CN109666099A - Core-shell polymers microballoon and preparation method thereof - Google Patents
Core-shell polymers microballoon and preparation method thereof Download PDFInfo
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- CN109666099A CN109666099A CN201710977799.3A CN201710977799A CN109666099A CN 109666099 A CN109666099 A CN 109666099A CN 201710977799 A CN201710977799 A CN 201710977799A CN 109666099 A CN109666099 A CN 109666099A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 239000011258 core-shell material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 80
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 239000003999 initiator Substances 0.000 claims abstract description 46
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 58
- -1 azo compound Chemical class 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 49
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 229920002401 polyacrylamide Polymers 0.000 claims description 27
- 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
- 150000001875 compounds Chemical class 0.000 claims description 20
- 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 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- 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 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical group [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 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
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 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
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class 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
- 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
- 239000002585 base Substances 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 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
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-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
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 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
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 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
- 239000001294 propane Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 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
- 235000019345 sodium thiosulphate Nutrition 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
- 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 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NVKHKMBMLSFNNU-UHFFFAOYSA-N C=CC1=CC=CC=C1.[S] Chemical compound C=CC1=CC=CC=C1.[S] NVKHKMBMLSFNNU-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims 1
- 229920003192 poly(bis maleimide) Polymers 0.000 claims 1
- WBABZTXAPOBPNZ-UHFFFAOYSA-N prop-2-enoylazanium;sulfamate Chemical compound NS([O-])(=O)=O.[NH3+]C(=O)C=C WBABZTXAPOBPNZ-UHFFFAOYSA-N 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 150000003440 styrenes Chemical class 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000032683 aging Effects 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000008346 aqueous phase Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007039 two-step reaction Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 105
- 239000003921 oil Substances 0.000 description 70
- 235000019198 oils Nutrition 0.000 description 70
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 33
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 33
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 33
- 229910052708 sodium Inorganic materials 0.000 description 25
- 239000011734 sodium Substances 0.000 description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 18
- 239000004971 Cross linker Substances 0.000 description 18
- 229940047670 sodium acrylate Drugs 0.000 description 18
- 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 17
- HVUMOYIDDBPOLL-UHFFFAOYSA-N 2-(3,4-Dihydroxyoxolan-2-yl)-2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)C1OCC(O)C1O HVUMOYIDDBPOLL-UHFFFAOYSA-N 0.000 description 16
- 150000003926 acrylamides Chemical class 0.000 description 16
- 239000000203 mixture Substances 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 10
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 9
- 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 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 9
- 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 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 239000001590 sorbitan monolaureate Substances 0.000 description 8
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 8
- 239000001587 sorbitan monostearate Substances 0.000 description 8
- 235000011076 sorbitan monostearate Nutrition 0.000 description 8
- 229940035048 sorbitan monostearate Drugs 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000009671 shengli Substances 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
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 241000406668 Loxodonta cyclotis Species 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
- 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
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004005 microsphere Substances 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
- 239000002245 particle Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-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
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical group C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 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
- JKPQNHCFWGLWBJ-UHFFFAOYSA-N N[Na].C(C=C)(=O)N Chemical compound N[Na].C(C=C)(=O)N JKPQNHCFWGLWBJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 description 1
- UFAGAQUHRODLFO-UHFFFAOYSA-M [Cl-].CC=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 Chemical compound [Cl-].CC=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 UFAGAQUHRODLFO-UHFFFAOYSA-M 0.000 description 1
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940060038 chlorine Drugs 0.000 description 1
- 235000017168 chlorine Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 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
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229940001474 sodium thiosulfate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 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
Abstract
The present invention relates to a kind of core-shell polymers microballoon and preparation method thereof, mainly solve the problems, such as that the polymer micro-emulsion of the prior art is unstable, polymer microballoon temperature-resistant anti-salt performance is poor, plugging effect is poor after long-term ageing.The present invention is under the effect of redox composite initiator, as made from the aggregated reaction of reverse micro emulsion by using core-shell polymers microballoon；The reverse micro emulsion includes based on parts by weight following components: 50 parts of oil-dissolving solvent；3~20 parts of emulsifier；10~60 parts of hydrophilic monomer；0.5~10 part of hydrophobic monomer；10~50 parts of water；Using the method for two-step reaction, the technical solution that the oil containing emulsifier mutually carries out polymerization reaction will be added with the aqueous phase solution substep of other hydrophilic monomers, hydrophobic monomer containing acrylamide, it preferably solves the problems, such as this, can be used for the tertiary oil recovery of high temperature and high salinity oil reservoir.
Description
Technical field
The present invention relates to a kind of core-shell polymers microballoons and preparation method thereof.
Background technique
Domestic each elephant is by primary, secondary oil recovery, and crude oil water content is continuously increased, and part elephant successively enters three
The secondary oil recovery stage.Polymer flooding is the main technique methods of tertiary oil recovery, and mechanism of oil displacement understands that technique is relatively easy, technology day
Become mature, is an effective raising recovery efficiency technique measure.However for inhomogeneous formation, displacement is only capable of acting on Thief zone
Layer, involves the less permeable layer less than oil-containing, this recovery ratio for having resulted in crude oil reduces, and cost increases.Generally directed to non-
Homogeneous formation is frequently with Profile Control in Injection Well and producing well water-plugging technique, but this technology effective range is only limitted near wellbore zone, no
It can be deep into well deep part, the purpose for increasing substantially oil recovery factor is not achieved, be badly in need of finding novel deep profile controlling thus
Water shutoff agent.
