CN107337762A - A kind of hydrophobic association cross-linked polymer microsphere, preparation method and application - Google Patents
A kind of hydrophobic association cross-linked polymer microsphere, preparation method and application Download PDFInfo
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- CN107337762A CN107337762A CN201710697349.9A CN201710697349A CN107337762A CN 107337762 A CN107337762 A CN 107337762A CN 201710697349 A CN201710697349 A CN 201710697349A CN 107337762 A CN107337762 A CN 107337762A
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- Prior art keywords
- linked polymer
- hydrophobic association
- hydrophobic
- polymer microsphere
- parts
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- Granted
Links
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 79
- 239000004005 microsphere Substances 0.000 title claims abstract description 53
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000000178 monomer Substances 0.000 claims abstract description 39
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 23
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000001632 sodium acetate Substances 0.000 claims abstract description 21
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002091 cationic group Chemical group 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract 2
- 239000003995 emulsifying agent Substances 0.000 claims description 40
- 239000003921 oil Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 28
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 18
- 229920000053 polysorbate 80 Polymers 0.000 claims description 18
- 239000003795 chemical substances by application Substances 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 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 14
- 238000012688 inverse emulsion polymerization Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 235000019394 potassium persulphate Nutrition 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- -1 propylene Acid amides Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 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 8
- 230000000694 effects Effects 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 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 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- NWGKJDSIEKMTRX-MDZDMXLPSA-N Sorbitan oleate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(O)C1OCC(O)C1O NWGKJDSIEKMTRX-MDZDMXLPSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 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
- BFOCLBAICAUQTA-UHFFFAOYSA-N 2-methylpropane;prop-2-enamide Chemical compound CC(C)C.NC(=O)C=C BFOCLBAICAUQTA-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 239000008267 milk Substances 0.000 claims 1
- 210000004080 milk Anatomy 0.000 claims 1
- 235000013336 milk Nutrition 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 230000001960 triggered effect Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 3
- UHQADSBKMJUJEK-UHFFFAOYSA-N 2-methylidenetetradecanamide Chemical class CCCCCCCCCCCCC(=C)C(N)=O UHQADSBKMJUJEK-UHFFFAOYSA-N 0.000 abstract 1
- LYZHOFRUQBPSMA-UHFFFAOYSA-N n-(2-butylphenyl)prop-2-enamide Chemical class CCCCC1=CC=CC=C1NC(=O)C=C LYZHOFRUQBPSMA-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 17
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 235000010265 sodium sulphite Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XQPVIMDDIXCFFS-UHFFFAOYSA-N n-dodecylprop-2-enamide Chemical group CCCCCCCCCCCCNC(=O)C=C XQPVIMDDIXCFFS-UHFFFAOYSA-N 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 206010068516 Encapsulation reaction Diseases 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002349 well water Substances 0.000 description 2
- 235000020681 well water Nutrition 0.000 description 2
- FGRJGEWVJCCOJJ-UHFFFAOYSA-N 2,2-dimethylaziridine Chemical compound CC1(C)CN1 FGRJGEWVJCCOJJ-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical class NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical class CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NVXPGYQFMHYZPB-UHFFFAOYSA-N CCCl(C)(C)(C)OC(=O)C=C Chemical compound CCCl(C)(C)(C)OC(=O)C=C NVXPGYQFMHYZPB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 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
- 239000005864 Sulphur Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical class O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
Abstract
The present invention relates to a kind of hydrophobic association cross-linked polymer microsphere, the hydrophobic association cross-linked polymer microsphere is obtained by acrylamide, sodium acetate, hydrophobic monomer, olefin sulfonic acid, cationic monomer and the inverted emulsion polymerization of crosslinking agent；One or more of the hydrophobic monomer in methyl methacrylate, styrene, vinyl trimethylsilane, N dodecylacrylamides, N n-butylphenyl acrylamides.Hydrophobic association cross-linked polymer microsphere provided by the invention has significant heat and salinity tolerance performance, space crosslink density is big, network structure is stable, and has preferable viscoplasticity, while can control the speed of expansion of hydrophobic association crosslinked microsphere to a certain extent, hydrophobic association crosslinked microsphere viscosity is low,, can be by oil field waste prepared and diluted, in the presence of pump with preferable stability, lower pressure can smoothly enter earth formation deep, and the stratum that matches is blocked after water-swellable.
Description
Technical field
The present invention relates to the profile control and water plugging technology field of oil field oil reservoir, more particularly to a kind of hydrophobic association cross-linked polymer are micro-
Ball, preparation method and application.
