CN109666099B - Core-shell polymer microsphere and preparation method thereof - Google Patents
Core-shell polymer microsphere and preparation method thereof Download PDFInfo
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- CN109666099B CN109666099B CN201710977799.3A CN201710977799A CN109666099B CN 109666099 B CN109666099 B CN 109666099B CN 201710977799 A CN201710977799 A CN 201710977799A CN 109666099 B CN109666099 B CN 109666099B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 69
- 239000004005 microsphere Substances 0.000 title claims abstract description 56
- 239000011258 core-shell material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012071 phase Substances 0.000 claims abstract description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 78
- 239000000178 monomer Substances 0.000 claims abstract description 75
- 239000003999 initiator Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008346 aqueous phase Substances 0.000 claims abstract description 17
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- 230000009471 action Effects 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 70
- 239000003638 chemical reducing agent Substances 0.000 claims description 68
- -1 azo compound Chemical class 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 229920002401 polyacrylamide Polymers 0.000 claims description 32
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 30
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 20
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 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 13
- 239000002736 nonionic surfactant Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 4
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims description 2
- CRGOPMLUWCMMCK-UHFFFAOYSA-M benzyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)CC1=CC=CC=C1 CRGOPMLUWCMMCK-UHFFFAOYSA-M 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-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
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 229940001474 sodium thiosulfate Drugs 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 2
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 claims 1
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 238000012703 microemulsion polymerization Methods 0.000 claims 1
- 150000003440 styrenes Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 230000032683 aging Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 119
- 235000019198 oils Nutrition 0.000 description 119
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 28
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 18
- 229940047670 sodium acrylate Drugs 0.000 description 18
- 229920001213 Polysorbate 20 Polymers 0.000 description 16
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 16
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 16
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229940035044 sorbitan monolaurate Drugs 0.000 description 8
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- 239000002245 particle Substances 0.000 description 6
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 6
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 238000000605 extraction Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007957 coemulsifier Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- WRHHVVPVKLLPFT-UHFFFAOYSA-N 2-o-ethyl 1-o-methyl oxalate Chemical compound CCOC(=O)C(=O)OC WRHHVVPVKLLPFT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 229910052731 fluorine Chemical group 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a core-shell polymer microsphere and a preparation method thereof, which mainly solve the problems of unstable polymer microemulsion, poor temperature resistance and salt resistance of the polymer microsphere and poor plugging effect after long-term aging in the prior art. The invention adopts core-shell polymer microsphere, which is prepared by inverse microemulsion through polymerization reaction under the action of redox composite initiator; the reverse microemulsion comprises the following components in parts by weight: 50 parts of an oil-soluble solvent; 3-20 parts of emulsifying agent; 10-60 parts of hydrophilic monomer; 0.5 to 10 parts of hydrophobic monomer; 10-50 parts of water; by adopting a two-step reaction method, the technical scheme that aqueous phase solution containing acrylamide, other hydrophilic monomers and hydrophobic monomers is added into oil phase containing emulsifying agent step by step for polymerization reaction is adopted, so that the problem is well solved, and the method can be used for tertiary oil recovery of high-temperature high-mineralization oil reservoirs.
Description
Technical Field
The invention relates to a core-shell polymer microsphere and a preparation method thereof.
Background
The water content of crude oil is continuously increased after primary oil extraction and secondary oil extraction of various domestic large oil fields, and part of large oil fields enter the tertiary oil extraction stage successively. Polymer flooding is a main technical method for tertiary oil recovery, has clear oil displacement mechanism and relatively simple process, and is a technical measure for effectively improving recovery efficiency. However, for heterogeneous formations, displacement can only act on high permeability layers, but does not reach low permeability layers containing oil, which results in lower recovery of crude oil and increased cost. Generally, a water injection well profile control and production well water shutoff technology is adopted aiming at heterogeneous stratum, but the effective range of the technology is limited to near-wellbore zones, the technology cannot go deep into the deep part of an oil well, the purpose of greatly improving the crude oil recovery ratio cannot be achieved, and a novel deep profile control water shutoff agent is needed to be found.
The polyacrylamide microsphere is used as one of the most commonly used organic water shutoff and profile control agents, has obvious selectivity to water, has unchanged volume when meeting oil and expands when meeting water, so the polyacrylamide microsphere has good water shutoff effect, and has the characteristics of long effective period, no pollution to stratum, simple construction, short operation time and the like. Because of different permeability and serious heterogeneity of oil reservoirs, polymer microspheres with different sizes are needed to meet the profile control and plugging requirements of different stratum.