The one kind of polyacrylamide microsphere as most common organic water plugging profile control agent, has apparent selectivity to water, it
It is constant to meet oil volume, meets water then volume expansion, therefore has good water plugging effect, while having that validity period is long, do not pollute stratum, apply
The features such as work is simple, the activity duration is short.Since the permeability of oil reservoir is different and heterogeneity is more serious, need various sizes of
The profile control that polymer microballoon is just able to satisfy Different Strata, which blocks, to be required.
Recent domestic researcher polyacrylamide reverse microemulsion in terms of oil deposit deep part transfer drive material
There is more research, and achieves preferable progress and achievement.Patent CN1903974A has synthesized a kind of terpolymer nanometer ruler
Very little microgel oil displacing material makes decomposition of initiator using ultraviolet light using the low temperature photoinitiator of non-oxide reduction initiating system,
It generates living radical and causes polymerization, this is conducive to the stabilization of reverse micro emulsion, is conducive to the control of partial size, but emulsify in system
Agent content is up to 25% or more, is bound to cause high production cost.It is poly- that patent CN101759838A provides a kind of low interfacial tension
The preparation method of acrylamide nanosphere transfer drive system, have rated Shengli Oil Field stake because oil recovery factory stake 106 wells under the conditions of to original
The drop tension situation of oil, but the expansion character of polymer microballoon is not stated, therefore system is for the transfer drive ability of oil reservoir
It has no way of investigating.
Summary of the invention
The first technical problem to be solved by the present invention is that polymer micro-emulsion existing in the prior art is unstable, polymerize
Object microballoon temperature-resistant anti-salt performance is poor, after long-term ageing plugging effect difference problem, a kind of hud typed polyacrylamide microsphere is provided,
Polymer micro-emulsion of the invention have the characteristics that it is stable, and the polymer microballoon in the polymer micro-emulsion have heatproof
Anti-salt property is good, the good advantage of plugging effect after long-term ageing.
The second technical problem to be solved by the present invention is micro- with the core-shell polymers described in one of above-mentioned technical problem
The preparation method of ball.
The third technical problem to be solved by the present invention is the core-shell polymers microballoon in high temperature and high salinity oil
Hide the application in tertiary oil recovery.
One of to solve above-mentioned technical problem, technical scheme is as follows: a kind of core-shell polymers microballoon, be
Under the effect of redox composite initiator, as made from the aggregated reaction of reverse micro emulsion；The reverse micro emulsion, with weight
Number meter includes following components:
A) 50 parts of oil-dissolving solvent；
B) 3~20 parts of emulsifier；
C) 10~60 parts of hydrophilic monomer；
D) 0.5~10 part of hydrophobic monomer；
E) 10~50 parts of water.
In above-mentioned technical proposal, the composite initiator, in terms of above-mentioned whole weight percent monomers, comprising with the following group
Point:
(a) 0.02~1.0% oxidant；
(b) 0.02~2.0% reducing agent；
(c) 0.03~2.0% azo compound；
(d) 0.01~1.0% crosslinking agent；
(e) 0.1~10% urea, thiocarbamide；
(f) 0.01~0.5% complexones；
(g) 0.5~5% electrolytic salt.
Oil-dissolving solvent described in above-mentioned technical proposal preferably is selected from least one of hydrocarbon and ester.The hydrocarbon can be rouge
Fat hydrocarbon, aromatic hydrocarbon, petroleum distillate；The preferred C of aliphatic hydrocarbon4~C8Aliphatic hydrocarbon, such as thiacyclohexane, hexane, heptane, octane and
Isooctane etc.；The preferred C of the aromatic hydrocarbon6~C10Aromatic hydrocarbons, such as benzene,toluene,xylene, trimethylbenzene, ethylbenzene, diethylbenzene,
Isopropylbenzene etc.；The preferred white oil of the petroleum distillate, atoleine, gasoline, kerosene, diesel oil, petroleum ether etc..The ester is preferred
Carboxylate, it may be more preferable to C4~C8Monoesters, such as ethyl acetate, propyl acetate etc.；It can also more preferable C4~C10Dibasic acid esters, example
Such as dimethyl oxalate, diethy-aceto oxalate, methyl ethyl oxalate；Can also more preferable vegetable oil, vegetable oil preferably is selected from peanut oil, big
Soya-bean oil, sunflower oil and castor oil.
In above-mentioned technical proposal, the HLB value of the emulsifier is preferably 5~8.The more preferable non-ionic surface of emulsifier
Activating agent.The emulsifier is preferably living by the non-ionic surface of the HLB nonionic surfactant for being 1~7 and HLB8~18
Property agent be re-dubbed HLB be 5~8 non-ionic surfactant mixture form.The nonionic surfactant, such as fat
Alcohol, alkyl phenol, fatty acid, aliphatic ester or amine alkoxy addition product, such as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxy second
Alkene ether, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether etc., then such as polyalcohol part of hydroxyl esterification product, example
Such as the part of hydroxyl or whole hydroxyl-oxethyls of sorbitan fatty acid ester namely well known spans and polyalcohol
And aliphatic ester compound, such as Tweens.
