CN118255932A - Polymer emulsion, preparation method and application thereof, and strong suspension fracturing fluid - Google Patents
Polymer emulsion, preparation method and application thereof, and strong suspension fracturing fluid Download PDFInfo
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- CN118255932A CN118255932A CN202211674625.7A CN202211674625A CN118255932A CN 118255932 A CN118255932 A CN 118255932A CN 202211674625 A CN202211674625 A CN 202211674625A CN 118255932 A CN118255932 A CN 118255932A
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- Prior art keywords
- monomer
- polymer emulsion
- weight
- polymer
- alkyl group
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- 229920000642 polymer Polymers 0.000 title claims abstract description 182
- 239000000839 emulsion Substances 0.000 title claims abstract description 137
- 239000012530 fluid Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000725 suspension Substances 0.000 title claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 275
- 239000012071 phase Substances 0.000 claims abstract description 117
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 62
- 239000008346 aqueous phase Substances 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 74
- 239000003921 oil Substances 0.000 claims description 67
- 125000000217 alkyl group Chemical group 0.000 claims description 60
- 239000004094 surface-active agent Substances 0.000 claims description 49
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 44
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 239000006184 cosolvent Substances 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- 230000033116 oxidation-reduction process Effects 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 230000002579 anti-swelling effect Effects 0.000 claims description 27
- 239000003446 ligand Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 229920005862 polyol Polymers 0.000 claims description 26
- 150000003077 polyols Chemical class 0.000 claims description 26
- 239000003638 chemical reducing agent Substances 0.000 claims description 25
- 239000003431 cross linking reagent Substances 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 25
- -1 polyoxyethylene Polymers 0.000 claims description 25
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 20
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 20
- 239000002562 thickening agent Substances 0.000 claims description 20
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 19
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 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 10
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- 229920001983 poloxamer Polymers 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 7
- 235000019743 Choline chloride Nutrition 0.000 claims description 7
- 229960003178 choline chloride Drugs 0.000 claims description 7
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 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 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 6
- 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 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- 238000011534 incubation Methods 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- 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 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- PERHPCPROKAJEC-UHFFFAOYSA-N hydrogen peroxide;methylcyclohexane Chemical compound OO.CC1CCCCC1 PERHPCPROKAJEC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002432 hydroperoxides Chemical class 0.000 claims description 5
- 229920000136 polysorbate Polymers 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 4
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 4
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
- CGQZIFGCHVCAHE-UHFFFAOYSA-L disodium;ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [Na+].[Na+].[O-]P([O-])(=O)C=C CGQZIFGCHVCAHE-UHFFFAOYSA-L 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- SYPKYPCQNDILJH-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(CC)NC(=O)C=C SYPKYPCQNDILJH-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 238000010008 shearing Methods 0.000 description 15
- 238000010907 mechanical stirring Methods 0.000 description 7
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 6
- 229960003237 betaine Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 6
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 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 description 5
- COYVWKMZTCAFHO-UHFFFAOYSA-N n-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)N(C)C(=O)C=C COYVWKMZTCAFHO-UHFFFAOYSA-N 0.000 description 5
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 5
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229920005615 natural polymer Polymers 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- 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 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- ZZGCWICUHCMQAR-UHFFFAOYSA-N n-(3-hydroxypropyl)-n-methylprop-2-enamide Chemical compound C=CC(=O)N(C)CCCO ZZGCWICUHCMQAR-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ZDWZXBJFITXZBL-UHFFFAOYSA-N S(=O)(=O)(O)C=CC1=CC=CC=C1.[Na] Chemical compound S(=O)(=O)(O)C=CC1=CC=CC=C1.[Na] ZDWZXBJFITXZBL-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- FXYIRRFBFHHNIC-UHFFFAOYSA-N ethenylphosphonic acid;sodium Chemical compound [Na].OP(O)(=O)C=C FXYIRRFBFHHNIC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FPVSUJTZRASPAK-UHFFFAOYSA-N (2,3-dimethylbenzoyl) 2,3-dimethylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C(=C(C)C=CC=2)C)=C1C FPVSUJTZRASPAK-UHFFFAOYSA-N 0.000 description 1