Background technology
Extensive problems faced when well water turns into crude oil extraction, these problems can largely effect on production and the effect in oil field
Benefit, the oilfield exploitation that water drive is carried out is wherein impacted especially serious place.Often sent out during the waterflooding development in later stage
Raw well water.So Water in Water Shutoff in Oil Field profile control problem is more and more severeer.At present, it is at most polyacrylamide aqueous amine that oil field, which uses,
Solution carries out selective water plugging with cross-linking agents.The polyacrylamide profile control and water plugging technology used at present still has many offices
It is sex-limited, it have impact on it and apply scale.It is primarily present following several respects problem：First, polyacrylamide is mostly pulvis, dispersing and dissolving
Difficulty, site operation are inconvenient；Second, gelation time and gelling strength are difficult to control, often near wellbore zone is stifled adjusts effect good, and
It is difficult to reach earth formation deep and plays a role；Third, the temperature tolerance of conventional polypropylene acid amides profile-controlling and plugging agent, salt tolerance are poor, intensity
Low, the term of validity is short, is subject to certain restrictions in many applications.
Inverse emulsion polymerization is a kind of important technology for preparing polymer.It refers to the solution of water-soluble monomer in emulsifying agent
In the presence of (generally nonionic emulsifier), it is scattered in oil phase (aliphatic hydrocarbon or aromatic hydrocarbon), is stirred vigorously down, forms breast
Liquid, then trigger polymerization, obtain polymer.It is domestic by the preparation that inverse emulsion polymerization method is applied to oil field oil reservoir water shutoff agent
A kind of emerging technology.Using inverse emulsion polymerization method prepare and can obtain relatively stable reaction rate, higher
Polymer molecular weight.But there is also it is following the problem of：
(1) reversed-phase emulsion volume stability is poor, sensitiveer to temperature, mixing speed etc., easily occurs emulsifying not thorough
Phenomenon, be layered.
(2) oligomer present in the easy encapsulation reaction system in polymer microballoon surface, cause polymer microballoon viscosity high,
It is not easily accessible bottom deep or needs elevated pressures to enter earth formation deep.
(3) polymer microballoon space crosslink density is small, and network structure portion is unstable, poor flexibility, in water lower ground layer
Block inefficient.
(4) polymer microballoon heat and salinity tolerance performance is poor, and the use on high mineralization stratum is restricted.
The content of the invention
(1) technical problems to be solved
The present invention is to solve existing when preparing oil field oil reservoir water shutoff agent using inverse emulsion polymerization method ask as follows
Topic：Reversed-phase emulsion volume stability is poor, sensitiveer to temperature, mixing speed etc., easily occurs emulsifying halfway phenomenon, hair
Oligomer present in layer estranged, the easy encapsulation reaction system in polymer microballoon surface, cause polymer microballoon viscosity high, be not easy
Into bottom deep or small, the netted knot that needs elevated pressures to enter earth formation deep, polymer microballoon space crosslink density
Structure portion is unstable, poor flexibility, and in water, lower ground layer closure inefficient, polymer microballoon heat and salinity tolerance performance are poor, in Gao Kuang
The use for changing stratum is restricted.
(2) technical scheme
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
1st, a kind of hydrophobic association cross-linked polymer microsphere, the hydrophobic association cross-linked polymer microsphere is by acrylamide, vinegar
Sour sodium, hydrophobic monomer, olefin sulfonic acid, cationic monomer and crosslinking agent is aggregated obtains；
The hydrophobic monomer is selected from methyl methacrylate, styrene, vinyl trimethylsilane, N- dodecyl propylene
One or more in acid amides, N- n-butylphenyl acrylamides.
2nd, preferably, the acrylamide, the sodium acetate, the hydrophobic monomer, the olefin sulfonic acid, the cation
The mass ratio of monomer and the crosslinking agent is (200-350)：(15-25)：(0.5-3)：(5-15)：(10-20)：(0.2-1.5).
3rd, preferably, in parts by weight, the hydrophobic association cross-linked polymer microsphere be by 200-350 parts acrylamide,
15-25 parts sodium acetate, 0.5-3 parts hydrophobic monomer, 5-15 parts olefin sulfonic acid, 10-20 parts cationic monomer and the crosslinking of 0.2-1.5 parts
Agent is mixed in 240-300 parts oil-based solvent and 290-430 part deionized waters, under the effect of 12-30 parts emulsifying agent, with 0.003-
1.5 parts of initiators trigger, and are prepared by inverse emulsion polymerization, and 25 parts of phase inversion agent octyl phenols are added in obtained light yellow emulsion
APEO, hydrophobic association crosslinked microsphere is obtained after being sufficiently mixed.