In recent years, researchers at home and abroad have more researches on the aspect of applying the polyacrylamide reverse microemulsion to oil reservoir deep profile control materials, and have better progress and achievement. Patent CN1903974A synthesizes a terpolymer nano-size microgel oil displacement material, adopts a low-temperature photoinitiator of a non-redox initiation system, and utilizes ultraviolet light to decompose the initiator to generate active free radical initiation polymerization, which is beneficial to the stability of inverse microemulsion and the control of particle size, but the content of emulsifier in the system is up to more than 25 percent, which tends to cause high production cost. Patent CN101759838A provides a preparation method of a low interfacial tension polyacrylamide nanoparticle profile control system, which evaluates the tension reduction condition of a victory oilfield pile on crude oil under the condition of a pile 106 well of an oil extraction factory, but does not express the expansion performance of polymer microspheres, so that the profile control capability of the system on an oil reservoir is not examined.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the polymer microemulsion is unstable, the temperature and salt resistance of the polymer microsphere is poor, and the plugging effect after long-term aging is poor in the prior art, and the core-shell type polyacrylamide microsphere is provided.
The second technical problem to be solved by the invention is a preparation method of the core-shell polymer microsphere.
The third technical problem to be solved by the invention is the application of the core-shell polymer microsphere in tertiary oil recovery of high-temperature and high-mineralization oil reservoirs.
In order to solve one of the technical problems, the technical scheme of the invention is as follows: the core-shell polymer microsphere is prepared by polymerization of reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent;
b) 3-20 parts of emulsifying agent;
c) 10-60 parts of hydrophilic monomer;
d) 0.5 to 10 parts of hydrophobic monomer;
e) 10-50 parts of water.
In the technical scheme, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.02-1.0% of oxidant;
(b) 0.02-2.0% of reducing agent;
(c) 0.03 to 2.0 percent of azo compound;
(d) 0.01 to 1.0 percent of cross-linking agent;
(e) Urea and thiourea in 0.1-10 wt%;
(f) 0.01 to 0.5 percent of aminocarboxylic complexing agent;
(g) 0.5 to 5 percent of electrolyte salt.
The oil-soluble solvent in the technical proposalPreferably at least one selected from hydrocarbons and esters. The hydrocarbon can be aliphatic hydrocarbon, aromatic hydrocarbon, petroleum fraction; the aliphatic hydrocarbon is preferably C 4 ～C 8 Aliphatic hydrocarbons such as cyclohexane, hexane, heptane, octane, isooctane, etc.; the aromatic hydrocarbon is preferably C 6 ～C 10 Aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, isopropylbenzene, etc.; the petroleum fraction is preferably white oil, liquid paraffin, gasoline, kerosene, diesel oil, petroleum ether and the like. The esters are preferably carboxylic acid esters, more preferably C 4 ～C 8 Monoesters of (a) such as ethyl acetate, propyl acetate, etc.; and may even more preferably C 4 ～C 10 Such as dimethyl oxalate, diethyl oxalate, methyl ethyl oxalate, etc.; vegetable oils may be more preferred, preferably from peanut oil, soybean oil, sunflower oil and castor oil.
In the above technical scheme, the HLB value of the emulsifier is preferably 5-8. The emulsifier is more preferably a nonionic surfactant. The emulsifier is preferably in the form of a nonionic surfactant mixture with HLB of 5-8, which is prepared by compounding a nonionic surfactant with HLB of 1-7 and a nonionic surfactant with HLB of 8-18. Such as fatty alcohols, alkylphenols, fatty acids, fatty acid esters or amine alkoxylates, for example fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, fatty amine polyoxyethylene ethers, etc., and further for example products of partial hydroxy esterification of polyols, for example sorbitan fatty acid esters, also known as span-like, and also partial or total hydroxy ethoxylation and fatty acid esters of polyols, for example tween-like.
In the above technical solution, the emulsifier may further include a co-emulsifier. The auxiliary emulsifier can be small molecular alcohols. The small molecule alcohol is preferably C 3 ～C 12 Such as isopropanol, t-butanol, n-pentanol, etc. The co-emulsifier content is preferably from 5 to 30wt% of the nonionic surfactant in the emulsifier.
In the above technical solution, the hydrophilic monomer is at least one selected from nonionic monomers, anionic monomers and cationic monomers, more preferably selected from nonionic monomers, anionic monomers and cationic monomers, most preferably selected from at least one nonionic monomer, at least two anionic monomers and at least one cationic monomer, and at this time, the four monomers have better synergistic effect and the blocking efficiency is highest; the nonionic hydrophilic monomer is at least one selected from acrylamide, methacrylamide, N-isopropyl acrylamide, N-methylolacrylamide, tert-butyl acrylamide, N-vinyl pyrrolidone, N-dimethyl acrylamide and N, N-diethyl acrylamide; the anionic hydrophilic monomer is at least one selected from acrylic acid, methacrylic acid, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, vinylbenzenesulfonic acid, allylsulfonic acid, methacrylic sulfonic acid, styrenesulfonic acid and/or water-soluble alkali metal, alkaline earth metal and ammonium salt; the cationic hydrophilic monomer is at least one selected from dimethyl diallyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl dimethyl benzyl ammonium chloride, methacryloxyethyl dimethyl benzyl ammonium chloride and methacryloxypropyl trimethyl ammonium chloride.