- OPRIWFSSXKQMPB-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(C)(C)NC(=O)C=C OPRIWFSSXKQMPB-UHFFFAOYSA-N 0.000 description 1
- KJMGIINCIYPCFQ-UHFFFAOYSA-N 2-methylhex-2-enedioic acid Chemical compound OC(=O)C(C)=CCCC(O)=O KJMGIINCIYPCFQ-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229920002752 Konjac Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000000252 konjac Substances 0.000 description 1
- 235000019823 konjac gum Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- GBSRRQISIWGCNC-UHFFFAOYSA-N methyl propane-1-sulfonate Chemical compound CCCS(=O)(=O)OC GBSRRQISIWGCNC-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 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
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- RUMMJKMQGVFYDJ-XYJRJTJESA-M sodium;(z)-4-hexadecoxy-4-oxobut-2-enoate Chemical compound [Na+].CCCCCCCCCCCCCCCCOC(=O)\C=C/C([O-])=O RUMMJKMQGVFYDJ-XYJRJTJESA-M 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Abstract
The invention discloses a preparation method of polymer emulsion, which comprises the following steps: step (1), preparing an oil phase and emulsifier mixed solution: adding the oil phase with the formula amount and the emulsifier with the formula amount into a reaction container, and uniformly stirring in the atmosphere of nitrogen or inert gas to obtain an oil phase and emulsifier mixed solution; step (2), preparing an aqueous phase: dissolving the monomer A, the monomer B, the monomer C and the monomer D in water, and uniformly mixing to obtain a water phase; and (3) performing polymerization reaction to prepare polymer emulsion. The invention also discloses a polymer emulsion. The invention also discloses application of the polymer emulsion in preparation of oilfield fracturing fluid. The invention also discloses a strong suspension fracturing fluid which comprises 0.6-3 parts by weight of the polymer emulsion.
Description
Technical Field
The invention belongs to the technical field of petroleum exploitation, and particularly relates to a polymer emulsion, a preparation method and application thereof, and a strong suspension fracturing fluid.
Background
The fracturing fluid is very important for fracturing construction, and is responsible for the task of transmitting pressure to fracture the stratum to form artificial cracks and carrying propping agents, so that the matched fracturing fluid has the characteristics of low friction resistance, low cost, low injury, strong suspension, high temperature resistance, shearing resistance, mineralization resistance, easiness in flowback and easiness in operation.
The substances commonly used at present as thickeners of fracturing fluids mainly have three main categories: natural high molecular thickeners (e.g., guar gum, xanthan gum, konjac gum, etc.), viscoelastic surfactant thickeners (e.g., VES), and synthetic high molecular thickeners.
All three kinds of thickeners have certain advantages, the natural polymer thickeners are applied for nearly 50 years and are relatively mature, but the natural polymer thickeners need a longer dissolution process, so that the natural polymer thickeners are inconvenient to mix on site, are not suitable for large-scale operation, and have no breakthrough development on temperature resistance.
Viscoelastic surfactant thickeners (such as VES) have the property of being residue-free, but are costly, poor in temperature resistance and large in fluid loss, making their use range very limited.
In recent years, synthetic polymer thickeners are increasingly valued in the industry due to the characteristics of simple and convenient molecular structure design, diversified forms, good temperature resistance and shearing resistance, convenient preparation and the like.
For example, U.S. patent No. 6579947B 2 discloses a synthetic polymeric fracturing fluid system that can be used at 180 ℃ and wherein the surfactant is a diblock or multiblock copolymer of monomers such as styrene, methacrylic acid, 2-carboxyethylmethacrylic acid, and the like.
The invention patent application (application number: 2008100516698) entitled "a temperature resistant water-based fracturing fluid thickener and method for preparing same" discloses a ternary polymerization system of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and N-vinylpyrrolidone, which the inventors claim that a 0.5% aqueous solution of the system can retain 65% of the viscosity at 170s-1 at 95 ℃, but the application does not describe the use of such fracturing fluid.
The invention relates to a high-temperature resistant cleaning emulsion or microemulsion fracturing fluid and its preparation method, chinese patent application publication No. CN101845301A discloses an association type cleaning fracturing fluid system which can be used under the condition of high temperature of 180 ℃ (the highest is applicable to 230 ℃), and the components of the association type cleaning fracturing fluid system are acrylamide, acrylic acid, propenyl sulfonate and methacryloyloxyethyl trimethyl ammonium chloride, and also add hydrophobic monomer maleic acid mono hexadecyl ester sodium salt, and the invention is characterized in that the association type cleaning fracturing fluid system can be used without adding cross-linking agent.