4th, preferably, the emulsifying agent is compound emulsifying agent, and the compound emulsifying agent includes Tween 80, sorbester p17 and 12
Alcohol sodium maleate, and the compound emulsifying agent HLB value (Hydrophile-Lipophile Balance Number, i.e., it is hydrophilic
Lipophilic balance value) it is 4.5~6.0.
5th, preferably, the preparation method of the lauryl alcohol sodium maleate includes：
Lauryl alcohol, maleic anhydride and organic solvent are mixed, under catalyst action, reacted under conditions of 80-85 DEG C,
Obtain lauryl alcohol sodium maleate；
Preferably, the mol ratio of the lauryl alcohol and the maleic anhydride is 1:1；With
The catalyst is S2O8 2-/ZrO2-SiO2。
6th, preferably, the initial particle of the hydrophobic association cross-linked polymer microsphere is 100-350nm.
7th, preferably, the olefin sulfonic acid is selected from 2- acrylamide-2-methyl propane sulfonics, vinyl sulfonic acid, pi-allyl sulphur
One or more in acid, methacrylic sulfonic acid；
The cationic monomer is selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl chlorination
One or more in ammonium, dimethyl diallyl ammonium chloride；And/or
The crosslinking agent is selected from N,N methylene bis acrylamide, N, N- DMAAs, the allyl of pentaerythrite three
One or more in base ether.
8th, preferably, the initiator includes azodiisobutyronitrile, potassium peroxydisulfate and sodium hydrogensulfite；And/or
The oil-based solvent is in thiacyclohexane, hexane, heptane, octane, isooctane, white oil, gasoline, diesel oil, kerosene
It is one or more.
9th, a kind of preparation method of hydrophobic association cross-linked polymer microsphere, the preparation method comprise the following steps：
By acrylamide, sodium acetate, hydrophobic monomer, olefin sulfonic acid, cationic monomer and crosslinking agent are mixed in water, regulation
The pH of mixed solution is 6.8-7.0；
Oxidant, oil-based solvent and the emulsifying agent added in initiator, stirring, then letting nitrogen in and deoxidizing, then 16~18
The reducing agent added at DEG C in initiator triggers inverse emulsion polymerization, and phase inversion agent is added after the completion of reaction and obtains the hydrophobic association
Cross-linked polymer microsphere；Wherein, polymerization temperature is controlled to be no more than 40 DEG C, polymerization time is 3~4h.
10th, application of the hydrophobic association cross-linked polymer microsphere in water shutoff agent.
(3) beneficial effect
The above-mentioned technical proposal of the present invention has the following advantages that：
Hydrophobic association cross-linked polymer microsphere provided by the invention has significant heat and salinity tolerance performance, space crosslink density
Greatly, network structure is stable, and has preferable viscoplasticity, while can control the swollen of hydrophobic association crosslinked microsphere to a certain extent
Swollen speed, hydrophobic association crosslinked microsphere viscosity is low, has preferable stability, can be by oil field waste prepared and diluted, in pump
Under effect, lower pressure can smoothly enter earth formation deep, and the stratum that matches is blocked after water-swellable.
Brief description of the drawings
Fig. 1 is the cosmetic variation comparison diagram after hydrophobic association cross-linked polymer microsphere made from embodiment 1 is placed 3 months,
Wherein, a shows the initial state of product, and b shows the apparent condition after placing 3 months；
Fig. 2 is the cosmetic variation comparison diagram after hydrophobic association cross-linked polymer microsphere made from comparative example 2 is placed 3 months,
Wherein, a shows the initial state of product, and b shows the apparent condition after placing 3 months.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical scheme is clearly and completely described.Obviously, described embodiment is the part of the embodiment of the present invention, and
The embodiment being not all of.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative work
On the premise of the every other embodiment that is obtained, belong to the scope of protection of the invention.
The invention provides a kind of hydrophobic association cross-linked polymer microsphere, the hydrophobic association cross-linked polymer microsphere is by third
Acrylamide, sodium acetate, hydrophobic monomer, olefin sulfonic acid, cationic monomer and crosslinking agent is aggregated obtains；
The hydrophobic monomer is selected from methyl methacrylate, styrene, vinyl trimethylsilane, N- dodecyl propylene
One or more in acid amides, N- n-butylphenyl acrylamides.
Preferably, the hydrophobic monomer is N- dodecylacrylamides, and the chain alkyl of one end is introduced into microballoon space
In network structure, microballoon elasticity is improved, and high conjugated structure possessed by the acrylamido of the other end improves microballoon space and handed over
Connection degree.
