CN115043999A - Post-hydrolysis preparation method and application of nano zirconia-titanium oxide grafted polyacrylamide - Google Patents
Post-hydrolysis preparation method and application of nano zirconia-titanium oxide grafted polyacrylamide Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 70
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 101
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 98
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 238000006073 displacement reaction Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 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 11
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 11
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 229940047670 sodium acrylate Drugs 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 3
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 63
- 230000000694 effects Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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- 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
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
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Abstract
The invention discloses a post-hydrolysis preparation method and application of nano zirconia/titania grafted polyacrylamide, and relates to the fields of functional polymer, nano material modification and the like; mixing acrylamide and a functional monomer according to a certain proportion, cooling, introducing nitrogen, sequentially adding a complexing agent, a chain transfer agent, an initiator, a vinyl modified nano-zirconia/titania precursor solution and the like for sealing reaction, hydrolyzing a rubber block, and finally drying and crushing to obtain a sample. The polyacrylamide prepared by the method is a micro-crosslinked structure containing nano zirconium oxide and nano titanium oxide, improves the high temperature resistance, salt resistance and shear resistance of the polyacrylamide, and has certain tackiness, so that the polyacrylamide becomes a novel oil displacement agent for high-salt high-temperature strata of oil fields.
Description
Technical Field
The invention belongs to the field of functional polymer and nano material modification, and particularly relates to a post-hydrolysis preparation method and application of nano zirconia/titanium oxide grafted polyacrylamide.
Background
In China, partially hydrolyzed polyacrylamide is most widely used in polymer flooding and more experiences are accumulated. The widely used partially hydrolyzed polyacrylamides are generally obtained by copolymerization of acrylamide with acrylates or by post-hydrolysis of polyacrylamides. In clear water, the electrostatic repulsion of carboxylic acid groups (salts) in the molecules of the partially hydrolyzed polyacrylamide enables the molecular chain of the polymer to be in a stretching state, so that the modified polyacrylamide has extremely strong tackifying capability. However, in saline water, the polyacrylamide molecules are in a curled state due to electrostatic shielding, and the thickening ability of the polyacrylamide molecules is greatly reduced. This is also the main reason for the poor salt resistance of conventional polyacrylamides.
Although the polyacrylamide has good tackifying effect and high cost performance, the polyacrylamide has the following problems of poor temperature resistance in the using process, and the polyacrylamide can generate obvious hydrolysis and thermal decomposition under the high-temperature condition, so that the viscosity of the polyacrylamide solution is reduced; the salt tolerance is poor, the obvious salt sensitivity effect is achieved, and in an oil reservoir with high salinity, particularly high-valence metal ion content, polyacrylamide molecules are in a curling state, and the viscosity of the polyacrylamide molecules can be greatly reduced; long-term stability of polyacrylamide is also poor; the high-temperature thermal degradation causes the polymer molecular chain to be broken, the viscosity of the solution is reduced quickly, and the actual effect of polymer flooding is greatly reduced.
Based on the above, the invention utilizes the hydrophilic nano zirconium dioxide and the nano titanium dioxide to modify the polyacrylamide to form the micro-crosslinked polyacrylamide, utilizes the high nano effect, the chemical stability, the thermal stability, the super-hydrophilicity and the non-migration of the hydrophilic nano zirconium dioxide and the nano titanium dioxide to effectively improve the rigidity and the structural stability of the molecular structure, improve the shear resistance, the high temperature resistance and the salt resistance of the molecular structure, and more conveniently adjust the crosslinking degree through the post-hydrolysis process, thereby achieving the purpose of improving the shear resistance, the high temperature resistance and the salt resistance of the molecular structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a post-hydrolysis preparation method and application of nano zirconia/titania grafted polyacrylamide.
