydrophobic monomer is grafted on one side of graphene oxide; in the aqueous phase, by Ce 4+ Is initiated by acrylamide CB [ n ]]Polymerization of monomers, CB [ n ]]Grafted on the other side of the graphene oxide. Prepared PS-co-PMMA/GO/CB [ n ]]The Janus nano sheet has the advantages that as styrene and methyl methacrylate are added into the oil phase simultaneously, the hydrophobic surface of the graphene oxide has two chain segment structures simultaneously, so that the property of the hydrophobic side can be regulated and controlled; the other side of the graphene oxide is introduced with CB [ n ]]Calabash [ n ]]Urea (CB [ n ]]) Is a macrocyclic compound of rigid structure having a hydrophobic cavity, each having n terminal carbonyl groups at each end, thus CB [ n ]]Not only can hold molecules or ions with proper dimensions, but also can form complexes with charged metal ions, charged parts of organic molecules or molecules with larger polarity through ion-dipole, hydrogen bond and other interactions, due to CB [ n ]]The supermolecular action of (C) to make rigid calabash [ n ]]The urea is grafted on the surface of the nano material, so that the affinity of the material surface and the material can be effectively changedThe wettability of the surface can improve the curling of the nano fluid under the conditions of high temperature and high salt, and the temperature resistance and the salt resistance of the polymer are improved. The graphene oxide nano-sheet prepared by the method not only has good temperature resistance and salt resistance, but also is CB [ n ] on the surface]The cavity has the interaction capability of a host and a guest, is favorable for regulating and controlling the interface performance through simple supermolecule modification, and has a superior effect in the tertiary oil recovery field.
The graphene oxide nanosheets (PS-co-PMMA/GO/CB [ n ] Janus nanosheets) provided by the invention have good temperature resistance and salt resistance; when the nano-fluid oil displacement agent is used as a displacement agent, the nano-fluid oil displacement agent can be gathered on an oil-water interface to form an interface membrane with viscoelasticity, the interface membrane has good stability, and the oil displacement efficiency of the nano-fluid can be remarkably improved under low concentration. The graphene oxide nanosheets (PS-co-PMMA/GO/CB [ n ] Janus nanosheets) provided by the invention are used as tertiary oil recovery displacement agents, can effectively reduce oil-water interfacial tension and change rock wettability under low concentration, obviously improve the oil displacement efficiency of nanofluid, and also reduce economic cost, so that the graphene oxide nanosheets have wide application prospects.
The graphene oxide nanosheets provided by the invention are prepared by adopting the copolymerization grafting of the in-situ polystyrene and the polymethyl methacrylate, so that the proportion of the polystyrene to the polymethyl methacrylate chain segment can be conveniently regulated and controlled, and the controllable synthesis of the graphene oxide hydrophobic surface is realized; the preparation method is simple to operate, high in modification efficiency and capable of performing large-scale synthesis in a liquid phase.
Drawings
FIG. 1 is a nuclear magnetic spectrum of CB [6] acrylamide provided by the invention;
FIG. 2 is a nuclear magnetic spectrum of CB [7] acrylamide provided by the invention;
FIG. 3 is an infrared spectrum of CB [6] -C1, CB [6] -S2, CB [6] -S3, CB [6] -S4 provided by the invention;
FIG. 4 is an infrared spectrum of CB [6] -S4, CB [6] -S5, CB [6] -S6 provided by the present invention;
FIG. 5 is an infrared spectrum of CB [7] -S7 provided by the present invention;
FIG. 6 is a graph of the hydrophilic side and hydrophobic side contact angles of graphene oxide nanoplatelets CB [6] -S4 provided in example 3 of the present invention;
fig. 7 is a graph of the hydrophilic side and hydrophobic side contact angles of graphene oxide nanoplatelets CB [7] -S7 provided in example 6 of the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific examples.