In certain embodiments, the acrylamide, sodium acetate, the hydrophobic monomer, the olefin sulfonic acid, described
The mass ratio of cationic monomer and the crosslinking agent is (200-350)：(15-25)：(0.5-3)：(5-15)：(10-20)：
(0.2-1.5)。
Preferably, in parts by weight, the hydrophobic association cross-linked polymer microsphere is by 200-350 parts acrylamide, 15-
25 parts of sodium acetates, 0.5-3 parts hydrophobic monomer, 5-15 parts olefin sulfonic acid, 10-20 parts cationic monomer and 0.2-1.5 part crosslinking agents
It is mixed in 240-300 parts oil-based solvent and 290-430 part deionized waters, under the effect of 12-30 parts emulsifying agent, with 0.003-1.5
Part initiator triggers, and is prepared by inverse emulsion polymerization, and 25 parts of phase inversion agent octylphenol polyethylenes are added in obtained light yellow emulsion
Oxygen vinethene, hydrophobic association crosslinked microsphere is obtained after being sufficiently mixed.
In certain embodiments, the emulsifying agent is compound emulsifying agent, and the compound emulsifying agent includes Tween 80, sorbester p17
With lauryl alcohol sodium maleate, and the HLB value of the compound emulsifying agent be 4.5~6.0.
The preparation method of the lauryl alcohol sodium maleate includes：
Lauryl alcohol, maleic anhydride and organic solvent are mixed, under catalyst action, reacted under conditions of 80-85 DEG C,
Obtain lauryl alcohol sodium maleate；
Preferably, the mol ratio of the lauryl alcohol and the maleic anhydride is 1:1；With
The catalyst is S2O8 2-/ZrO2-SiO2。
Lauryl alcohol sodium maleate used in the present invention is to synthesize monoesters by esterification by lauryl alcohol and maleic anhydride, so
It is with obtained reactive emulsifier lauryl alcohol sodium maleate, its preparation method afterwards plus in alkali：It is 1 by mol ratio:1 lauryl alcohol and
Maleic anhydride mixes, and adds organic solvent, is such as the petroleum ether of monomer mass 50%, four-hole boiling flask is added to after being sufficiently mixed
In, condenser pipe, agitator, thermometer, by 0.8% catalyst S are filled on four-hole boiling flask2O8 2-/ZrO2-SiO2Add four-hole boiling flask
In, reacted under conditions of 80-85 DEG C, obtain lauryl alcohol sodium maleate.
In order to improve purity, can after cooling, by the white precipitate crude product petroleum ether being collected into recrystallize 3 times, most
It is 7 to be neutralized to pH value with sodium hydroxide solution afterwards, after heating, drying, produces the lauryl alcohol sodium maleate of high-purity.
The initial particle of hydrophobic association cross-linked polymer microsphere provided by the present invention is 100-350nm.
Olefin sulfonic acid used is selected from 2- acrylamide-2-methyl propane sulfonics, vinyl sulfonic acid, allyl sulphonic acid, methyl
One or more in propene sulfonic acid；
Cationic monomer used is selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl chlorine
Change the one or more in ammonium, dimethyl diallyl ammonium chloride；And/or
Crosslinking agent used is selected from N,N methylene bis acrylamide, N, N- DMAAs, pentaerythrite triolefin
One or more in propyl ether.
Preferably, the initiator is composite initiator, includes azo-initiator and redox initiator；The idol
Nitrogen class initiator is double (the 4- cyanogen of the NSC 18620 dihydrochloride of azo two, ABVN, azodiisobutyronitrile and 4,4 '-azo
Base valeric acid) in one or more, preferably azodiisobutyronitrile；Redox initiator is preferably potassium peroxydisulfate and sulfurous acid
Hydrogen sodium, wherein azo-initiator and potassium peroxydisulfate add in batch mixing, sodium hydrogensulfite in polymerization process several times
Add.
The present invention oil-based solvent used in polymerization is selected from thiacyclohexane, hexane, heptane, octane, isooctane, white oil, vapour
One or more in oil, diesel oil, kerosene.
Present invention also offers a kind of preparation method of hydrophobic association cross-linked polymer microsphere, the preparation method is included such as
Lower step：
By acrylamide, sodium acetate, hydrophobic monomer, olefin sulfonic acid, cationic monomer and crosslinking agent are mixed in water, regulation
The pH of mixed solution is 6.8-7.0；
Oxidant, oil-based solvent and the emulsifying agent added in initiator, stirring, then letting nitrogen in and deoxidizing, then 16~18
The reducing agent added at DEG C in initiator triggers inverse emulsion polymerization, and phase inversion agent is added after the completion of reaction and obtains the hydrophobic association
Cross-linked polymer microsphere；
Preferably, polymerization temperature is controlled to be no more than 40 DEG C, polymerization time is 3~4h.