The technical scheme of the invention is summarized as follows:
a post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide comprises the following steps:
s1: preparing a mixed monomer solution: mixing 320-350 parts by mass of acrylamide, 2.0-2.8 parts by mass of sodium acrylate, 12-15.6 parts by mass of functional monomer and 1135-1170 parts by mass of distilled water, uniformly stirring, and adjusting the pH to 6.0-7.0 to obtain a mixed monomer solution;
the functional monomer is prepared from 2-acrylamide-2-methylpropanesulfonic acid, sodium vinylsulfonate and 4-vinylbenzene sulfonate according to the weight ratio of 1: (0.6-1.2): (0.6-1.2) by mass;
s2: preparing a nano zirconia/titania precursor solution: adding 8-12 parts by mass of tetra-n-propyl zirconate and 8-12 parts by mass of tetrabutyl titanate into 50 parts of 40-50 wt% ethanol solution, adjusting the pH to 5.0-6.0, stirring and reacting in a water bath at 50-70 ℃ for 1-2 hours, adding 4-6 parts by mass of itaconic acid, and continuing stirring and reacting at 60-80 ℃ for 0.5-1 hour to obtain a nano zirconium oxide/titanium oxide precursor solution;
s3: cooling the mixed monomer solution to 0-5 ℃, then moving the mixed monomer solution into a reaction container, adding an azo initiator, introducing nitrogen for 10min, adding a complexing agent, further introducing nitrogen for 20min to drive out oxygen, adding a chain transfer agent, introducing nitrogen for 20min, adding an oxidant and a reducing agent to initiate polymerization reaction, sealing and preserving heat for 1.5-2 h after the reaction system is heated to the highest temperature, then adding a nano zirconium oxide/titanium oxide precursor solution, and continuing preserving heat and stirring for 0.5-2 h;
s4: granulating the rubber block obtained in the step S3, uniformly mixing the prepared rubber particles with a hydrolytic agent, and controlling the mass ratio of the rubber particles to the hydrolytic agent to be (3.7-10): hydrolysis reaction is carried out for 1-2 h at the temperature of 75-85 ℃;
s5: and (3) drying, crushing and sieving the hydrolyzed S4 colloidal particles to obtain the nano zirconia/titania grafted polyacrylamide.
Preferably, the amount of the azo initiator is 0.1-0.3% of the mass of the acrylamide monomer, and the azo initiator is selected from one or more of azobisisobutylamidine hydrochloride AIBA, azobisisobutylimidazoline hydrochloride AIBI, azobisisobutyronitrile AIBN and azobisisoheptonitrile ABVN.
Preferably, the amount of the complexing agent is 0.001-0.01% of the mass of the acrylamide monomer, and the complexing agent is selected from one or more of a chelating agent SF51-03, an ethylenediaminetetraacetic acid disodium salt and a chelating dispersant TPD-540.
Preferably, the amount of the chain transfer agent is 0.008-0.02% of the mass of the acrylamide monomer, and the chain transfer agent is selected from one or more of sodium formate, an alpha-methyl styrene linear dimer, dodecyl mercaptan and isooctyl 3-mercaptopropionate.
Preferably, the amount of the oxidant is 0.012-0.02% of the mass of the acrylamide monomer, and the oxidant is one or more selected from ammonium persulfate, sodium persulfate, tert-butyl hydroperoxide and methyl ethyl ketone peroxide.
Preferably, the mass ratio of the reducing agent to the oxidizing agent is (2-3): 1, and the reducing agent is selected from one or more of sodium metabisulfite, sodium bisulfite and ferrous sulfate.
Preferably, the dosage of the nano zirconia/titania precursor solution is 1.0-10% of the mass of the acrylamide monomer.
Preferably, the amount of the hydrolytic agent is 16-20% of the mass of the acrylamide monomer, and the hydrolytic agent is selected from one or more of 30 wt% sodium hydroxide solution, 30 wt% sodium carbonate solution and solid sodium hydroxide.
Preferably, the molecular weight of the nano zirconia/titania grafted polyacrylamide is more than or equal to 3000 ten thousand, the apparent viscosity is more than or equal to 20mPa & s, the shear viscosity retention rate is more than or equal to 90 percent, and the thermal stability is as follows: more than or equal to 95 percent in 1 month and more than or equal to 90 percent in 3 months.
The nano zirconia/titania grafted polyacrylamide prepared by the preparation method is applied to an oil displacement agent.