In above-mentioned technical proposal, assistant for emulsifying agent can further include in the emulsifier.The assistant for emulsifying agent is optional
Small molecule alcohol.The preferred C of small molecular alcohol3~C12Alcohol, such as isopropanol, the tert-butyl alcohol, n-amyl alcohol etc..Assistant for emulsifying agent content
It is preferred that accounting for 5~30wt% of nonionic surfactant described in emulsifier.
In above-mentioned technical proposal, the hydrophilic monomer is in non-ionic monomer, anionic monomer and cationic monomer
At least one is further preferably selected from non-ionic monomer, anionic monomer and cationic monomer, most preferably selected from least one
Non-ionic monomer, at least two anionic monomers and at least one cationic monomer, four kinds of monomers have preferable collaboration at this time
Effect blocks efficiency highest；Non-ionic hydrophilic monomer is selected from acrylamide, Methacrylamide, n-isopropyl acrylamide, N-
Hydroxymethyl acrylamide, N-tert-butyl acrylamide, n-vinyl pyrrolidone, N, N- dimethylacrylamide, N, N- diethyl
At least one of acrylamide；Anionic hydrophilic monomer is selected from acrylic acid, methacrylic acid, itaconic acid, 2- acrylamido-
2- methyl propane sulfonic acid, vinyl sulfonic acid, vinylbenzenesulfonic acid, allyl sulphonic acid, methacrylic sulfonic acid, styrene sulfonic acid and/or
At least one of water-soluble alkali, alkaline-earth metal and ammonium salt；Cationic hydrophilic monomer is selected from dimethyl diallyl chlorination
Ammonium, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloxyethyldimethyl benzyl
Ammonium chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, in methacryl hydroxypropyltrimonium chloride at least
It is a kind of.
In above-mentioned technical proposal, the hydrophobic monomer is selected from N-phenylmaleimide, maleic anhydride, styrene and its spreads out
Biology, carbochain number be 8~18 acrylamide azanyl sodium sulfonate, carbochain number be 8~18 alkyl or fluorine replace alkyl
At least one of acid esters.
In above-mentioned technical proposal, the oxidant is selected from potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate or benzoyl peroxide
At least one of；Reducing agent is selected from sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, sodium thiosulfate, chlorine
Change at least one of ferrous iron；The azo compound is selected from azo diisobutyl amidine hydrochloride, 2,2'- azo [2- (2- miaow
Oxazoline -2- base) propane] dihydrochloride, azodiisobutyronitrile, at least one of azobisisoheptonitrile；Crosslinking agent is selected from methylene
Base bisacrylamide, divinylbenzene, polyethyleneglycol diacrylate, pentaerythritol triacrylate, N, N '-penylene span
Carry out at least one of acid imide；The complexones is selected from ethylenediamine tetra-acetic acid and its alkali metal salt, diethylenetriamine
At least one of pentaacetic acid and its alkali metal salt；The preferably water-soluble inorganic salts of the electrolytic salt or acylate.Institute
State inorganic salts preferred as alkali hydrochloride (such as sodium chloride, potassium chloride), alkali metal sulfates (such as sodium sulphate, potassium sulfate)；
The acylate preferred as alkali acylate, more preferable C2~C6The salt of the alkali metal of carboxylic acid, such as potassium acetate or acetic acid
Sodium.
In order to solve the above-mentioned technical problem two, the invention adopts the following technical scheme: the core-shell polymers are micro-
The preparation method of ball, comprising the following steps:
(a) oil is mutually prepared: emulsifier being dissolved in oil-dissolving solvent, is stirred evenly, oily phase I is obtained；Oil-soluble is crosslinked
Agent and oil-soluble azo initiator are dissolved in oil-dissolving solvent, are stirred evenly, and oily phase II is obtained；Oil-soluble hydrophobic monomer is dissolved in
It in oil-dissolving solvent, stirs evenly, obtains oily phase III.
(b) water phase is prepared: the hydrophilic monomer of 40~70wt%, the Water Soluble Compound initiator in addition to reducing agent are dissolved in water
In, stir evenly, obtain core water phase；By remaining hydrophilic monomer, the Water Soluble Compound initiator in addition to reducing agent it is soluble in water,
It stirs evenly, obtains shell water phase；It dissolves reduce agent in and forms reducing agent aqueous solution in water；
(c) reactor is added in oily phase I, the oily phase II and core water phase of 40~70wt% is added, stirs evenly, then be added dropwise also
Former agent aqueous solution reacts 1~4 hour at 40~80 DEG C, obtains polyacrylamide reverse microemulsion；15 are dropped back to reaction temperature~
35 DEG C, remaining oil phase II, oily phase III and shell water phase are added again, stirs evenly, then reducing agent aqueous solution is added dropwise, at 40~80 DEG C
Reaction 1~4 hour, finally obtains hud typed polyacrylamide reverse microemulsion.