Application of the hydrophobic association cross-linked polymer microsphere provided by the invention in water shutoff agent.
Hydrophobic association cross-linked polymer disclosed by the invention is made using inverse emulsion polymerization, during inverse emulsion polymerization
Caused heat smoothly can timely exclude reaction system, and reaction rate is relatively steady, it is hereby achieved that higher molecular weight
Polymer, and system stability is preferable, can deposit for a long time.
Cation chain link is introduced in the present invention in main chain, not only makes polymer that there is anti-polyelectrolyte solution behavior, is increased
The heat and salt resistance of strength polymer, and make polymer that there is preferable viscoplasticity, when the contraction-diverging hole for entering stratum
When, show significant dilatant type feature.
Preparing raw material of the present invention carries out inverse emulsion polymerization, polymer is formed spacial framework, meanwhile, hydrophobic association
Polymer can be formed poly- with three-dimensional space network structure by the association between hydrophobic grouping on polymer molecule side chain
Adduct molecule aggregation, strengthen the spacial framework of hydrophobic association crosslinked microsphere, so as to control hydrophobic association crosslinked microsphere
Speed of expansion.
Reactive emulsifier lauryl alcohol sodium maleate is introduced in the emulsion system of the present invention, the emulsifying agent does not only have surface
Parents' group of activity, can also make emulsifying agent participate in reacting in the course of the polymerization process, micelle table is bonded in a manner of covalent bond
Face, emulsifier molecules are made not degrade, hydrophobic association crosslinked microsphere is more stable under various conditions.
Hydrophobic association crosslinked microsphere disclosed by the invention has significant heat and salinity tolerance performance, the spacial framework of formation
Crosslink density is big, and network structure is stable, and has preferable viscoplasticity, while hydrophobic association can be controlled to be crosslinked to a certain extent
The speed of expansion of microballoon, hydrophobic association crosslinked microsphere viscosity is low, has preferable stability, can be prepared by oil field waste dilute
Release, in the presence of pump, lower pressure can smoothly enter earth formation deep, and the stratum that matches is blocked after water-swellable.
It is several embodiments that the present invention enumerates below.
Embodiment 1
Parts by weight of raw materials is：Acrylamide 240, sodium acetate 17, N- dodecylacrylamides 1.5,2- acrylamides -2-
Methyl propane sulfonic acid 7, dimethyl diallyl ammonium chloride 17, N, N- methylene-bisacrylamides 0.7, sodium hydroxide 1.3, deionization
Water 385.5, white oil 275, Tween804, Span80 22.1, reactive emulsifier lauryl alcohol sodium maleate 3 (Tween80,
5.5) Span80 and the mixed HLB value of reactive emulsifier is, OPEO 25, azodiisobutyronitrile 0.3, mistake
Potassium sulfate 0.02, sodium sulfite 0.3.
Preparation method is：Acrylamide, sodium acetate, N- dodecylacrylamides, 2- third are sequentially added in mixing kettle
Acrylamide -2- methyl propane sulfonic acids, dimethyl diallyl ammonium chloride, N, N- methylene-bisacrylamides and water, it is sufficiently mixed
PH value is adjusted to 6.8 with sodium hydroxide after even, is adding white oil, Tween80, Span80, reactive emulsifier and initiator
High-speed stirred 2min, is transferred in reactor after azodiisobutyronitrile, potassium peroxydisulfate, leads to nitrogen deoxygenation 60min, is pumped at 16 DEG C
Sodium sulfite triggers polymerization, and by refrigeration plant controlling reaction temperature, the polymerisation 4h at 34 DEG C is light yellow what is obtained
OPEO is added in emulsion, hydrophobic association cross-linked polymer microsphere is obtained after being sufficiently mixed.
As shown in figure 1, the hydrophobic association cross-linked polymer microsphere of gained is faint yellow emulsion, system is uniform, not stratified.
After placing 3 months, still so.
Embodiment 2
Parts by weight of raw materials is：Acrylamide 270, sodium acetate 22, styrene 1,2- acrylamide-2-methyl propane sulfonics 11,
Dimethyl diallyl ammonium chloride 12, N, N- methylene-bisacrylamides 0.3, sodium hydroxide 2.1, deionized water 351.6, white oil
285, Tween80 2.7, Span80 15, reactive emulsifier lauryl alcohol sodium maleate 2 (Tween80, Span80 and reactivity
5.0) the mixed HLB value of emulsifying agent is, OPEO 25, azodiisobutyronitrile 0.3, potassium peroxydisulfate 0.02, sub-
Sodium sulphate 0.3.