The invention has the beneficial effects that:
1. the invention utilizes salt-resistant monomers such as 2-acrylamide-2-methylpropanesulfonic acid, sodium vinylsulfonate, 4-vinylbenzene sulfonate and the like to be copolymerized with acrylamide, avoids the curling and entanglement in molecules and among molecules due to the mutual repulsion of hydrophilic groups and lipophilic groups in molecular side chains, forms a certain independent structure of the molecular side chains, and improves the rigidity and the structural stability of the molecular main chains while increasing the molecular weight of polyacrylamide.
2. The invention utilizes the hydrolysis of tetra-n-propyl zirconate and tetrabutyl titanate to generate Zr 4+ 、Ti 4+ And [ Zr (OH) n ] (4-n)+ 、[Ti(OH) n ] (4-n)+ The compound can further react with itaconic acid to form a coordination bond, further generate a vinyl-containing nano zirconia/titanium oxide precursor solution, and then carry out chemical graft copolymerization through an unsaturated bond and realize physical crosslinking through a hydrogen bond, so that the nano zirconia, the nano titanium oxide and polyacrylamide generate a micro-crosslinking effect, a three-dimensional interpenetrating network structure is formed, and the molecular weight and the structural stability are improved; meanwhile, under the crosslinking action of the nano-zirconia and nano-titania particles and the side group functional salt-resistant monomer, the rigidity of a polyacrylamide molecular chain is synergistically improved, and the resistance of polyacrylamide is further improvedHigh temperature, salt resistance and shear resistance, and effectively maintains the viscosity and profile control effect of polyacrylamide.
3. The invention further carries out post-hydrolysis process treatment on the polyacrylamide, effectively improves the molecular weight and viscosity, and ensures the solubility of the polyacrylamide.
Drawings
FIG. 1 is a flow chart of the post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide of the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example one
A post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide comprises the following steps:
s1: preparing a mixed monomer solution: mixing 320g of acrylamide, 2.3g of sodium acrylate, 12g of functional monomer and 1165.5g of distilled water, uniformly stirring, and adjusting the pH value to 6.0 to obtain a mixed monomer solution;
the functional monomer is formed by mixing 6g of 2-acrylamide-2-methylpropanesulfonic acid, 3.6g of sodium vinyl sulfonate and 3.6g of sodium 4-vinylbenzene sulfonate;
s2: preparing a nano zirconia/titania precursor solution: adding 8g of tetra-n-propyl zirconate and 8g of tetrabutyl titanate into 50g of 40 wt% ethanol solution, adjusting the pH to 5.0, stirring and reacting in a water bath at 55 ℃ for 1 hour, adding 4g of itaconic acid, and continuing to stir and react at 60 ℃ for 0.5 hour to obtain a nano zirconia/titania precursor solution;
s3: cooling the mixed monomer solution to 1 ℃, moving the mixed monomer solution to a reaction container, adding 0.4g of azobisisobutylamidine hydrochloride AIBA, introducing nitrogen (the purity of the nitrogen is more than or equal to 99.99%) for 10min, adding 0.016g of disodium ethylenediamine tetraacetic acid, continuing to introduce nitrogen and drive oxygen for 20min, adding 0.05g of sodium formate, introducing nitrogen for 20min, adding 0.04g of ammonium persulfate and 0.08g of sodium metabisulfite to initiate polymerization, heating the reaction system to the highest temperature, sealing and keeping the temperature for 1.5h, adding 3.2g of nano zirconium oxide/titanium oxide precursor solution, and continuing to keep the temperature and stir for 0.5 h;
s4: granulating the rubber block obtained in S3, uniformly mixing 200g of prepared rubber particles with 18g of 30 wt% sodium hydroxide solution, and carrying out hydrolysis reaction at 85 ℃ for 1.5 h;
s5: and (3) drying, crushing and sieving the hydrolyzed S4 colloidal particles to obtain the nano zirconia/titania grafted polyacrylamide.