In the technical scheme, the hydrophobic monomer is at least one selected from N-phenylmaleimide, maleic anhydride, styrene and derivatives thereof, sodium acrylamide nitrogen alkyl sulfonate with a carbon chain number of 8-18, alkyl or fluorine substituted alkyl acrylate with a carbon chain number of 8-18.
In the above technical solution, the oxidizing agent is at least one selected from potassium persulfate, sodium persulfate, ammonium persulfate and benzoyl peroxide; the reducing agent is at least one selected from sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium thiosulfate and ferrous chloride; the azo compound is selected from azo diisobutyl amidine hydrochloride and 2,2' -azo [2- (2-imidazoline-2-yl) propane]At least one of dihydrochloride, azobisisobutyronitrile, azobisisoheptonitrile; the cross-linking agent is at least one selected from methylene bisacrylamide, divinylbenzene, polyethylene glycol diacrylate, pentaerythritol triacrylate and N, N' -m-phenylene bismaleimide; the ammonia carboxyl complexing agentAt least one selected from ethylenediamine tetraacetic acid and alkali metal salts thereof, diethylenetriamine pentaacetic acid and alkali metal salts thereof; the electrolyte salt is preferably a water-soluble inorganic salt or organic acid salt. The inorganic salt is preferably an alkali metal salt (e.g., sodium chloride, potassium chloride), alkali metal sulfate (e.g., sodium sulfate, potassium sulfate); the organic acid salt is preferably an alkali metal organic acid salt, more preferably C 2 ～C 6 Alkali metal salts of carboxylic acids, such as potassium acetate or sodium acetate.
In order to solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the core-shell polymer microsphere comprises the following steps:
(a) Preparing an oil phase: dissolving an emulsifier in an oil-soluble solvent, and uniformly stirring to obtain an oil phase I; dissolving an oil-soluble cross-linking agent and an oil-soluble azo initiator in an oil-soluble solvent, and uniformly stirring to obtain an oil phase II; and dissolving the oil-soluble hydrophobic monomer in an oil-soluble solvent, and uniformly stirring to obtain an oil phase III.
(b) Preparing an aqueous phase: dissolving 40-70 wt% of hydrophilic monomer and a water-soluble composite initiator except a reducing agent in water, and uniformly stirring to obtain a nuclear water phase; dissolving the rest hydrophilic monomers and a water-soluble composite initiator except a reducing agent in water, and uniformly stirring to obtain a shell water phase; dissolving a reducing agent in water to form a reducing agent aqueous solution;
(c) Adding the oil phase I into a reactor, adding 40-70wt% of the oil phase II and the nuclear water phase, uniformly stirring, then dropwise adding a reducing agent aqueous solution, and reacting for 1-4 hours at the temperature of 40-80 ℃ to obtain the polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 15-35 ℃, adding the residual oil phase II, the oil phase III and the shell water phase again, stirring uniformly, dripping the aqueous solution of the reducing agent, and reacting for 1-4 hours at 40-80 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
As a more preferable embodiment, the step (c) is as follows:
(c) Adding the oil phase I into a reactor, adding 40-70wt% of the oil phase II and the nuclear water phase, uniformly stirring, then dropwise adding a reducing agent aqueous solution, and reacting for 2-3 hours at 50-60 ℃ to obtain the polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 25-30 ℃, adding the residual oil phase II, the oil phase III and the shell water phase again, stirring uniformly, dripping the aqueous solution of the reducing agent, and reacting for 2-3 hours at 50-60 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
In order to solve the third technical problem, the technical scheme of the invention is as follows: the core-shell polymer microsphere is applied to tertiary oil recovery of a high-temperature high-mineralization oil reservoir.
The polymer microsphere of the invention is suitable for high temperature of 80-120 ℃ and 10 multiplied by 10 4 ～30×10 4 mg/L of highly mineralized oil reservoir.
By adopting the technical scheme of the invention, the obtained polymer microemulsion is not layered after standing for 3 months, and in addition, the polymer microsphere in the polymer microemulsion has the total mineralization degree of 20 multiplied by 10 at 90 DEG C 4 mg/L、Ca 2+ +Mg 2+ : the expansion multiple of the microsphere particle size can reach more than 8 times after 15 days under the condition of 6000mg/L brine, and the plugging rate of the 300mD artificial rock core can reach more than 85 percent, so that a better technical effect is achieved, and the method can be used in tertiary oil recovery of high-temperature and high-mineralization oil reservoirs.