Preparation method is：Acrylamide, sodium acetate, styrene, 2- acrylamide -2- methyl are sequentially added in mixing kettle
Propane sulfonic acid, dimethyl diallyl ammonium chloride, N, N- methylene-bisacrylamides and water, sodium hydroxide is used after being sufficiently mixed uniformly
PH value is adjusted to 7.0, is adding white oil, Tween80, Span80, reactive emulsifier and initiator azodiisobutyronitrile, mistake
High-speed stirred 2min after potassium sulfate, is transferred in reactor, leads to nitrogen deoxygenation 60min, and it is poly- that sodium sulfite initiation is pumped at 17 DEG C
Close, and by refrigeration plant controlling reaction temperature, the polymerisation 3h at 40 DEG C, added in obtained light yellow emulsion pungent
Base phenol polyethenoxy ether, hydrophobic association cross-linked polymer microsphere is obtained after being sufficiently mixed.
Embodiment 3
Parts by weight of raw materials is：Acrylamide 330, sodium acetate 19, methyl methacrylate 2,2- acrylamide -2- methyl-props
Sulfonic acid 13, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 10, N, N- methylene-bisacrylamides 1, sodium hydroxide 2.5, go from
Sub- water 292.5, white oil 279, Tween803.3, Span80 18.7, reactive emulsifier lauryl alcohol sodium maleate 4 (Tween80,
5.2) Span80 and the mixed HLB value of reactive emulsifier is, OPEO 25, azodiisobutyronitrile 0.3, mistake
Potassium sulfate 0.02, sodium sulfite 0.3.
Preparation method is：Acrylamide, sodium acetate, methyl methacrylate, 2- acryloyls are sequentially added in mixing kettle
Amine -2- methyl propane sulfonic acids, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, N, N- methylene-bisacrylamides and water, it is fully mixed
PH value is adjusted to 6.9 with sodium hydroxide after closing uniformly, is being added white oil, Tween80, Span80, reactive emulsifier and is being drawn
High-speed stirred 2min after hair agent azodiisobutyronitrile, potassium peroxydisulfate, is transferred in reactor, leads to nitrogen deoxygenation 60min, at 18 DEG C
It is pumped into sodium sulfite and triggers polymerization, and by refrigeration plant controlling reaction temperature, the polymerisation 4h at 38 DEG C is shallow what is obtained
OPEO is added in yellow emulsion, hydrophobic association cross-linked polymer microsphere is obtained after being sufficiently mixed.
Embodiment 4
Parts by weight of raw materials is：Acrylamide 260, sodium acetate 19, N- dodecylacrylamides 2,2- acrylamide -2- first
Base propane sulfonic acid 10, dimethyl diallyl ammonium chloride 17, N,N-DMAA 1, sodium hydroxide 1.9, deionized water
359.1, white oil 276, Tween80 3.1, Span80 21.5, reactive emulsifier lauryl alcohol sodium maleate 3.5 (Tween80,
5.6) Span80 and the mixed HLB value of reactive emulsifier is, OPEO 25, azodiisobutyronitrile 0.5, mistake
Potassium sulfate 0.03, sodium sulfite 0.5.
Embodiment 5
Parts by weight of raw materials is：Acrylamide 285, sodium acetate 23, N- n-butylphenyls acrylamide 1.2,2- acrylamides-
2- methyl propane sulfonic acids 12, acrylyl oxy-ethyl-trimethyl salmiac 17, N, N- methylene-bisacrylamides 1.2, sodium hydroxide
2.3, deionized water 328.3, white oil 278, Tween80 2.9, Span80 20.1, reactive emulsifier lauryl alcohol sodium maleate
2.8 (Tween80, Span80 and the mixed HLB value of reactive emulsifier for 5.3), OPEO 25, azo two
Isobutyronitrile 0.4, potassium peroxydisulfate 0.05, sodium sulfite 0.4.
Embodiment 6
Parts by weight of raw materials is：Acrylamide 200, sodium acetate 15, vinyl trimethylsilane 0.5,2- acrylamide -2- first
Base propane sulfonic acid 5, acrylyl oxy-ethyl-trimethyl salmiac 15, N, N- methylene-bisacrylamides 0.2, sodium hydroxide 1, deionization
Water 425, white oil 280, Tween801.5, Span80 7.5, reactive emulsifier lauryl alcohol sodium maleate 3 (Tween80,
5.9) Span80 and the mixed HLB value of reactive emulsifier is, OPEO 25, azodiisobutyronitrile 0.35,
Potassium peroxydisulfate 0.02, sodium sulfite 0.3.