The detection result of the prepared polyacrylamide according to Q/SH10201572-2017 is shown in Table 1:
TABLE 1
Example two
A post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide comprises the following steps:
s1: preparing a mixed monomer solution: mixing 340g of acrylamide, 2.3g of sodium acrylate, 15.6g of functional monomer and 1142.1g of distilled water, uniformly stirring, and adjusting the pH value to 6.2 to obtain a mixed monomer solution;
the functional monomer is formed by mixing 6g of 2-acrylamide-2-methylpropanesulfonic acid, 4.8g of sodium vinyl sulfonate and 4.8g of 4-vinylbenzene sulfonate;
s2: preparing a nano zirconia/titania precursor solution: adding 10g of tetra-n-propyl zirconate and 10g of tetrabutyl titanate into 50g of 45 wt% ethanol solution, adjusting the pH to 5.5, stirring and reacting in a water bath at 60 ℃ for 1.5h, adding 5g of itaconic acid, and continuing to stir and react at 70 ℃ for 0.5h to obtain a nano zirconia/titania precursor solution;
s3: cooling the mixed monomer solution to 0 ℃, transferring the mixed monomer solution to a reaction vessel, adding 0.68g of azobisisobutyronitrile AIBN, introducing nitrogen (the purity of the nitrogen is more than or equal to 99.99%) for 10min, adding 0.026g of chelating dispersant TPD-540, introducing nitrogen and removing oxygen for 20min, adding 0.051g of isooctyl 3-mercaptopropionate, introducing the nitrogen for 20min, adding 0.05g of ammonium persulfate and 0.10g of sodium metabisulfite to initiate polymerization reaction, heating the reaction system to the highest temperature, sealing and keeping the temperature for 2h, adding 8.5g of nano zirconium oxide/titanium oxide precursor solution, and keeping the temperature and stirring for 1 h;
s4: granulating the rubber block obtained in the step S3, uniformly mixing 200g of prepared rubber particles with 7.4g of solid sodium hydroxide, and carrying out hydrolysis reaction at 75 ℃ for 1.5 h;
s5: and (3) drying, crushing and sieving the hydrolyzed S4 colloidal particles to obtain the nano zirconia/titania grafted polyacrylamide.
The detection result of the prepared polyacrylamide according to Q/SH10201572-2017 is shown in Table 2:
TABLE 2
EXAMPLE III
A post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide comprises the following steps:
s1: preparing a mixed monomer solution: mixing 346g of acrylamide, 2.8g of sodium acrylate, 15g of functional monomer and 1136.2g of distilled water, uniformly stirring, and adjusting the pH value to 6.0 to obtain a mixed monomer solution;
the functional monomer is formed by mixing 5g of 2-acrylamide-2-methylpropanesulfonic acid, 5g of sodium vinyl sulfonate and 5g of 4-vinylbenzene sulfonate;
s2: preparing a nano zirconia/titania precursor solution: adding 10g of tetra-n-propyl zirconate and 10g of tetrabutyl titanate into 50g of 45 wt% ethanol solution, adjusting the pH value to 5.8, stirring and reacting in a water bath at 65 ℃ for 1.5h, adding 5.5g of itaconic acid, and continuously stirring and reacting at 75 ℃ for 1h to obtain a nano zirconia/titania precursor solution;
s3: cooling the mixed monomer solution to 0 ℃, then transferring the mixed monomer solution to a reaction container, adding 0.88g of azo diisobutyl amidine hydrochloride AIBA, introducing nitrogen (the purity of the nitrogen is more than or equal to 99.99%) for 10min, adding 0.028g of chelating agent SF51-03, continuing to introduce the nitrogen and drive oxygen for 20min, adding 0.055g of dodecyl mercaptan, introducing the nitrogen for 20min, adding 0.062g of tert-butyl hydroperoxide and 0.124g of sodium bisulfite to initiate polymerization, after the temperature of the reaction system is raised to the highest temperature, sealing and keeping the temperature for 2h, then adding 17.3g of nano zirconium oxide/titanium oxide precursor solution, continuing to keep the temperature and stir for 1 h;
s4: granulating the rubber block obtained in the step S3, uniformly mixing 200g of prepared rubber particles with 7.8g of solid sodium hydroxide, and carrying out hydrolysis reaction at 80 ℃ for 1.5 h;
s5: and (3) drying, crushing and sieving the hydrolyzed S4 colloidal particles to obtain the nano zirconia/titania grafted polyacrylamide.