The invention is further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
The polymer microsphere of the embodiment is prepared by polymerization reaction of reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 6 parts of sodium acrylate, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 5 parts of dimethyl diallyl ammonium chloride;
d) 5 parts of hydrophobic monomer: sodium 2-acrylamido-N-hexadecyl sulfonate;
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of an oil-soluble azo compound; the oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 40 parts of the white oil, and uniformly stirring to obtain an oil phase I; dissolving azodiisobutyronitrile in 5 parts of the white oil, and uniformly stirring to obtain an oil phase II; dissolving 2-acrylamide-N-hexadecyl sodium sulfonate into 5 parts of the white oil, and uniformly stirring to obtain an oil phase III.
(b) Preparing an aqueous phase: 9 parts of acrylamide, 3 parts of sodium acrylate, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5 parts of dimethyl diallyl ammonium chloride and a half amount of water-soluble composite initiator except sodium bisulfate are dissolved in 13 parts of water and uniformly stirred to obtain a nuclear water phase; dissolving the rest hydrophilic monomer and the rest water-soluble composite initiator except sodium bisulphite in 13 parts of water, and uniformly stirring to obtain a shell water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding half of the oil phase II and all the nuclear water phase, uniformly stirring, then dropwise adding half of the reducing agent aqueous solution, and reacting for 2 hours at 50 ℃ to obtain the polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the residual oil phase II, the oil phase III and all shell water phases again, uniformly stirring, dripping the residual reducing agent aqueous solution, and reacting for 2 hours at 50 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
Characterization of polymer microemulsions and wherein polymer microspheres:
testing initial particle size of microsphere according to measurement method of Q/SH1020 China petrochemical group victory Petroleum administration enterprise standard (Polymer microsphere deep profile control and flooding agent technical Condition) and total mineralization degree of 20×10 at 90 DEG C 4 mg/L，Ca 2+ +Mg 2+ : the expansion times of the particle sizes of the microspheres after aging for 7 days, 15 days and 30 days under the condition of 6000mg/L saline are measured by using a core displacement device, the blocking rate of the microspheres to 300mD artificial cores is measured, and the state of the obtained microemulsion system after standing for 3 months is observed, and the results are shown in table 1.
[ comparative example 1 ]
The polymer microsphere of the comparative example is prepared by polymerization of inverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; span 40 with an emulsifier HLB value of 6.7;
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 6 parts of sodium acrylate, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 5 parts of dimethyl diallyl ammonium chloride;
d) 5 parts of hydrophobic monomer: sodium 2-acrylamido-N-hexadecyl sulfonate;
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of an oil-soluble azo compound; the oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving the emulsifier span 40 with the HLB of 6.7 in 40 parts of the white oil, and uniformly stirring to obtain an oil phase I; dissolving azodiisobutyronitrile in 5 parts of the white oil, and uniformly stirring to obtain an oil phase II; dissolving 2-acrylamide-N-hexadecyl sodium sulfonate into 5 parts of the white oil, and uniformly stirring to obtain an oil phase III.
(b) Preparing an aqueous phase: 9 parts of acrylamide, 3 parts of sodium acrylate, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5 parts of dimethyl diallyl ammonium chloride and a half amount of water-soluble composite initiator except sodium bisulfate are dissolved in 13 parts of water and uniformly stirred to obtain a nuclear water phase; dissolving the rest hydrophilic monomer and the rest water-soluble composite initiator except sodium bisulphite in 13 parts of water, and uniformly stirring to obtain a shell water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding half of the oil phase II and all the nuclear water phase, uniformly stirring, then dropwise adding half of the reducing agent aqueous solution, and reacting for 2 hours at 50 ℃ to obtain the polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the residual oil phase II, the oil phase III and all shell water phases again, uniformly stirring, dripping the residual reducing agent aqueous solution, and reacting for 2 hours at 50 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
The characterization of the polymer microemulsion and the polymer microspheres therein was the same as in example 1, and the results are shown in table 1.
The present inventors have found that the emulsifier used in the present invention is preferably a nonionic surfactant mixture having an HLB of from 1 to 7 and a nonionic surfactant having an HLB of from 8 to 18, and that the nonionic surfactant having an HLB of from 1 to 7 and the nonionic surfactant having an HLB of from 8 to 18 in the resulting nonionic surfactant mixture have a synergistic effect in improving the stability of the polyacrylamide microemulsion and in improving the swelling properties of the polymer microspheres in the polyacrylamide microemulsion. This can be seen visually from the same ratio data of example 1 and comparative example 1.
[ example 2 ]
The polymer microsphere of the embodiment is prepared by polymerization reaction of reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 6 parts of sodium acrylate, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 5 parts of dimethyl diallyl ammonium chloride;
d) 5 parts of hydrophobic monomer: stearyl methacrylate;
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of an oil-soluble azo compound; the oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 40 parts of the white oil, and uniformly stirring to obtain an oil phase I; dissolving azodiisobutyronitrile in 5 parts of the white oil, and uniformly stirring to obtain an oil phase II; and (3) dissolving the stearyl methacrylate into 5 parts of the white oil, and uniformly stirring to obtain an oil phase III.