Technical solution more preferably, above-mentioned steps (c) are as follows:
(c) reactor is added in oily phase I, the oily phase II and core water phase of 40~70wt% is added, stirs evenly, then be added dropwise also
Former agent aqueous solution reacts 2~3 hours at 50~60 DEG C, obtains polyacrylamide reverse microemulsion；25 are dropped back to reaction temperature~
30 DEG C, remaining oil phase II, oily phase III and shell water phase are added again, stirs evenly, then reducing agent aqueous solution is added dropwise, at 50~60 DEG C
Reaction 2~3 hours, finally obtains hud typed polyacrylamide reverse microemulsion.
To solve above-mentioned technical problem three, technical scheme is as follows: the core-shell polymers microballoon exists
Application in high temperature and high salinity oil reservoir tertiary oil recovery.
Polymer microballoon of the invention is suitable for 80~120 DEG C of high temperature and 10 × 104~30 × 104The high mine of mg/L
The oil reservoir of change degree.
Using technical solution of the present invention, obtained polymer micro-emulsion stand 3 months it is not stratified, it is in addition of the invention poly-
The polymer microballoon in object microemulsion is closed in 90 DEG C, total salinity 20 × 104mg/L、Ca2++Mg2+: under 6000mg/L brines
The expansion multiple of microspherulite diameter is up to 8 times or more after 15 days, while to the sealing ratiod of 300mD artificial core up to 85% or more,
Preferable technical effect is achieved, can be used in the tertiary oil recovery of high temperature and high salinity oil reservoir.
Below by specific embodiment, the present invention will be further elaborated.
Specific embodiment
[embodiment 1]
The polymer microballoon of the present embodiment, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 6 parts of sodium acrylate, 6 parts of 2- acrylamido -2- methyl-props
Sodium sulfonate and 5 parts of dimethyl diallyl ammonium chloride compositions；
D) 5 parts of hydrophobic monomer: 2- acrylamido-N- sodium cetanesulfonate；
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% oil-soluble azo compound；Oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 40 parts of white oils, stir evenly, obtain oily phase I；Azodiisobutyronitrile is dissolved in 5 parts of white oils
In, it stirs evenly, obtains oily phase II；2- acrylamido-N- sodium cetanesulfonate is dissolved in 5 parts of white oils, is stirred
Uniformly, oily phase III is obtained.
(b) water phase prepare: by 9 parts of acrylamides, 3 parts of sodium acrylate, 3 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium,
5 parts of dimethyl diallyl ammonium chlorides, the Water Soluble Compound initiator of half amount is dissolved in 13 parts of water in addition to sodium hydrogensulfite, is stirred
It mixes uniformly, obtains core water phase；By remaining hydrophilic monomer, remaining Water Soluble Compound initiator is dissolved in 13 in addition to sodium hydrogensulfite
In part water, stirs evenly, obtain shell water phase；Sodium hydrogensulfite is dissolved in the water of surplus and forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, the oily phase II and whole core water phases of half amount is added, stirs evenly, then be added dropwise one
The reducing agent aqueous solution of half amount, reacts 2 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion；30 are dropped back to reaction temperature
DEG C, remaining oil phase II, oily phase III and whole shell water phases are added again, stirs evenly, then remaining reducing agent aqueous solution is added dropwise,
50 DEG C are reacted 2 hours, and hud typed polyacrylamide reverse microemulsion is finally obtained.
The characterization of polymer micro-emulsion and wherein polymer microballoon:
By Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technology
Condition " measuring method test microballoon initial particle and in 90 DEG C, total salinity 20 × 104Mg/L, Ca2++Mg2+: 6000mg/L
Under brines after aging 7 days, 15 days, 30 days microspherulite diameter expansion multiple, utilize rock core displacement device to test microballoon pair
The sealing ratiod of 300mD artificial core, and the state after gained microemulsion system is stood 3 months is observed, the results are shown in Table 1.
[comparative example 1]
The polymer microballoon of this comparative example, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；The span 40 that emulsifier hlb value is 6.7；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 6 parts of sodium acrylate, 6 parts of 2- acrylamido -2- methyl-props
Sodium sulfonate and 5 parts of dimethyl diallyl ammonium chloride compositions；
D) 5 parts of hydrophobic monomer: 2- acrylamido-N- sodium cetanesulfonate；
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% oil-soluble azo compound；Oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: the HLB emulsifier span 40 for being 6.7 is dissolved in 40 parts of white oils, is stirred evenly,
Obtain oily phase I；Azodiisobutyronitrile is dissolved in 5 parts of white oils, is stirred evenly, oily phase II is obtained；By 2- acrylamido-
N- sodium cetanesulfonate is dissolved in 5 parts of white oils, is stirred evenly, and oily phase III is obtained.
(b) water phase prepare: by 9 parts of acrylamides, 3 parts of sodium acrylate, 3 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium,
5 parts of dimethyl diallyl ammonium chlorides, the Water Soluble Compound initiator of half amount is dissolved in 13 parts of water in addition to sodium hydrogensulfite, is stirred
It mixes uniformly, obtains core water phase；By remaining hydrophilic monomer, remaining Water Soluble Compound initiator is dissolved in 13 in addition to sodium hydrogensulfite
In part water, stirs evenly, obtain shell water phase；Sodium hydrogensulfite is dissolved in the water of surplus and forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, the oily phase II and whole core water phases of half amount is added, stirs evenly, then be added dropwise one
The reducing agent aqueous solution of half amount, reacts 2 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion；30 are dropped back to reaction temperature
DEG C, remaining oil phase II, oily phase III and whole shell water phases are added again, stirs evenly, then remaining reducing agent aqueous solution is added dropwise,
50 DEG C are reacted 2 hours, and hud typed polyacrylamide reverse microemulsion is finally obtained.
The characterizing method of polymer micro-emulsion and wherein polymer microballoon is same as Example 1, and the results are shown in Table 1.