When the graphene oxide nanosheets are prepared, firstly, the graphene oxide nanosheets (GO) are dispersed in a sodium chloride aqueous solution, and then a kerosene solution in which styrene (St), methyl Methacrylate (MMA) and azodiisobutyronitrile are dissolved is added, so that an oil-water system forms an emulsion with a high inward degree; then adding ammonium ceric nitrate aqueous solution, stirring, then adding CB n acrylamide aqueous solution to form a reaction system; the GO sheets are positioned at the interface of the organic phase and the water phase, hydroxyl groups on the surfaces of the GO sheets of the water phase and ammonium cerium nitrate form an oxidation-reduction initiation system, and CB [ n ] acrylamide monomers can be initiated at a lower temperature, and CB [ n ] is grafted on one surface of the graphene oxide sheets; in the organic phase, at a higher temperature, azodiisobutyronitrile is decomposed, styrene and methyl methacrylate can be initiated to carry out in-situ free radical copolymerization on the other side of GO, and a copolymer of the styrene and the methyl methacrylate is grafted on the other side of graphene oxide, so that the PS-co-PMMA/GO/CB [ n ] Janus nano-sheet with excellent performance is finally obtained.
Wherein, graphene oxide sheets (GO), styrene (St), methyl Methacrylate (MMA), azodiisobutyronitrile and ceric ammonium nitrate are all obtained by purchase.
CB [ n ] acrylamide is obtained by the preparation process as follows.
1. Preparation of CB [6] acrylamide
400mg of HO-CB [6] are dissolved in 12mL of methanesulfonic acid, cooled in an ice bath, 6.4 mL of acrylonitrile and 3mL of trifluoromethanesulfonic acid are added, and reacted at 50℃for 5 hours. And (3) after the reaction is finished, acetone is used for precipitation, the obtained solid is washed by acetone for three times, and then the solid is put into a vacuum drying oven for drying for 12 hours, so that CB [6] acrylamide is obtained. The nuclear magnetic spectrum of CB [6] acrylamide is shown in figure 1.
2. Preparation of CB [7] acrylamide
500mg of HO-CB [7] are dissolved in 12mL of methanesulfonic acid, cooled in an ice bath, and 7.0 mL of acrylonitrile and 3mL of trifluoromethanesulfonic acid are added to react at 50℃for 5 hours. And (3) precipitating with acetone after the reaction is finished, cleaning the obtained solid with acetone for three times, and then placing the solid into a vacuum drying oven to be dried for 12 hours to obtain CB 7 acrylamide. The nuclear magnetic spectrum of CB [7] acrylamide is shown in FIG. 2.
In the following examples, the equipment and reagents used, unless otherwise specified, were all commercially available.
Example 1
The embodiment provides a graphene oxide nanosheet, which is prepared by the following steps:
adding 50mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
0.05g of azobisisobutyronitrile, 2.4mL of methyl methacrylate and 1.2mL of styrene (the molar ratio of the methyl methacrylate to the styrene is 2.2:1) are taken and dissolved in 12mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.09g CB 6 acrylamide, dissolving in 15 mL water to prepare solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, electrically stirring, adding the solution 3, stirring for 2 minutes, adding the solution 4, reacting for 12 hours under 40 ℃ electrically stirring, heating to 85 ℃ and continuously reacting for 8 hours, and ending the reaction. Collecting solid powder, washing the solid powder with tetrahydrofuran for 3 times to obtain graphene oxide nano-sheet PS-co-PMMA/GO/CB 6 Janus nano-sheet, which is named as CB 6-S2.
Example 2
The embodiment provides a graphene oxide nanosheet, which is prepared by the following steps:
adding 50mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
0.05g of azobisisobutyronitrile, 2.8mL of methyl methacrylate and 0.8mL of styrene (the molar ratio of the methyl methacrylate to the styrene is 3.8:1) are taken and dissolved in 12mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.09g CB 6 acrylamide, dissolving in 15 mL water to prepare solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, electrically stirring, adding the solution 3, stirring for 2 minutes, adding the solution 4, reacting for 12 hours under 40 ℃ electrically stirring, heating to 85 ℃ and continuously reacting for 8 hours, and ending the reaction. Collecting solid powder, washing the solid powder with tetrahydrofuran for 3 times to obtain graphene oxide nano-sheet PS-co-PMMA/GO/CB 6 Janus nano-sheet, which is named as CB 6-S3.