(b) Preparing an aqueous phase: 9 parts of acrylamide, 3 parts of sodium acrylate, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5 parts of dimethyl diallyl ammonium chloride and a half amount of water-soluble composite initiator except sodium bisulfate are dissolved in 13 parts of water and uniformly stirred to obtain a nuclear water phase; dissolving the rest hydrophilic monomer and the rest water-soluble composite initiator except sodium bisulphite in 13 parts of water, and uniformly stirring to obtain a shell water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding half of the oil phase II and all the nuclear water phase, uniformly stirring, then dropwise adding half of the reducing agent aqueous solution, and reacting at 60 ℃ for 2 hours to obtain the polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the residual oil phase II, the oil phase III and all shell water phases again, uniformly stirring, dripping the residual reducing agent aqueous solution, and reacting at 60 ℃ for 2 hours to finally obtain the core-shell type polyacrylamide reverse microemulsion.
The characterization of the polymer microemulsion and the polymer microspheres therein was the same as in example 1, and the results are shown in table 1.
[ example 3 ]
The polymer microsphere of the embodiment is prepared by polymerization reaction of reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 6 parts of sodium acrylate, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 5 parts of dimethyl diallyl ammonium chloride;
d) 5 parts of hydrophobic monomer: p-tert-butylstyrene;
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of water-soluble azo compound; the water-soluble azo compound is 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 45 parts of the white oil, and uniformly stirring to obtain an oil phase I; and (3) dissolving the p-tert-butylstyrene in 5 parts of the white oil, and uniformly stirring to obtain an oil phase II.
(b) Preparing an aqueous phase: 9 parts of acrylamide, 3 parts of sodium acrylate, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5 parts of dimethyl diallyl ammonium chloride and a half amount of water-soluble composite initiator except sodium bisulfate are dissolved in 13 parts of water and uniformly stirred to obtain a nuclear water phase; dissolving the rest hydrophilic monomer and the rest water-soluble composite initiator except sodium bisulphite in 13 parts of water, and uniformly stirring to obtain a shell water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding all the nuclear water phase, uniformly stirring, then dropwise adding a half amount of reducer aqueous solution, and reacting for 3 hours at 50 ℃ to obtain polyacrylamide reverse microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the oil phase II and all shell water phases again, stirring uniformly, dripping the rest aqueous solution of the reducing agent, and reacting for 3 hours at 50 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
The characterization of the polymer microemulsion and the polymer microspheres therein was the same as in example 1, and the results are shown in table 1.
[ example 4 ]
The polymer microsphere of the embodiment is prepared by polymerization reaction of reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 6 parts of sodium acrylate, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 5 parts of dimethyl diallyl ammonium chloride;
d) 5 parts of hydrophobic monomer: n-phenylmaleimide;
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of water-soluble azo compound; the water-soluble azo compound is 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 45 parts of the white oil, and uniformly stirring to obtain an oil phase I; dissolving N-phenylmaleimide into 5 parts of the white oil, and uniformly stirring to obtain an oil phase II.
(b) Preparing an aqueous phase: 9 parts of acrylamide, 3 parts of sodium acrylate, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5 parts of dimethyl diallyl ammonium chloride and a half amount of water-soluble composite initiator except sodium bisulfate are dissolved in 13 parts of water and uniformly stirred to obtain a nuclear water phase; dissolving the rest hydrophilic monomer and the rest water-soluble composite initiator except sodium bisulphite in 13 parts of water, and uniformly stirring to obtain a shell water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding all the nuclear water phase, uniformly stirring, then dropwise adding a half amount of reducer aqueous solution, and reacting for 3 hours at 50 ℃ to obtain polyacrylamide reverse microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the oil phase II and all shell water phases again, stirring uniformly, dripping the rest aqueous solution of the reducing agent, and reacting for 3 hours at 50 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
The characterization of the polymer microemulsion and the polymer microspheres therein was the same as in example 1, and the results are shown in table 1.
[ example 5 ]
The polymer microsphere of the embodiment is prepared by polymerization reaction of reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 6 parts of sodium acrylate, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 5 parts of acryloyloxyethyl trimethyl ammonium chloride;
d) 5 parts of hydrophobic monomer: maleic anhydride
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of water-soluble azo compound; the water-soluble azo compound is 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 45 parts of the white oil, and uniformly stirring to obtain an oil phase I; and (3) dissolving maleic anhydride in 5 parts of the white oil, and uniformly stirring to obtain an oil phase II.