It was found by the inventors of the present invention that the non-ionic surface that it is 1~7 by HLB that emulsifier used in the present invention, which is preferably, is living
Property agent and HLB be 8~18 nonionic surfactant be re-dubbed the non-ionic surfactant mixture that HLB is 5~8, this
When HLB is 1~7 in obtained non-ionic surfactant mixture nonionic surfactant and HLB be 8~18 it is non-
Ionic surface active agent is micro- in the polymer for improving pam microemulsion stability of emulsion with improving in polyacrylamide microemulsion
There is synergistic effect in terms of ball dilatancy.This can intuitively find out from embodiment 1, the year-on-year data of comparative example 1.
[embodiment 2]
The polymer microballoon of the present embodiment, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 6 parts of sodium acrylate, 6 parts of 2- acrylamido -2- methyl-props
Sodium sulfonate and 5 parts of dimethyl diallyl ammonium chloride compositions；
D) 5 parts of hydrophobic monomer: octadecyl methacrylate；
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% oil-soluble azo compound；Oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 40 parts of white oils, stir evenly, obtain oily phase I；Azodiisobutyronitrile is dissolved in 5 parts of white oils
In, it stirs evenly, obtains oily phase II；Octadecyl methacrylate is dissolved in 5 parts of white oils, is stirred evenly, oily phase is obtained
Ⅲ。
(b) water phase prepare: by 9 parts of acrylamides, 3 parts of sodium acrylate, 3 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium,
5 parts of dimethyl diallyl ammonium chlorides, the Water Soluble Compound initiator of half amount is dissolved in 13 parts of water in addition to sodium hydrogensulfite, is stirred
It mixes uniformly, obtains core water phase；By remaining hydrophilic monomer, remaining Water Soluble Compound initiator is dissolved in 13 in addition to sodium hydrogensulfite
In part water, stirs evenly, obtain shell water phase；Sodium hydrogensulfite is dissolved in the water of surplus and forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, the oily phase II and whole core water phases of half amount is added, stirs evenly, then be added dropwise one
The reducing agent aqueous solution of half amount, reacts 2 hours at 60 DEG C, obtains polyacrylamide reverse microemulsion；30 are dropped back to reaction temperature
DEG C, remaining oil phase II, oily phase III and whole shell water phases are added again, stirs evenly, then remaining reducing agent aqueous solution is added dropwise,
60 DEG C are reacted 2 hours, and hud typed polyacrylamide reverse microemulsion is finally obtained.
The characterizing method of polymer micro-emulsion and wherein polymer microballoon is same as Example 1, and the results are shown in Table 1.
[embodiment 3]
The polymer microballoon of the present embodiment, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 6 parts of sodium acrylate, 6 parts of 2- acrylamido -2- methyl-props
Sodium sulfonate and 5 parts of dimethyl diallyl ammonium chloride compositions；
D) 5 parts of hydrophobic monomer: p-tert-butylstyrene；
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% water-soluble azo class compound；Water-soluble azo class compound is 2,2'- azo [2- (2- imidazoline-
2- yl) propane] dihydrochloride
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 45 parts of white oils, stir evenly, obtain oily phase I；By p-tert-butylstyrene be dissolved in 5 parts it is described white
It in oil, stirs evenly, obtains oily phase II.
(b) water phase prepare: by 9 parts of acrylamides, 3 parts of sodium acrylate, 3 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium,
5 parts of dimethyl diallyl ammonium chlorides, the Water Soluble Compound initiator of half amount is dissolved in 13 parts of water in addition to sodium hydrogensulfite, is stirred
It mixes uniformly, obtains core water phase；By remaining hydrophilic monomer, remaining Water Soluble Compound initiator is dissolved in 13 in addition to sodium hydrogensulfite
In part water, stirs evenly, obtain shell water phase；Sodium hydrogensulfite is dissolved in the water of surplus and forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, whole core water phases is added, stir evenly, then be added dropwise half amount reducing agent it is water-soluble
Liquid reacts 3 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion；30 DEG C are dropped back to reaction temperature, oily phase II is added again
And whole shell water phases, it stirs evenly, then remaining reducing agent aqueous solution is added dropwise, reacts 3 hours, finally obtain hud typed at 50 DEG C
Polyacrylamide reverse microemulsion.
The characterizing method of polymer micro-emulsion and wherein polymer microballoon is same as Example 1, and the results are shown in Table 1.
[embodiment 4]
The polymer microballoon of the present embodiment, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 6 parts of sodium acrylate, 6 parts of 2- acrylamido -2- methyl-props
Sodium sulfonate and 5 parts of dimethyl diallyl ammonium chloride compositions；
D) 5 parts of hydrophobic monomer: N-phenylmaleimide；
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% water-soluble azo class compound；Water-soluble azo class compound is 2,2'- azo [2- (2- imidazoline-
2- yl) propane] dihydrochloride
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 45 parts of white oils, stir evenly, obtain oily phase I；N-phenylmaleimide is dissolved in described in 5 parts
It in white oil, stirs evenly, obtains oily phase II.