Example 3
The embodiment provides a graphene oxide nanosheet, which is prepared by the following steps:
adding 50mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
0.05g of azobisisobutyronitrile, 3.1mL of methyl methacrylate and 0.4mL of styrene (the molar ratio of the methyl methacrylate to the styrene is 8.4:1) are taken and dissolved in 12mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.09g CB 6 acrylamide, dissolving in 15 mL water to prepare solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, electrically stirring, adding the solution 3, stirring for 2 minutes, adding the solution 4, reacting for 12 hours under 40 ℃ electrically stirring, heating to 85 ℃ and continuously reacting for 8 hours, and ending the reaction. Collecting solid powder, washing the solid powder with tetrahydrofuran for 3 times to obtain graphene oxide nano-sheet PS-co-PMMA/GO/CB 6 Janus nano-sheet, which is named as CB 6-S4.
Example 4
The embodiment provides a graphene oxide nanosheet, which is different from embodiment 3 in that the concentration of CB [6] acrylamide in solution 4 is 12g/L, and the preparation process is as follows:
adding 50mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
0.05g of azobisisobutyronitrile, 3.1mL of methyl methacrylate and 0.4mL of styrene (the molar ratio of the methyl methacrylate to the styrene is 8.4:1) are taken and dissolved in 12mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.18g CB 6 acrylamide, dissolving in 15 mL water to prepare solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, electrically stirring, adding the solution 3, stirring for 2 minutes, adding the solution 4, reacting for 12 hours under 40 ℃ electrically stirring, heating to 85 ℃ and continuously reacting for 8 hours, and ending the reaction. Collecting solid powder, washing the solid powder with tetrahydrofuran for 3 times to obtain graphene oxide nano-sheet PS-co-PMMA/GO/CB 6 Janus nano-sheet, which is marked as CB 6-S5.
Example 5
The present example provides a graphene oxide nanoplatelet, which differs from example 3 in that the concentration of CB [6] acrylamide in solution 4 is 18g/L, and the preparation process is:
adding 50mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
0.05g of azobisisobutyronitrile, 3.1mL of methyl methacrylate and 0.4mL of styrene (the molar ratio of the methyl methacrylate to the styrene is 8.4:1) are taken and dissolved in 12mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.27g CB [6] acrylamide, dissolving in 15 mL water to prepare solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, electrically stirring, adding the solution 3, stirring for 2 minutes, adding the solution 4, reacting for 12 hours under 40 ℃ electrically stirring, heating to 85 ℃ and continuously reacting for 8 hours, and ending the reaction. Collecting solid powder, washing the solid powder with tetrahydrofuran for 3 times to obtain graphene oxide nano-sheet PS-co-PMMA/GO/CB 6 Janus nano-sheet, which is named as CB 6-S6.
Example 6
The embodiment provides a graphene oxide nano-sheet, which is prepared by CB [7] acrylamide, and the preparation process is as follows:
adding 55mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
0.05g of azobisisobutyronitrile, 3.1mL of methyl methacrylate and 0.4mL of styrene (the molar ratio of the methyl methacrylate to the styrene is 8.4:1) are taken and dissolved in 12mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.21g CB 7 acrylamide, dissolving in 15 mL water to prepare solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, electrically stirring, adding the solution 3, stirring for 2 minutes, adding the solution 4, reacting for 12 hours under 40 ℃ electrically stirring, heating to 85 ℃ and continuously reacting for 8 hours, and ending the reaction. Collecting solid powder, washing the solid powder with tetrahydrofuran for 3 times to obtain graphene oxide nano-sheet PS-co-PMMA/GO/CB 7 Janus nano-sheet, which is marked as CB 7-S7.