The detection result of the prepared polyacrylamide according to Q/SH10201572-2017 is shown in Table 3:
TABLE 3
Example four
A post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide comprises the following steps:
s1: preparing a mixed monomer solution: mixing 336g of acrylamide, 2.0g of sodium acrylate, 13.6g of functional monomer and 1148.4g of distilled water, uniformly stirring, and adjusting the pH value to 6.0 to obtain a mixed monomer solution;
the functional monomer is formed by mixing 4g of 2-acrylamide-2-methylpropanesulfonic acid, 4.8g of sodium vinyl sulfonate and 4.8g of sodium 4-vinylbenzene sulfonate;
s2: preparing a nano zirconia/titania precursor solution: adding 12g of tetra-n-propyl zirconate and 12g of tetrabutyl titanate into 50g of 50 wt% ethanol solution, adjusting the pH to 6.0, stirring and reacting in a water bath at 70 ℃ for 2 hours, adding 6g of itaconic acid, and continuing stirring and reacting at 80 ℃ for 1 hour to obtain a nano zirconia/titania precursor solution;
s3: cooling the mixed monomer solution to 5 ℃, moving the mixed monomer solution to a reaction container, adding 0.67g of azobisisobutyronitrile hydrochloride AIBI, introducing nitrogen (the purity of the nitrogen is more than or equal to 99.99%) for 10min, adding 0.013g of disodium ethylenediamine tetraacetic acid, introducing nitrogen for 20min to drive oxygen, adding 0.04g of alpha-methylstyrene linear dimer, introducing the nitrogen for 20min, adding 0.062g of methyl ethyl ketone peroxide and 0.124g of ferrous sulfate to initiate polymerization, heating the reaction system to the highest temperature, sealing and keeping the temperature for 2h, adding the nano zirconium oxide/titanium oxide precursor solution, and keeping the temperature and stirring for 2 h;
s4: granulating the rubber block obtained in the step S3, uniformly mixing 200g of prepared rubber particles with 20g of 30 wt% sodium carbonate solution, and carrying out hydrolysis reaction at 85 ℃ for 2 h;
s5: and (3) drying, crushing and sieving the hydrolyzed S4 colloidal particles to obtain the nano zirconia/titania grafted polyacrylamide.
The detection result of the prepared polyacrylamide according to Q/SH10201572-2017 is shown in Table 4:
TABLE 4
Comparative example one: the difference is the same as the first embodiment: the nano zirconia/titania precursor solution is not added in the preparation process of S3.
Comparative example two: the difference is the same as the first embodiment: itaconic acid is not added in the preparation process of the S2 nano zirconia/titania precursor solution.
Comparative example three: the difference is the same as the first embodiment: tetrabutyl titanate is not added in the preparation process of the S2 precursor solution, and the specific operation steps are as follows: adding 16g of tetra-n-propyl zirconate into 50g of 40 wt% ethanol solution, adjusting the pH value to 5.0, stirring and reacting in a water bath at 55 ℃ for 1 hour, adding 4g of itaconic acid, and continuously stirring and reacting at 60 ℃ for 0.5 hour to obtain the nano zirconia precursor solution.
Comparative example four: the difference is the same as the first embodiment: in the preparation process of the S2 precursor solution, tetra-n-propyl zirconate is not added, and the specific operation steps are as follows: adding 16g of tetrabutyl titanate into 50g of 40 wt% ethanol solution, adjusting the pH value to 5.0, stirring and reacting in a water bath at 55 ℃ for 1 hour, adding 4g of itaconic acid, and continuing to stir and react at 60 ℃ for 0.5 hour to obtain the nano titanium oxide precursor solution.