(b) water phase prepare: by 9 parts of acrylamides, 3 parts of sodium acrylate, 3 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium,
5 parts of dimethyl diallyl ammonium chlorides, the Water Soluble Compound initiator of half amount is dissolved in 13 parts of water in addition to sodium hydrogensulfite, is stirred
It mixes uniformly, obtains core water phase；By remaining hydrophilic monomer, remaining Water Soluble Compound initiator is dissolved in 13 in addition to sodium hydrogensulfite
In part water, stirs evenly, obtain shell water phase；Sodium hydrogensulfite is dissolved in the water of surplus and forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, whole core water phases is added, stir evenly, then be added dropwise half amount reducing agent it is water-soluble
Liquid reacts 3 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion；30 DEG C are dropped back to reaction temperature, oily phase II is added again
And whole shell water phases, it stirs evenly, then remaining reducing agent aqueous solution is added dropwise, reacts 3 hours, finally obtain hud typed at 50 DEG C
Polyacrylamide reverse microemulsion.
The characterizing method of polymer micro-emulsion and wherein polymer microballoon is same as Example 1, and the results are shown in Table 1.
[embodiment 5]
The polymer microballoon of the present embodiment, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 6 parts of sodium acrylate, 6 parts of 2- acrylamido -2- methyl-props
Sodium sulfonate and 5 parts of acrylyl oxy-ethyl-trimethyl salmiac compositions；
D) 5 parts of hydrophobic monomer: maleic anhydride
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% water-soluble azo class compound；Water-soluble azo class compound is 2,2'- azo [2- (2- imidazoline-
2- yl) propane] dihydrochloride
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 45 parts of white oils, stir evenly, obtain oily phase I；Maleic anhydride is dissolved in 5 parts of white oils,
It stirs evenly, obtains oily phase II.
(b) water phase prepare: by 9 parts of acrylamides, 3 parts of sodium acrylate, 3 parts of 2- acrylamide-2-methylpro panesulfonic acid sodium,
5 parts of acrylyl oxy-ethyl-trimethyl salmiacs, the Water Soluble Compound initiator of half amount is dissolved in 13 parts of water in addition to sodium hydrogensulfite
In, it stirs evenly, obtains core water phase；By remaining hydrophilic monomer, the remaining Water Soluble Compound initiator in addition to sodium hydrogensulfite
It is dissolved in 13 parts of water, stirs evenly, obtain shell water phase；Sodium hydrogensulfite is dissolved in the water of surplus and forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, whole core water phases is added, stir evenly, then be added dropwise half amount reducing agent it is water-soluble
Liquid reacts 2 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion；30 DEG C are dropped back to reaction temperature, oily phase II is added again
And whole shell water phases, it stirs evenly, then remaining reducing agent aqueous solution is added dropwise, reacts 2 hours, finally obtain hud typed at 50 DEG C
Polyacrylamide reverse microemulsion.
The characterizing method of polymer micro-emulsion and wherein polymer microballoon is same as Example 1, and the results are shown in Table 1.
[comparative example 2]
The polymer microballoon of this comparative example, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 6 parts of sodium acrylate, 6 parts of 2- acrylamido -2- methyl-props
Sodium sulfonate and 5 parts of dimethyl diallyl ammonium chloride compositions；
D) 5 parts of hydrophobic monomer: 2- acrylamido-N- sodium cetanesulfonate；
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% oil-soluble azo compound；Oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 40 parts of white oils, stir evenly, obtain oily phase I；By azodiisobutyronitrile, 2- acrylamido-
N- sodium cetanesulfonate is dissolved in 10 parts of white oils, is stirred evenly, and oily phase II is obtained.
(b) water phase is prepared: by acrylamide, sodium acrylate, 2- acrylamide-2-methylpro panesulfonic acid sodium, dimethyl two
Allyl ammonium chloride, the Water Soluble Compound initiator in addition to sodium hydrogensulfite are dissolved in 26 parts of water, are stirred evenly, are obtained water phase；
Sodium hydrogensulfite is dissolved in the water of surplus and forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, oily phase II and whole water phases is added, stirs evenly, then that reducing agent is added dropwise is water-soluble
Liquid reacts 4 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion.
The characterizing method of polymer micro-emulsion and wherein polymer microballoon is same as Example 1, and the results are shown in Table 1.
[comparative example 3]
The polymer microballoon of this comparative example, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 40 parts of hydrophilic monomer: by 20 parts of acrylamides, 10 parts of sodium acrylate and 10 parts of 2- acrylamido -2- methyl
Propanesulfonate；
D) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% water-soluble azo class compound；Water-soluble azo class compound is 2,2'- azo [2- (2- imidazoline-
2- yl) propane] dihydrochloride
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 50 parts of white oils, stir evenly, obtain oily phase.