Comparative example 1
The comparative example provides a graphene oxide nanosheet, which is prepared by the following steps:
adding 50mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
0.05g of azobisisobutyronitrile and 3.5mL of methyl methacrylate are taken and dissolved in 12mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.09g CB 6 acrylamide, dissolving in 15 mL water to prepare solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, electrically stirring, adding the solution 3, stirring for 2 minutes, adding the solution 4, reacting for 12 hours under 40 ℃ electrically stirring, heating to 85 ℃ and continuously reacting for 8 hours, and ending the reaction. Collecting solid powder, washing the solid powder with tetrahydrofuran for 3 times to obtain graphene oxide nano-sheet PMMA/GO/CB 6 Janus nano-sheet, which is marked as CB 6-C1.
Comparative example 2
The comparative example provides a graphene oxide nanosheet, which is prepared by the following steps:
adding 50mg of graphene oxide sheets (GO) and 0.6g of NaCl into 50mL of deionized water, and performing ultrasonic treatment on the mixture for 1 h to obtain a dispersion liquid 1;
dissolving 0.3g of n-octylamine in 12.5mL of kerosene solution to prepare solution 2;
weighing 0.5g of ceric ammonium nitrate, and dissolving in 15 mL water to prepare a solution 3;
weighing 0.003g of 2-acrylamide-2-methylpropanesulfonic acid, dissolving in 15 mL water, and preparing 0.2 g/L of 2-acrylamide-2-methylpropanesulfonic acid aqueous solution to obtain solution 4;
under the protection of nitrogen, adding the solution 2 into the prepared dispersion liquid 1, stirring electrically, and reacting at 40 ℃ for 18 hours to obtain n-octylamine single-sided grafted graphene oxide; then adding the solution 3, stirring for 2 minutes, adding the solution 4, and then carrying out reaction for 12 hours at 40 ℃ under electric stirring, wherein the reaction is finished. The solid powder was collected and washed 3 times with tetrahydrofuran to give n-octylamine/GO/poly 2-acrylamido-2-methylpropanesulfonic acid (OtcA/GO/PAMPS) Janus nanoplatelets, designated PAMPS-C2.
The synthesized nanosheets of the present invention were characterized using FT-IR. The infrared spectra of CB [6] -C1, CB [6] -S2, CB [6] -S3, and CB [6] -S4 are shown in FIG. 3. Wherein a represents CB [6] -S2, b represents CB [6] -S3, C represents CB [6] -S4, and d represents CB [6] -C1.
CB[6]-S4、CB[6]-S5、CB[6]The IR spectrum of S6 is shown in FIG. 4, wherein a represents CB [6]]S4, b represents CB [6]]S5, c represents CB [6]]-S6. As can be seen from FIG. 4With CB [6]]Increased content, 1736 cm -1 CB [6] of the department]The carbonyl absorption peak intensity of (2) increases.
CB[7]The infrared spectrum of S7 is shown in FIG. 5, and 1713 and cm are shown in the infrared spectrum 5 -1 At CB [7]]Carbonyl absorbance peak of 1207 cm) -1 Is the characteristic absorption peak of GO.
Test example 1
Contact angle test: dispersing the Janus nano sheet prepared by the method on a water-kerosene interface, respectively obtaining a film on a hydrophilic surface and a film on a hydrophobic surface of the Janus nano sheet by a vertical pulling method and a horizontal attaching method after the kerosene volatilizes, and carrying out characterization test by using a contact angle measuring instrument.
Wherein, the hydrophilic side and hydrophobic side contact angle diagrams of the graphene oxide nanoplatelets CB [6] -S4 obtained in example 3 are shown in FIG. 6, the hydrophilic side and hydrophobic side contact angle diagrams of the graphene oxide nanoplatelets CB [7] -S7 obtained in example 6 are shown in FIG. 7, and in FIG. 6 and FIG. 7, a represents the hydrophilic side and b represents the hydrophobic side.
As can be seen from the graph, the contact angles of the Janus nano sheets prepared by the invention on the hydrophilic surfaces are all smaller than 5 degrees, and the contact angles of the Janus nano sheets on the hydrophobic surfaces are all larger than 90 degrees. This shows that the Janus nano-sheet prepared by the method is an amphiphilic Janus nano-sheet structure.