(b) Preparing an aqueous phase: 9 parts of acrylamide, 3 parts of sodium acrylate, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5 parts of acryloyloxyethyl trimethyl ammonium chloride and a half amount of water-soluble composite initiator except sodium bisulfate are dissolved in 13 parts of water and uniformly stirred to obtain a nuclear water phase; dissolving the rest hydrophilic monomer and the rest water-soluble composite initiator except sodium bisulphite in 13 parts of water, and uniformly stirring to obtain a shell water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding all the nuclear water phase, uniformly stirring, dropwise adding a half amount of reducer aqueous solution, and reacting for 2 hours at 50 ℃ to obtain polyacrylamide reverse microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the oil phase II and all shell water phases again, stirring uniformly, dripping the rest aqueous solution of the reducing agent, and reacting for 2 hours at 50 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
The characterization of the polymer microemulsion and the polymer microspheres therein was the same as in example 1, and the results are shown in table 1.
[ comparative example 2 ]
The polymer microsphere of the comparative example is prepared by polymerization of inverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 6 parts of sodium acrylate, 6 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 5 parts of dimethyl diallyl ammonium chloride;
d) 5 parts of hydrophobic monomer: sodium 2-acrylamido-N-hexadecyl sulfonate;
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of an oil-soluble azo compound; the oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 40 parts of the white oil, and uniformly stirring to obtain an oil phase I; and dissolving azodiisobutyronitrile and 2-acrylamide-N-hexadecyl sodium sulfonate into 10 parts of the white oil, and uniformly stirring to obtain an oil phase II.
(b) Preparing an aqueous phase: dissolving acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium, dimethyl diallyl ammonium chloride and a water-soluble composite initiator except sodium bisulphite in 26 parts of water, and uniformly stirring to obtain a water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding the oil phase II and all the water phases, uniformly stirring, then dropwise adding the aqueous solution of the reducing agent, and reacting for 4 hours at 50 ℃ to obtain the polyacrylamide reverse microemulsion.
The characterization of the polymer microemulsion and the polymer microspheres therein was the same as in example 1, and the results are shown in table 1.
[ comparative example 3 ]
The polymer microsphere of the comparative example is prepared by polymerization of inverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 40 parts of hydrophilic monomer: consists of 20 parts of acrylamide, 10 parts of sodium acrylate and 10 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt;
d) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of water-soluble azo compound; the water-soluble azo compound is 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: and dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 50 parts of the white oil, and uniformly stirring to obtain an oil phase.
(b) Preparing an aqueous phase: dissolving acrylamide, sodium acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium and a water-soluble composite initiator except sodium bisulphite in 26 parts of water, and uniformly stirring to obtain a water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase into a reactor, adding half of aqueous phase solution serving as a nuclear aqueous phase, uniformly stirring, dropwise adding half of reducing agent aqueous solution, and reacting at 50 ℃ for 2 hours to obtain polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the rest aqueous phase solution again to serve as a shell aqueous phase, uniformly stirring, dripping the rest reducing agent aqueous solution, and reacting for 2 hours at 50 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
The characterization of the polymer microemulsion and the polymer microspheres therein was the same as in example 1, and the results are shown in table 1.
The inventor of the invention discovers that the microemulsion prepared by the invention can well solve the problems of unstable and easy layering of the polyacrylamide microemulsion in the prior art, and poor expansibility and poor plugging effect of polymer microspheres in the microemulsion after long-term aging, and can be intuitively seen from the data of the same ratio of examples 1-5 and comparative examples 2 and 3.
[ example 6 ]
The polymer microsphere of the embodiment is prepared by polymerization reaction of reverse microemulsion under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent; the oil-soluble solvent is white oil;
b) 10 parts of an emulsifier; the HLB value of the emulsifier is 6.7 (prepared by mixing span 60 (namely sorbitan monostearate) with HLB value of 4.7 and tween 20 (polyoxyethylene (20 EO) sorbitan monolaurate) with HLB value of 16.7);
c) 35 parts of hydrophilic monomer: consists of 18 parts of acrylamide, 12 parts of sodium acrylate and 5 parts of dimethyl diallyl ammonium chloride;
d) 5 parts of hydrophobic monomer: sodium 2-acrylamido-N-hexadecyl sulfonate;
e) 30 parts of water;
wherein, the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.5% of a water-soluble oxidant; the water-soluble oxidant is ammonium persulfate
(b) 0.8% of a water-soluble reducing agent; the water-soluble reducing agent is sodium bisulphite
(c) 1% of an oil-soluble azo compound; the oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% of a water-soluble cross-linking agent; the water-soluble cross-linking agent is N, N' -methylene bisacrylamide
(e) 5% urea;
(f) 0.3% disodium edetate;
(g) 1% sodium chloride.