(b) water phase is prepared: by acrylamide, sodium acrylate, 2- acrylamide-2-methylpro panesulfonic acid sodium, removing sulfurous acid
Water Soluble Compound initiator outside hydrogen sodium is dissolved in 26 parts of water, is stirred evenly, is obtained water phase；Sodium hydrogensulfite is dissolved in surplus
Reducing agent aqueous solution is formed in water；
(c) oil is added to reactor, the aqueous phase solution that half amount is added is stirred evenly as core water phase, then is added dropwise one
The reducing agent aqueous solution of half amount, reacts 2 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion；30 are dropped back to reaction temperature
DEG C, remaining aqueous phase solution is added again as shell water phase, stirs evenly, then remaining reducing agent aqueous solution is added dropwise, at 50 DEG C
Reaction 2 hours, finally obtains hud typed polyacrylamide reverse microemulsion.
The characterizing method of polymer micro-emulsion and wherein polymer microballoon is same as Example 1, and the results are shown in Table 1.
It was found by the inventors of the present invention that microemulsion prepared by the present invention can well solve the polypropylene of the prior art
The unstable easy layering of amide microemulsion, polymer microballoon dilatancy in microemulsion is poor, plugging effect difference asks after long-term ageing
Topic, this can intuitively find out from Examples 1 to 5 and the year-on-year data of comparative example 2 and 3.
[embodiment 6]
The polymer microballoon of the present embodiment, be redox composite initiator effect under, it is aggregated by reverse micro emulsion
Made from reaction；The reverse micro emulsion includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；Oil-dissolving solvent is white oil；
B) 10 parts of emulsifier；Emulsifier hlb value is 6.7 (by sorbester p18 (i.e. sorbitan monostearate) HLB value
4.7；Polysorbas20 (polyoxyethylene (20EO) sorbitanmonolaureate) HLB value 16.7 mixes)；
C) 35 parts of hydrophilic monomer: by 18 parts of acrylamides, 12 parts of sodium acrylate and 5 parts of dimethyl diallyl ammonium chlorides
Composition；
D) 5 parts of hydrophobic monomer: 2- acrylamido-N- sodium cetanesulfonate；
E) 30 parts of water；
Wherein, the composite initiator includes following components in terms of above-mentioned whole weight percent monomers:
(a) 0.5% water-soluble oxidizers；Water-soluble oxidizers are ammonium persulfate
(b) 0.8% water-soluble reducing agent；Water-soluble reducing agent is sodium hydrogensulfite
(c) 1% oil-soluble azo compound；Oil-soluble azo compound is azodiisobutyronitrile
(d) 0.5% water-soluble cross-linker；Water-soluble cross-linker is N, N '-methylene-bisacrylamide
(e) 5% urea；
(f) 0.3% disodium ethylene diamine tetraacetate；
(g) 1% sodium chloride.
The specific preparation step of polymer micro-emulsion are as follows:
(a) oil is mutually prepared: by the HLB sorbester p18 (HLB value 4.7) for being 6.7 and polysorbas20 (HLB value 16.7) group
At emulsifier be dissolved in 40 parts of white oils, stir evenly, obtain oily phase I；Azodiisobutyronitrile is dissolved in 5 parts of white oils
In, it stirs evenly, obtains oily phase II；2- acrylamido-N- sodium cetanesulfonate is dissolved in 5 parts of white oils, is stirred
Uniformly, oily phase III is obtained.
(b) water phase is prepared: by 9 parts of acrylamides, 6 parts of sodium acrylate, 5 parts of dimethyl diallyl ammonium chlorides, removing sulfurous
The Water Soluble Compound initiator of the outer half amount of sour hydrogen sodium is dissolved in 13 parts of water, is stirred evenly, is obtained core water phase；It will be remaining hydrophilic
Monomer, remaining Water Soluble Compound initiator is dissolved in 13 parts of water in addition to sodium hydrogensulfite, is stirred evenly, is obtained shell water phase；It will
Sodium hydrogensulfite, which is dissolved in the water of surplus, forms reducing agent aqueous solution；
(c) reactor is added in oily phase I, the oily phase II and whole core water phases of half amount is added, stirs evenly, then be added dropwise one
The reducing agent aqueous solution of half amount, reacts 2 hours at 50 DEG C, obtains polyacrylamide reverse microemulsion；30 are dropped back to reaction temperature
DEG C, remaining oil phase II, oily phase III and whole shell water phases are added again, stirs evenly, then remaining reducing agent aqueous solution is added dropwise,
50 DEG C are reacted 2 hours, and hud typed polyacrylamide reverse microemulsion is finally obtained.
The characterization of polymer micro-emulsion and wherein polymer microballoon:
By Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technology
Condition " measuring method test microballoon initial particle and in 90 DEG C, total salinity 20 × 104Mg/L, Ca2++Mg2+: 6000mg/L
Under brines after aging 7 days, 15 days, 30 days microspherulite diameter expansion multiple, utilize rock core displacement device to test microballoon pair
The sealing ratiod of 300mD artificial core, and the state after gained microemulsion system is stood 3 months is observed, the results are shown in Table 1.
Table 1
Claims (10)
1. a kind of core-shell polymers microballoon is made under the effect of redox composite initiator by conversed phase micro emulsion copolymerization；Institute
The reverse micro emulsion stated includes based on parts by weight following components:
A) 50 parts of oil-dissolving solvent；
B) 3~20 parts of emulsifier；
C) 10~60 parts of hydrophilic monomer；
D) 0.5~10 part of hydrophobic monomer；
E) 10~50 parts of water.