Test example 2
The Janus nano sheet prepared by the invention has the advantages of high temperature resistance, high salt resistance and the following experimental process.
(1) Simulated salty mineralized water was prepared with the composition shown in table 1:
TABLE 1 mineralized water inorganic salt ion composition
(2) Adding the Janus nano sheet solid powder prepared in the embodiment of the invention or the nano sheet solid powder prepared in the comparative example and polyvinylpyrrolidone and poly (2-acrylamide-2-methylpropanesulfonic acid) into simulated salt-containing mineralized water, wherein the mass ratio of the nano sheet solid powder to the polyvinylpyrrolidone to the poly (2-acrylamide-2-methylpropanesulfonic acid) is 10:1:1, the weight average molecular weight of the polyvinylpyrrolidone is 78000g/mol, and the weight average molecular weight of the poly (2-acrylamide-2-methylpropanesulfonic acid) is 67000g/mol;
magnetically stirring for 3h, and performing ultrasonic treatment for 15min to prepare a dispersion liquid with Janus nano sheets with the concentration of 100 g/L; the nanofluid transmittance was then measured by spectrophotometry after heating at 80 ℃ for 24 h. If the transmittance is increased, the nano particles are settled, and the dispersion performance is poor. After that, the sample was left at 80℃for 72 hours, and the transmittance was measured again.
The transmittance test results of the Janus nanoplatelets prepared in each example of the present invention and comparative example are shown in table 2. As can be seen from the data in Table 2, janus nanosheets prepared in each example of the present invention have good dispersion stability in mineralized water, and after 72 hours, the transmittance only increases slightly, indicating that the sedimentation of the dispersion is slower; the comparative example, however, showed a significant increase in transmittance after 72 hours of standing, indicating significant sedimentation and poor dispersion stability.
TABLE 2
As shown by the experiment, compared with the comparative example, the Janus nano sheet prepared by the embodiment of the invention has better temperature resistance and salt resistance, has good dispersion stability in a high-temperature and high-salt environment, and is not easy to cause aggregation and precipitation.
Test example 3
The displacement performance of the Janus nano sheet prepared by the invention is evaluated, and the experimental process is as follows.
Core displacement performance evaluation: adopting a cylindrical artificial rock core (diameter 2.5cm, length 10.0cm, permeability 400 mD) to carry out an oil displacement experiment;
experimental oil: crude oil at 80℃having a viscosity of 6.3 mPas and a density of 0.87g/cm 3 ;
Nanofluids for experiments: adding Janus nano-sheet solid powder prepared by the embodiment of the invention or nano-sheet solid powder prepared by the comparative example and polyvinylpyrrolidone and poly (2-acrylamide-2-methylpropanesulfonic acid) into simulated salt-containing mineralized water, wherein the mass ratio of the Janus nano-sheet solid powder to the polyvinylpyrrolidone to the poly (2-acrylamide-2-methylpropanesulfonic acid) is 10:1:1, the weight average molecular weight of the polyvinylpyrrolidone is 78000g/mol, and the weight average molecular weight of the poly (2-acrylamide-2-methylpropanesulfonic acid) is 67000g/mol;
magnetically stirring for 3h, and performing ultrasonic treatment for 15min to prepare a dispersion liquid with Janus nano sheets concentration of 100g/L for later use;
experimental water: table 1 shows simulated salinized water;
the specific experimental steps are as follows:
(1) Drying the core at 100 ℃ for 24 hours;
(2) Sequentially saturating mineralized water and crude oil at 80 ℃, and then aging the core for 72 hours at 80 ℃;
(3) Firstly, driving water at a flow rate of 0.1mL/min until the water content is more than 98%; then 0.3PV nanofluid is transferred at a flow rate of 0.1 mL/min; finally, water is driven at the flow rate of 0.1mL/min until the water content is more than 98%;
(4) The results of the water flooding recovery ratio and the nano-fluid flooding enhanced recovery ratio are calculated, and the recovery ratio results corresponding to Janus nano-sheets prepared in each example and comparative example of the invention are shown in Table 3.