The preparation method of the polymer microemulsion comprises the following specific steps:
(a) Preparing an oil phase: dissolving an emulsifier consisting of span 60 (HLB value is 4.7) with the HLB value of 6.7 and tween 20 (HLB value is 16.7) in 40 parts of the white oil, and uniformly stirring to obtain an oil phase I; dissolving azodiisobutyronitrile in 5 parts of the white oil, and uniformly stirring to obtain an oil phase II; dissolving 2-acrylamide-N-hexadecyl sodium sulfonate into 5 parts of the white oil, and uniformly stirring to obtain an oil phase III.
(b) Preparing an aqueous phase: 9 parts of acrylamide, 6 parts of sodium acrylate, 5 parts of dimethyl diallyl ammonium chloride and half of water-soluble composite initiator except sodium bisulphite are dissolved in 13 parts of water and uniformly stirred to obtain a nuclear water phase; dissolving the rest hydrophilic monomer and the rest water-soluble composite initiator except sodium bisulphite in 13 parts of water, and uniformly stirring to obtain a shell water phase; sodium bisulphite is dissolved in the rest water to form a reducer aqueous solution;
(c) Adding the oil phase I into a reactor, adding half of the oil phase II and all the nuclear water phase, uniformly stirring, then dropwise adding half of the reducing agent aqueous solution, and reacting for 2 hours at 50 ℃ to obtain the polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 30 ℃, adding the residual oil phase II, the oil phase III and all shell water phases again, uniformly stirring, dripping the residual reducing agent aqueous solution, and reacting for 2 hours at 50 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
Characterization of polymer microemulsions and wherein polymer microspheres:
testing initial particle size of microsphere according to measurement method of Q/SH1020 China petrochemical group victory Petroleum administration enterprise standard (Polymer microsphere deep profile control and flooding agent technical Condition) and total mineralization degree of 20×10 at 90 DEG C 4 mg/L，Ca 2+ +Mg 2+ : the expansion times of the particle sizes of the microspheres after aging for 7 days, 15 days and 30 days under the condition of 6000mg/L saline are measured by using a core displacement device, the blocking rate of the microspheres to 300mD artificial cores is measured, and the state of the obtained microemulsion system after standing for 3 months is observed, and the results are shown in table 1.
TABLE 1
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Claims (7)
1. The core-shell polymer microsphere is prepared by inverse microemulsion polymerization under the action of a redox composite initiator; the reverse microemulsion comprises the following components in parts by weight:
a) 50 parts of an oil-soluble solvent;
b) 3-20 parts of emulsifying agent;
c) 10-60 parts of hydrophilic monomer;
d) 0.5 to 10 parts of hydrophobic monomer;
e) 10-50 parts of water;
the composite initiator comprises the following components in percentage by weight of the total monomers:
(a) 0.02-1.0% of oxidant;
(b) 0.02-2.0% of reducing agent;
(c) 0.03 to 2.0 percent of azo compound;
(d) 0.01 to 1.0 percent of cross-linking agent;
(e) Urea and thiourea in 0.1-10 wt%;
(f) 0.01 to 0.5 percent of aminocarboxylic complexing agent;
(g) 0.5-5% of electrolyte salt;
the emulsifier is a nonionic surfactant mixture with HLB of 5-8, which is formed by compounding a nonionic surfactant with HLB of 1-7 and a nonionic surfactant with HLB of 8-18; the hydrophilic monomer is selected from at least one nonionic monomer, at least two anionic monomers, and at least one cationic monomer; the cross-linking agent is at least one selected from methylene bisacrylamide, polyethylene glycol diacrylate and pentaerythritol triacrylate;
the core-shell polymer microsphere is prepared by the following steps: (a) oil phase preparation: dissolving an emulsifier in an oil-soluble solvent, and uniformly stirring to obtain an oil phase I; dissolving an oil-soluble azo initiator in an oil-soluble solvent, and uniformly stirring to obtain an oil phase II; dissolving an oil-soluble hydrophobic monomer in an oil-soluble solvent, and uniformly stirring to obtain an oil phase III;
(b) Preparing an aqueous phase: dissolving 40-70 wt% of hydrophilic monomer and a water-soluble composite initiator except a reducing agent in water, and uniformly stirring to obtain a nuclear water phase; dissolving the rest hydrophilic monomers and a water-soluble composite initiator except a reducing agent in water, and uniformly stirring to obtain a shell water phase; dissolving a reducing agent in water to form a reducing agent aqueous solution;
(c) Adding the oil phase I into a reactor, adding 40-70wt% of the oil phase II and the nuclear water phase, uniformly stirring, then dropwise adding a reducing agent aqueous solution, and reacting for 1-4 hours at the temperature of 40-80 ℃ to obtain the polyacrylamide reverse phase microemulsion; after the reaction temperature is reduced to 20-30 ℃, adding the residual oil phase II, the oil phase III and the shell water phase again, stirring uniformly, dripping the aqueous solution of the reducing agent, and reacting for 1-4 hours at 40-80 ℃.