Embodiment 7
Parts by weight of raw materials is：Acrylamide 350, sodium acetate 20, styrene 3,2- acrylamide-2-methyl propane sulfonics 15,
Acrylyl oxy-ethyl-trimethyl salmiac 20, pentaerythritol triallyl ether 1.5, sodium hydroxide 3, deionized water 290, white oil
277, Tween80 3, Span80 21, reactive emulsifier lauryl alcohol sodium maleate 4 (Tween80, Span80 and reactivity breast
6.0) the mixed HLB value of agent is, OPEO 30, azodiisobutyronitrile 0.5, potassium peroxydisulfate 0.05, sulfurous
Sour sodium 0.5.
The preparation method of embodiment 4 to embodiment 7 is substantially the same with embodiment 1, and difference is shown in Table 1.
Comparative example 1
The preparation method of comparative example 1 is substantially the same with embodiment 1, and difference is：
Hydrophobic monomer differs with the embodiment of the present invention, using following monomer：
2,5- dimethyl-Isosorbide-5-Nitrae-two (1- methacryl amidos ethyl) benzene, this monomer synthesize in the following way：
Under nitrogen protection, by 10g sulfur trioxides, 9mL pyridines stir at room temperature, uniform dissolution is in filling 100mL ice
In the glass reaction kettle of acetic acid, then be slowly added dropwise into the mixed solution into 12g methacrylonitriles, after be added dropwise to 28g2,5- bis-
Methyl isophthalic acid, 4- divinylbenzenes, continuously stir and react 3.5 hours at 38 DEG C, import 350mL deionized waters, stir
After stand, it is filtered, washing, dry, obtain 2,5- dimethyl-Isosorbide-5-Nitrae-two (1- methacryl amidos ethyl) benzene.
Comparative example 2
The preparation method of comparative example 2 is substantially the same with embodiment 1, and difference is：
Emulsifying agent used only includes Tween 80 and sorbester p17.
As shown in a figures in Fig. 2, the hydrophobic association cross-linked polymer microsphere of gained is faint yellow emulsion, and system is uniform,
It is not stratified.But after placing 3 months, as shown in the b figures in Fig. 2, there is obvious layering in system.
Performance detection：
The emulsion microballoon in case study on implementation is tested by Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation's company standard, surveyed
Examination project includes testing emulsion microballoon initial particle with laser particle analyzer；With roller heating stove measure emulsion microballoon aging expansion times
Number：Aging 7 days, 15 in the salt solution that 95 DEG C, total salinity are 45000mg/L (wherein divalent cation concentration is 6500mg/L)
My god, particle diameter expansion multiple after 30 days；
Observe the cosmetic variation after microemulsion is placed 3 months.
Test result is shown in Table 2.
In a word, hydrophobic association cross-linked polymer microsphere provided by the invention has significant heat and salinity tolerance performance, formation
Spacial framework crosslink density is big, and network structure is stable, and has preferable viscoplasticity, while can control to a certain extent
The speed of expansion of hydrophobic association crosslinked microsphere, hydrophobic association crosslinked microsphere viscosity is low, has preferable stability, can be by oil field
Waste water prepared and diluted, in the presence of pump, lower pressure can smoothly enter earth formation deep, be blocked matchingly after water-swellable
Layer, suitable for Water in Water Shutoff in Oil Field profile control field.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (10)
1. a kind of hydrophobic association cross-linked polymer microsphere, it is characterised in that the hydrophobic association cross-linked polymer microsphere is by propylene
Acid amides, sodium acetate, hydrophobic monomer, olefin sulfonic acid, cationic monomer and the inverted emulsion polymerization of crosslinking agent obtain；
The hydrophobic monomer is selected from methyl methacrylate, styrene, vinyl trimethylsilane, N- dodecyl acryloyls
One or more in amine, N- n-butylphenyl acrylamides.
2. hydrophobic association cross-linked polymer microsphere according to claim 1, it is characterised in that the acrylamide, described
Sodium acetate, the hydrophobic monomer, the olefin sulfonic acid, the mass ratio of the cationic monomer and the crosslinking agent are (200-
350)：(15-25)：(0.5-3)：(5-15)：(10-20)：(0.2-1.5).