2. core-shell polymers microballoon according to claim 1, it is characterised in that the composite initiator is described complete to account for
Portion's weight percent monomer meter includes following components:
(a) 0.02~1.0% oxidant；
(b) 0.02~2.0% reducing agent；
(c) 0.03~2.0% azo compound；
(d) 0.01~1.0% crosslinking agent；
(e) 0.1~10% urea, thiocarbamide；
(f) 0.01~0.5% complexones；
(g) 0.5~5% electrolytic salt.
3. core-shell polymers microballoon according to claim 1, it is characterised in that the oil-dissolving solvent is selected from hydrocarbon or ester
At least one of.
4. core-shell polymers microballoon according to claim 1, it is characterised in that the HLB value of the emulsifier is 4~9.
5. core-shell polymers microballoon according to claim 1, it is characterised in that the hydrophilic monomer is selected from nonionic list
At least one of body, anionic monomer and cationic monomer.
6. core-shell polymers microballoon according to claim 5, it is characterised in that the non-ionic hydrophilic monomer is selected from third
Acrylamide, Methacrylamide, n-isopropyl acrylamide, N hydroxymethyl acrylamide, N-tert-butyl acrylamide, N- vinyl
Pyrrolidones, N, N- dimethylacrylamide, N, at least one of N- acrylamide；The anionic hydrophilic monomer
Selected from acrylic acid, methacrylic acid, itaconic acid, 2- acrylamide-2-methylpro panesulfonic acid, vinyl sulfonic acid, vinyl benzene sulphur
In acid, allyl sulphonic acid, methacrylic sulfonic acid, styrene sulfonic acid and/or water-soluble alkali, alkaline-earth metal and ammonium salt at least
It is a kind of；The cationic hydrophilic monomer is selected from dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methyl
Acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl benzyl ammonium chloride, methylacryoyloxyethyl dimethyl
At least one of benzyl ammonium chloride, methacryl hydroxypropyltrimonium chloride.
7. core-shell polymers microballoon according to claim 1, it is characterised in that the hydrophobic monomer is selected from N- phenyl horse
Come acid imide, maleic anhydride, styrene, styrene derivative, the acrylamide azanyl sulfonate that carbochain number is 8~18, carbon
At least one of alkyl acrylate or 8~18 fluorine substitution alkyl acrylate that chain number is 8~18.
8. core-shell polymers microballoon according to claim 2, it is characterised in that the oxidant is selected from potassium peroxydisulfate, mistake
At least one of sodium sulphate, ammonium persulfate or benzoyl peroxide；The reducing agent is selected from sodium sulfite, potassium sulfite, sub-
At least one of sodium bisulfate, potassium bisulfite, sodium thiosulfate, frerrous chloride；The azo compound is selected from azo
Diisobutyl amidine hydrochloride, 2,2'- azo [2- (2- imidazoline -2- base) propane] dihydrochloride, azodiisobutyronitrile, azo two
At least one of different heptonitrile；The crosslinking agent is selected from methylene-bisacrylamide, divinylbenzene, polyethylene glycol diacrylate
Ester, pentaerythritol triacrylate, N, at least one of N '-penylene bismaleimide；The complexones choosing
From at least one of ethylenediamine tetra-acetic acid and its alkali metal salt, diethylene triamine pentacetic acid (DTPA) and its alkali metal salt；The electrolysis
Matter salt is selected from least one of water-soluble inorganic salts or acylate.
9. the preparation method of any core-shell polymers microballoon of claim 1~8, comprising the following steps:
(a) oil is mutually prepared: emulsifier being dissolved in oil-dissolving solvent, is stirred evenly, oily phase I is obtained；By oil-soluble crosslinking agent and
Oil-soluble azo initiator is dissolved in oil-dissolving solvent, is stirred evenly, and oily phase II is obtained；It is molten that oil-soluble hydrophobic monomer is dissolved in oil
In property solvent, stirs evenly, obtain oily phase III；
(b) water phase is prepared: by the hydrophilic monomer of 40~70wt%, the Water Soluble Compound initiator in addition to reducing agent it is soluble in water,
It stirs evenly, obtains core water phase；By remaining hydrophilic monomer, the Water Soluble Compound initiator in addition to reducing agent is soluble in water, stirs
It mixes uniformly, obtains shell water phase；It dissolves reduce agent in and forms reducing agent aqueous solution in water；
(c) reactor is added in oily phase I, the oily phase II and core water phase of 40~70wt% is added, stirs evenly, then reducing agent is added dropwise
Aqueous solution reacts 1~4 hour at 40~80 DEG C, obtains polyacrylamide reverse microemulsion；20~30 are dropped back to reaction temperature
DEG C, remaining oil phase II, oily phase III and shell water phase are added again, stirs evenly, then reducing agent aqueous solution is added dropwise, it is anti-at 40~80 DEG C
It answers 1~4 hour, finally obtains hud typed polyacrylamide reverse microemulsion.
10. a kind of core-shell polymers microballoon answering in high temperature and high salinity oil reservoir tertiary oil recovery described in claim 1~8
With.
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