2. Core-shell polymer microspheres according to claim 1, characterized in that the oil-soluble solvent is selected from at least one of hydrocarbons or esters.
3. Core-shell polymer microspheres according to claim 1, characterized in that the non-ionic hydrophilic monomer is selected from at least one of acrylamide, methacrylamide, N-isopropylacrylamide, N-methylolacrylamide, t-butylacrylamide, N-vinylpyrrolidone, N-dimethylacrylamide, N-diethylacrylamide; the anionic hydrophilic monomer is selected from at least one of acrylic acid, methacrylic acid, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, vinylbenzenesulfonic acid, allylsulfonic acid, methacrylic acid, styrenesulfonic acid and/or water-soluble alkali metal, alkaline earth metal and ammonium salt; the cationic hydrophilic monomer is at least one selected from dimethyl diallyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl dimethyl benzyl ammonium chloride, methacryloxyethyl dimethyl benzyl ammonium chloride and methacryloxypropyl trimethyl ammonium chloride.
4. The core-shell polymer microsphere according to claim 1, wherein the hydrophobic monomer is at least one selected from the group consisting of N-phenylmaleimide, maleic anhydride, styrene derivatives, acrylamidoalkylsulfonates having a carbon chain number of 8 to 18, alkyl acrylates having a carbon chain number of 8 to 18, and fluoro-substituted alkyl acrylates having a carbon chain number of 8 to 18.
5. The core-shell polymer microsphere according to claim 1, characterized in that the oxidizing agent is selected from at least one of potassium persulfate, sodium persulfate, ammonium persulfate or benzoyl peroxide; the reducing agent is at least one selected from sodium sulfite, potassium sulfite, sodium bisulfite, potassium hydrogen sulfite, sodium thiosulfate and ferrous chloride; the azo compound is at least one selected from azo diisobutyl amidine hydrochloride, 2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride, azo diisobutyronitrile and azo diisoheptonitrile; the ammonia-carboxyl complexing agent is at least one selected from ethylenediamine tetraacetic acid and alkali metal salts thereof, diethylenetriamine pentaacetic acid and alkali metal salts thereof; the electrolyte salt is selected from at least one of water-soluble inorganic salt or organic acid salt.
6. The method for preparing the core-shell polymer microsphere according to any one of claims 1 to 5, comprising the following steps:
(a) Preparing an oil phase: dissolving an emulsifier in an oil-soluble solvent, and uniformly stirring to obtain an oil phase I; dissolving an oil-soluble azo initiator in an oil-soluble solvent, and uniformly stirring to obtain an oil phase II; dissolving an oil-soluble hydrophobic monomer in an oil-soluble solvent, and uniformly stirring to obtain an oil phase III;
(b) Preparing an aqueous phase: dissolving 40-70 wt% of hydrophilic monomer and a water-soluble composite initiator except a reducing agent in water, and uniformly stirring to obtain a nuclear water phase; dissolving the rest hydrophilic monomers and a water-soluble composite initiator except a reducing agent in water, and uniformly stirring to obtain a shell water phase; dissolving a reducing agent in water to form a reducing agent aqueous solution;
(c) Adding the oil phase I into a reactor, adding 40-70wt% of the oil phase II and the nuclear water phase, uniformly stirring, then dropwise adding a reducing agent aqueous solution, and reacting for 1-4 hours at the temperature of 40-80 ℃ to obtain the polyacrylamide reverse phase microemulsion; and (3) after the reaction temperature is reduced back to 20-30 ℃, adding the residual oil phase II, the oil phase III and the shell water phase again, stirring uniformly, dripping the aqueous solution of the reducing agent, and reacting for 1-4 hours at 40-80 ℃ to finally obtain the core-shell type polyacrylamide reverse microemulsion.
7. The use of a core-shell polymer microsphere according to any one of claims 1 to 5 in tertiary oil recovery of high temperature hypersalinity reservoirs.
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| CN102304201A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Hydrophobic association crosslinked polymer coil and preparation method thereof |
| CN104448126A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Harsh oil deposit reversed-phase microemulsion profile-control flooding system and preparation method thereof |
| CN104558402A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polymer microemulsion for deep profile control of oil reservoir |
| CN106866877A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | Oil deposit deep part transfer drive polymer microemulsion system and preparation method thereof |
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| CN102304201A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Hydrophobic association crosslinked polymer coil and preparation method thereof |
| CN104448126A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Harsh oil deposit reversed-phase microemulsion profile-control flooding system and preparation method thereof |
| CN104558402A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polymer microemulsion for deep profile control of oil reservoir |
| CN106866877A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | Oil deposit deep part transfer drive polymer microemulsion system and preparation method thereof |
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