TABLE 3 Table 3
As can be seen from the data in Table 3, the Janus nanosheets prepared in the examples of the present invention have better displacement effect and high total recovery ratio.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (8)
1. The graphene oxide nanosheets are characterized by comprising graphene oxide sheets, wherein one surface of each graphene oxide sheet is grafted with CB [ n ], the other surface of each graphene oxide sheet is grafted with a styrene-methyl methacrylate copolymer, and the structure of each graphene oxide nanosheet comprises: PS-co-PMMA/GO/CB [ n ]; and the CB [ n ] is CB [6] or CB [7].
2. A method for preparing the graphene oxide nanoplatelets according to claim 1, comprising the steps of:
(1) Dispersing graphene oxide sheets in NaCl aqueous solution to prepare a dispersion liquid 1;
dissolving azodiisobutyronitrile, methyl methacrylate and styrene in kerosene to prepare a solution 2;
dissolving ceric ammonium nitrate in water to prepare a solution 3;
dissolving CB [ n ] acrylamide in water to prepare solution 4; in the solution 4, the concentration of the CB [ n ] acrylamide is 6-18g/L, and the CB [ n ] acrylamide is CB [6] acrylamide or CB [7] acrylamide;
the preparation method of the CB [6] acrylamide comprises the following steps: 400mg HO-CB 6 is dissolved in 12mL methane sulfonic acid, cooled in ice bath, 6.4 mL acrylonitrile and 3mL trifluoro methane sulfonic acid are added, reaction is carried out for 5h at 50 ℃, acetone is used for precipitation after the reaction is finished, the obtained solid is washed three times by acetone, and then the obtained solid is put into a vacuum drying box for drying for 12h, thus obtaining CB 6 acrylamide;
the preparation method of the CB [7] acrylamide comprises the following steps: dissolving 500mg HO-CB 7 in 12mL methane sulfonic acid, cooling in ice bath, adding 7.0 mL acrylonitrile and 3mL trifluoromethane sulfonic acid, reacting at 50deg.C for 5h, precipitating with acetone, washing the obtained solid with acetone for three times, and drying in vacuum drying oven for 12h to obtain CB 7 acrylamide;
(2) Under the protection of nitrogen, firstly adding the solution 2 into the dispersion liquid 1, then adding the solution 3, stirring, then adding the solution 4, then reacting for 10-15 hours at 35-45 ℃, then heating to 70-90 ℃ for continuous reaction for 5-10 hours, collecting solid powder after the reaction is finished, and washing the obtained solid powder to obtain the graphene oxide nanosheets.
3. The preparation method according to claim 2, wherein the content of graphene oxide sheets in the dispersion liquid 1 is 0.8-1.2g/L, and the concentration of NaCl in the NaCl aqueous solution is 10-15 g/L.
4. The method according to claim 2, wherein the concentration of azobisisobutyronitrile in the solution 2 is 0.015 to 0.030mol/L, the concentration of methyl methacrylate is 1.2 to 2.0mol/L, and the concentration of styrene is 0.2 to 0.7mol/L.
5. The method according to claim 4, wherein the molar ratio of the methyl methacrylate to the styrene in the solution 2 is (2-9): 1.
6. the preparation method according to claim 2, wherein the concentration of the ceric ammonium nitrate in the solution 3 is 30-35g/L.
7. The method according to any one of claims 2 to 6, wherein the dispersion 1, the solution 2, the solution 3, the solution 4 are in a volume ratio (3 to 4): (1-1.5): (1-1.2): (1-1.2) carrying out a mixing reaction.
8. An oil extraction displacement agent, which comprises polyvinylpyrrolidone, poly (2-acrylamide-2-methylpropanesulfonic acid) and the graphene oxide nano-sheets according to claim 1, wherein the graphene oxide nano-sheets, the polyvinylpyrrolidone and the poly (2-acrylamide-2-methylpropanesulfonic acid) are mixed in a mass ratio of 10:1:1.
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