The polyacrylamides prepared in comparative examples one to four were tested according to Q/SH10201572-2017, and the product test results are shown in Table 5:
TABLE 5
The method for measuring the shear viscosity retention rate and the thermal stability is as follows:
shear viscosity retention: the polyacrylamides prepared in the examples and the comparative examples were prepared into 1500mg/L aqueous polymer solutions, and the apparent viscosity W of the solutions was measured at a rotation speed of 6r/min 1 . The capillary tube was connected to the lower part of a 500mL cylindrical stainless steel container, the solution to be measured was filled into the stainless steel container, a nitrogen gas cylinder was connected to the top of the container through a pressure regulator to make the container reach a pressure of 0.1MPa and to be kept constant, and after the ball valve at the lower part of the container was fully opened to flow about 50mL of the sample to be measured into the sampling container, the ball valve was closed. Measuring the apparent viscosity W of the sheared solution at a rotation speed of 6r/min 2 And according to the formula 100% xW 2 /W 1 The viscosity retention was calculated. The stainless steel container is required to be tested before use, and no leakage is ensured.
Thermal stability: 1500mg/L of the test solution was prepared, and the apparent viscosity was measured and recorded as W 3 And (3) subpackaging 180mL of the solution into 6 ampoules, evacuating to 13.3Pa, filling nitrogen into the ampoules, sealing by using a flame sealing and cutting device when the air pressure in the ampoules reaches the daily atmospheric pressure, and storing in an oven at 70 ℃. After the heat aging time (one and three months) had been reached, the ampoule was removed and the apparent viscosity was measured and recorded as W 4 And according to the formula 100% xW 4 /W 3 The thermal stability was calculated.
In the embodiments 1-4, salt-resistant monomers such as 2-acrylamide-2-methylpropanesulfonic acid, sodium vinylsulfonate and 4-vinylbenzene sulfonate are copolymerized with acrylamide, and due to mutual repulsion of hydrophilic groups and lipophilic groups in molecular side chains, curling and entanglement in molecules and among molecules are avoided, so that a certain independent structure of the molecular side chains is formed, the molecular weight of polyacrylamide is increased, and meanwhile, the rigidity and the structural stability of the molecular main chains are improved.
Examples 1 to 4 hydrolysis of Zr produced by tetra-n-propylzirconic acid and tetrabutyl titanate 4+ 、Ti 4+ And [ Zr (OH) ] n ] (4-n)+ 、[Ti(OH) n ] (4-n)+ The vinyl-containing nano-zirconia/titanium oxide precursor solution can further react with itaconic acid to form a coordination bond, then a vinyl-containing nano-zirconia/titanium oxide precursor solution is generated, chemical graft copolymerization is carried out through an unsaturated bond, physical crosslinking is realized through a hydrogen bond, and then micro-crosslinking effect is generated among nano-zirconia, nano-titanium oxide and polyacrylamide to form a three-dimensional interpenetrating network structure, so that the molecular weight and the structural stability are improved; meanwhile, under the crosslinking action of the nano-zirconia and nano-titania particles and the side group functional salt-resistant monomer, the rigidity of a polyacrylamide molecular chain is synergistically improved, the high temperature resistance, salt resistance and shear resistance of polyacrylamide are further improved, and the viscosity and profile control and flooding effects of the polyacrylamide are effectively maintained.