The fracturing fluid has better effects, such as temperature resistance and use convenience, has larger progress than natural polymer thickeners and viscoelastic surfactant thickeners, but has obvious defects in mineralization resistance, residue content and cost, and the biggest problem is that the friction resistance is difficult to overcome when the fracturing fluid is used in high concentration (such as deep wells and ultra-deep wells).
Disclosure of Invention
In view of the above problems, a first object of the present invention is to disclose a polymer emulsion having the characteristics of low friction, temperature-controlled crosslinking, strong suspending ability, low dosage and low cost.
A second object of the present invention is to disclose a method for preparing a polymer emulsion.
A third object of the present invention is to disclose the use of the above polymer emulsion.
A fourth object of the present invention is to disclose a strong suspension fracturing fluid containing the polymer emulsion described above.
The technical scheme is as follows: a polymer emulsion comprising a polymer (I) or a polymer (ii), wherein:
The polymer (I) has rigid units
The polymer (II) has rigid unitsWherein:
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
Further, the structural formula of the polymer (I) is as follows:
Wherein:
x and y are a ratio of 20:1 to 40:1;
(x+y) m is a ratio of 1:0.005 to 1:0.05;
(x+y): n is a ratio of 1:0.05 to 1:0.2.
Further, the structural formula of the polymer (II) is as follows:
Wherein:
x and y are a ratio of 20:1 to 40:1;
(x+y) m is a ratio of 1:0.05 to 1:0.2;
(x+y) n is a ratio of 1:0.0025 to 1:0.025;
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
Still further, the polymer emulsion is composed of the following components:
30-50 parts by weight of an oil phase of a continuous phase;
50 to 60 parts by weight of a disperse phase aqueous phase containing the polymer (I) or the polymer (II);
2 to 5 weight portions of emulsifying agent.
Still further, the oil phase is at least one selected from the group consisting of white oil, kerosene, diesel oil, cyclohexane, toluene.
Still further, the emulsifier is at least one selected from the group consisting of fatty alcohol polyoxyethylene ether, polyoxyethylene alkylphenol ether, nonylphenol polyoxyethylene ether, polyether type surfactant, polyol surfactant, and oleamide.
Still further, the fatty alcohol-polyoxyethylene ether is one of a flat O series (peregal O) fatty alcohol-polyoxyethylene ether and an AEO series fatty alcohol-polyoxyethylene ether;
the polyoxyethylene alkylphenol ether is OP series polyoxyethylene alkylphenol ether;
the nonylphenol polyoxyethylene ether is TX series nonylphenol polyoxyethylene ether;
The polyether surfactant is Pluronic surfactant;
the polyol surfactant is Span series polyol surfactant or Tween series polyol surfactant.
Still further, the content of polymer (I) or the content of polymer (II) in the aqueous phase is 25 to 35% of the total weight of the polymer emulsion.
For the second object of the invention:
the preparation method of the polymer emulsion comprises the following steps:
step (1), preparing an oil phase and emulsifier mixed solution:
adding the oil phase with the formula amount and the emulsifier with the formula amount into a reaction container, and uniformly stirring in the atmosphere of nitrogen or inert gas to obtain an oil phase and emulsifier mixed solution;
Step (2), preparing an aqueous phase:
dissolving the monomer A, the monomer B, the monomer C and the monomer D in water, and uniformly mixing to obtain a water phase
Step (3), carrying out polymerization reaction to prepare polymer emulsion:
(31) Dropwise adding the water phase obtained in the step (2) into the mixed solution of the oil phase obtained in the step (1) and the emulsifier to form a reaction solution;
(32) And (3) dropwise adding an oxidation-reduction initiator, a water-soluble thermal initiator and an oil-soluble thermal initiator into the reaction liquid obtained in the step (31) under the condition of nitrogen atmosphere or inert atmosphere for polymerization reaction, and then preserving heat for a period of time to obtain the polymer emulsion.