3. hydrophobic association cross-linked polymer microsphere according to claim 1, it is characterised in that in parts by weight, described to dredge
Water association cross-linked polymer microsphere is by 200-350 parts acrylamide, 15-25 parts sodium acetate, 0.5-3 parts hydrophobic monomer, 5-15
Part olefin sulfonic acid, 10-20 parts cationic monomer and 0.2-1.5 part crosslinking agents are mixed in 240-300 parts oil-based solvent and 290-430 parts
In deionized water, under the effect of 12-30 parts emulsifying agent, triggered with 0.003-1.5 parts initiator, prepared by inverse emulsion polymerization,
25 parts of phase inversion agent OPEOs are added in obtained light yellow emulsion, hydrophobic association friendship is obtained after being sufficiently mixed
Join microballoon.
4. hydrophobic association cross-linked polymer microsphere according to claim 3, it is characterised in that the emulsifying agent is Composite Milk
Agent, the compound emulsifying agent include Tween 80, sorbester p17 and lauryl alcohol sodium maleate, and the HLB value of the compound emulsifying agent
For 4.5~6.0.
5. hydrophobic association cross-linked polymer microsphere according to claim 4, it is characterised in that the lauryl alcohol sodium maleate
Preparation method include：
Lauryl alcohol, maleic anhydride and organic solvent are mixed, under catalyst action, reacts, obtains under conditions of 80-85 DEG C
Lauryl alcohol sodium maleate；
Preferably, the mol ratio of the lauryl alcohol and the maleic anhydride is 1:1；With
The catalyst is S2O8 2-/ZrO2-SiO2。
6. hydrophobic association cross-linked polymer microsphere according to claim 1, it is characterised in that the hydrophobic association crosslinking is poly-
The initial particle of compound microballoon is 100-350nm.
7. hydrophobic association cross-linked polymer microsphere according to claim 1, it is characterised in that the olefin sulfonic acid is selected from 2-
One or more in acrylamide-2-methyl propane sulfonic, vinyl sulfonic acid, allyl sulphonic acid, methacrylic sulfonic acid；
The cationic monomer be selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac,
One or more in dimethyl diallyl ammonium chloride；And/or
The crosslinking agent is selected from N,N methylene bis acrylamide, N, N- DMAAs, pentaerythritol triallyl ether
In one or more.
8. hydrophobic association cross-linked polymer microsphere according to claim 3, it is characterised in that the initiator includes azo
Bis-isobutyronitrile, potassium peroxydisulfate and sodium hydrogensulfite；And/or
The one kind of the oil-based solvent in thiacyclohexane, hexane, heptane, octane, isooctane, white oil, gasoline, diesel oil, kerosene
It is or a variety of.
9. the preparation method of any one of claim 1 to the 8 hydrophobic association cross-linked polymer microsphere, it is characterised in that described
Preparation method comprises the following steps：
By acrylamide, sodium acetate, hydrophobic monomer, olefin sulfonic acid, cationic monomer and crosslinking agent are mixed in water, regulation mixing
The pH of solution is 6.8-7.0；
Oxidant, oil-based solvent and the emulsifying agent added in initiator, stirring, then letting nitrogen in and deoxidizing, then at 16~18 DEG C
The reducing agent added in initiator triggers inverse emulsion polymerization, and phase inversion agent is added after the completion of reaction and obtains the hydrophobic association crosslinking
Polymer microballoon；
Wherein, polymerization temperature is controlled to be no more than 40 DEG C, polymerization time is 3~4h.
10. application of any one of claim 1 to the 9 hydrophobic association cross-linked polymer microsphere in water shutoff agent.
Priority Applications (1)
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| CN110204653A (en) * | 2019-06-17 | 2019-09-06 | 黑龙江益瑞化工有限公司 | A kind of oilfield chemistry oil recovery profile-controlling and plugging agent amphoteric ion polymer particle |
| CN110950996A (en) * | 2018-09-27 | 2020-04-03 | 中国石油化工股份有限公司 | Water plugging polymer and preparation method and application thereof |
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| CN115322760A (en) * | 2022-10-11 | 2022-11-11 | 山东诺尔生物科技有限公司 | Zwitterionic water shutoff profile control agent and preparation method thereof |
| CN115322760B (en) * | 2022-10-11 | 2022-12-20 | 山东诺尔生物科技有限公司 | Zwitterionic water shutoff profile control agent and preparation method thereof |
| CN116831822A (en) * | 2023-07-31 | 2023-10-03 | 诺宸股份有限公司 | Absorbent article and preparation method thereof |
| CN116831822B (en) * | 2023-07-31 | 2024-02-09 | 诺宸股份有限公司 | Absorbent article and preparation method thereof |
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