The embodiment 1-4 further performs post-hydrolysis process treatment on the polyacrylamide, effectively improves the molecular weight and viscosity, and ensures the solubility of the polyacrylamide.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. A post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide is characterized by comprising the following steps:
s1: preparing a mixed monomer solution: mixing 320-350 parts by mass of acrylamide, 2.0-2.8 parts by mass of sodium acrylate, 12-15.6 parts by mass of functional monomer and 1135-1170 parts by mass of distilled water, uniformly stirring, and adjusting the pH to 6.0-7.0 to obtain a mixed monomer solution;
the functional monomer is prepared from 2-acrylamide-2-methylpropanesulfonic acid, sodium vinylsulfonate and 4-vinylbenzene sulfonate according to the weight ratio of 1: (0.6-1.2): (0.6-1.2) by mass;
s2: preparing a nano zirconia/titania precursor solution: adding 8-12 parts by mass of tetra-n-propyl zirconate and 8-12 parts by mass of tetrabutyl titanate into 50 parts of 40-50 wt% ethanol solution, adjusting the pH to 5.0-6.0, stirring and reacting in a water bath at 50-70 ℃ for 1-2 hours, adding 4-6 parts by mass of itaconic acid, and continuing stirring and reacting at 60-80 ℃ for 0.5-1 hour to obtain a nano zirconium oxide/titanium oxide precursor solution;
s3: cooling the mixed monomer solution to 0-5 ℃, then moving the mixed monomer solution into a reaction container, adding an azo initiator, introducing nitrogen for 10min, adding a complexing agent, further introducing nitrogen for 20min to drive out oxygen, adding a chain transfer agent, introducing nitrogen for 20min, adding an oxidant and a reducing agent to initiate polymerization reaction, sealing and preserving heat for 1.5-2 h after the reaction system is heated to the highest temperature, then adding a nano zirconium oxide/titanium oxide precursor solution, and continuing preserving heat and stirring for 0.5-2 h;
s4: and (2) granulating the rubber block obtained in the step (S3), uniformly mixing the prepared rubber particles with a hydrolytic agent, and controlling the mass ratio of the rubber particles to the hydrolytic agent to be (3.7-10): hydrolysis reaction is carried out for 1-2 h at the temperature of 75-85 ℃;
s5: and (3) drying, crushing and sieving the hydrolyzed S4 colloidal particles to obtain the nano zirconia/titania grafted polyacrylamide.
2. The post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide according to claim 1, wherein the amount of the azo initiator is 0.1-0.3% by mass of the acrylamide monomer, and is selected from one or more of azobisisobutylamidine hydrochloride AIBA, azobisisobutylimidazoline hydrochloride AIBI, azobisisobutyronitrile AIBN and azobisisoheptonitrile ABVN.
3. The post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide as claimed in claim 1, wherein the amount of the complexing agent is 0.001-0.01% of the mass of acrylamide monomer, and is selected from one or more of chelating agent SF51-03, disodium ethylenediaminetetraacetate, chelating dispersant TPD-540.
4. The post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide according to claim 1, wherein the amount of the chain transfer agent is 0.008-0.02% of the mass of acrylamide monomer, and is selected from one or more of sodium formate, alpha-methyl styrene linear dimer, dodecyl mercaptan, and isooctyl 3-mercaptopropionate.
5. The post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide according to claim 1, wherein the amount of the oxidant is 0.012-0.02% of the mass of acrylamide monomer, and is selected from one or more of ammonium persulfate, sodium persulfate, hydrogen peroxide tert-butyl and methyl ethyl ketone peroxide.
6. The post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide according to claim 1, wherein the mass ratio of the reducing agent to the oxidizing agent is (2-3): 1, and the reducing agent is selected from one or more of sodium metabisulfite, sodium bisulfite and ferrous sulfate.
7. The post-hydrolysis preparation method of nano zirconia/titania grafted polyacrylamide according to claim 1, wherein the amount of the nano zirconia/titania precursor solution is 1.0-10% by mass of acrylamide monomer.
8. The method for preparing nano zirconia/titania grafted polyacrylamide according to claim 1, wherein the hydrolytic agent is one or more selected from 30 wt% sodium hydroxide solution, 30 wt% sodium carbonate solution and solid sodium hydroxide.
9. The nano zirconia/titania grafted polyacrylamide prepared by the preparation method according to any one of claims 1 to 8, wherein the molecular weight of the nano zirconia/titania grafted polyacrylamide is not less than 3000 ten thousand, the apparent viscosity is not less than 20mPa s, the shear viscosity retention rate is not less than 90%, and the thermal stability is as follows: more than or equal to 95 percent in 1 month and more than or equal to 90 percent in 3 months.
10. Application of the nano zirconia/titania grafted polyacrylamide prepared by the preparation method of any one of claims 1-8 in an oil displacement agent.
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| CN104109525A (en) * | 2013-04-17 | 2014-10-22 | 中国石油大学(北京) | Preparation method of polyacrylamide nano composite fracturing fluid |
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