Further, the monomer A in the step (2) is selected from one of acrylamide, (methyl) acrylamide, N-hydroxypropyl (methyl) acrylamide and N-isopropyl (methyl) acrylamide;
The monomer B is at least one selected from (methyl) acrylic acid, maleic anhydride, fumaric acid and itaconic acid;
The monomer C is selected from one of 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-methylbutyric acid, vinylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium, 2-acrylamide-2-methylbutyric acid sodium, vinylsulfonic acid sodium, styrenesulfonic acid sodium and vinylphosphonic acid sodium;
The monomer D is a monomer D 1, which has the following structure:
monomer D 1, or
The monomer D has the following structure:
wherein:
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
Further, in the step (2), the weight ratio of the monomer A, the monomer B, the monomer C and the monomer D is (75-90): (1-5): (5-20): (0.25-1).
Further, the polymerization reaction in step (32) is carried out at a temperature of 10 to 20℃for at least 3 hours, preferably 3 to 6 hours;
The incubation time is at least 14 hours, preferably 14 to 18 hours.
Further, the oxidation-reduction initiator in the step (32) is formed by mixing an oxidant and a reducing agent according to a weight ratio of 1:6-1:8, wherein:
the oxidant is at least one selected from ammonium persulfate, potassium persulfate, hydrogen peroxide, organic hydrogen peroxide and dimethylbenzene acyl peroxide;
the reducing agent is at least one selected from sodium sulfite, ferrous sulfate, sodium thiosulfate or fatty amine.
Still further, the organic hydroperoxide is at least one of tert-butyl hydroperoxide, cumene hydroperoxide, methylcyclohexane hydroperoxide.
Further, the addition amount of the oxidation-reduction initiator is 0.01-0.08% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the water-soluble thermal initiator is 0.01-0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the oil-soluble thermal initiator is 0.01-0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D.
Further, the water-soluble thermal initiator in the step (32) is one of water-soluble azo diiso Ding Mi hydrochloride, azo diisobutyl amidine hydrochloride, water-soluble sodium persulfate and hydrogen peroxide.
Further, the oil-soluble thermal initiator in the step (32) is one of oil-soluble azobisisobutyronitrile, benzoyl peroxide and diacetyl peroxide.
Further, in the step (1), the stirring speed is 250-350 RPM, and the temperature of the whole system is controlled at 28-35 ℃ during stirring.
Further, the weight ratio of the total mass of the monomer A, the monomer B, the monomer C and the monomer D to water in the step (2) is (20.5-40.25): (13.25-36.25).
Further, EDTA disodium salt is added into the water phase in the step (2), and the addition amount of the EDTA disodium salt is 0.01-0.1% of the total mass of the monomer A, the monomer B, the monomer C and the monomer D.
For the third object of the present invention:
The application of the polymer emulsion in preparing oilfield fracturing fluid.
Further, the polymer emulsion of any one of the above is used for preparing the oilfield fracturing fluid again to serve as a thickening agent.
For the fourth object of the present invention:
The strong suspension fracturing fluid comprises 0.6-3 parts by weight of any one of the polymer emulsions.
Further, the composition also comprises 0.3 to 0.5 weight parts of star ligand cross-linking agent, 0.1 to 0.3 weight parts of anti-swelling agent and 90 to 100 weight parts of water, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is one selected from H, methyl and ethyl;
m is one of chromium, aluminum, titanium, boron and zirconium;
The anti-swelling agent is 0.1 to 0.5 percent of aqueous solution of choline chloride with mass concentration or 0.1 to 0.5 percent of aqueous solution of benzyl trimethyl ammonium chloride with mass concentration.
Further comprises 0.1 to 0.3 weight part of cleanup additive, the cleanup additive is an anionic surfactant or a nonionic surfactant.
Further, the organic acid catalyst also comprises 0.01 to 0.2 weight part of cosolvent, wherein the cosolvent is betaine cosolvent and/or MOA-9 cosolvent. Because the dissolution time of the polymer emulsion is 40-60 s, the fracturing fluid can pump the cosolvent into water in advance to achieve the best effect, and the main component of the fracturing fluid is one or a compound of betaine cosolvent or MOA-9 cosolvent.
The field use method of the strong suspension fracturing fluid comprises the following steps: the cosolvent is pumped into a water inlet of the sand mixing vehicle, the thickener, the anti-swelling agent and the cleanup additive are pumped into a sand mixing tank opening on the sand mixing vehicle, and the star-shaped ligand cross-linking agent is pumped into a low-pressure manifold at the fracturing fluid outlet of the sand mixing vehicle by using a high-pressure pump.
The beneficial effects are that: the polymer emulsion disclosed by the invention, the preparation method and application thereof, and the strong suspension fracturing fluid have the following beneficial effects:
1. The dissolution time of the emulsion is short, so that on-site real-time mixing can be realized;
2. The emulsion molecular main chain or side group has a rigid group, so that the molecular chain has larger viscosity retention rate in a hypersalinity and high-temperature state, and has very strong proppant suspending capability;
3. the processing cost is low, the using amount is low, so the cost of the fracturing fluid is also low;
4. The strong suspension fracturing fluid disclosed by the invention is easy to break gel, has the characteristics of low residue and low reservoir damage, and is beneficial to increasing the oil and gas yield and improving the efficiency;
5. The strong suspension fracturing fluid disclosed by the invention has a certain capacity of inhibiting clay expansion.
Drawings
FIG. 1 is an electron micrograph of the polymer emulsion (HAPAM) prepared in example 1.
FIG. 2 is a graph of infrared spectra (FT-IR) of the polymer emulsion (HAPAM) prepared in example 1 versus the polymer emulsion (PAM) prepared in comparative example.
FIG. 3 is a thermogravimetric analysis (TG) plot of the polymer emulsion (HAPAM) prepared in example 1 versus the polymer emulsion (PAM) prepared in comparative example.
FIG. 4 is a 1 H NMR spectrum of the polymer emulsion (HAPAM) prepared in example 1.
FIG. 5 is a schematic diagram of the frictional resistance of the strong suspension fracturing fluid SWJX-1 prepared in example 1.
FIG. 6 is a schematic representation of the resistivity of the strong suspension fracturing fluid SWJX-1 prepared in example 1.
The specific embodiment is as follows:
The following detailed description of specific embodiments of the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
A polymer emulsion comprising a polymer (I) or a polymer (ii), wherein:
The polymer (I) has rigid units
The polymer (II) has rigid unitsWherein:
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
Further, the structural formula of the polymer (I) is as follows:
Wherein:
x and y are a ratio of 20:1 to 40:1;
(x+y) m is a ratio of 1:0.005 to 1:0.05;
(x+y): n is a ratio of 1:0.05 to 1:0.2.
Further, the structural formula of the polymer (II) is as follows:
Wherein:
x and y are a ratio of 20:1 to 40:1;
(x+y) m is a ratio of 1:0.05 to 1:0.2;
(x+y) n is a ratio of 1:0.0025 to 1:0.025;
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
Still further, the polymer emulsion is composed of the following components:
30-50 parts by weight of an oil phase of a continuous phase;
50 to 60 parts by weight of a disperse phase aqueous phase containing the polymer (I) or the polymer (II);
2 to 5 weight portions of emulsifying agent.
Still further, the oil phase is at least one selected from the group consisting of white oil, kerosene, diesel oil, cyclohexane, toluene.
Still further, the emulsifier is at least one selected from the group consisting of fatty alcohol polyoxyethylene ether, polyoxyethylene alkylphenol ether, nonylphenol polyoxyethylene ether, polyether type surfactant, polyol surfactant, and oleamide.
Still further, the fatty alcohol-polyoxyethylene ether is one of a flat O series (peregal O) fatty alcohol-polyoxyethylene ether and an AEO series fatty alcohol-polyoxyethylene ether;
the polyoxyethylene alkylphenol ether is OP series polyoxyethylene alkylphenol ether;
the nonylphenol polyoxyethylene ether is TX series nonylphenol polyoxyethylene ether;
The polyether surfactant is Pluronic surfactant;
the polyol surfactant is Span series polyol surfactant or Tween series polyol surfactant.
Still further, the content of polymer (I) or the content of polymer (II) in the aqueous phase is 25 to 35% of the total weight of the polymer emulsion.
For the second object of the invention:
the preparation method of the polymer emulsion comprises the following steps:
step (1), preparing an oil phase and emulsifier mixed solution:
adding the oil phase with the formula amount and the emulsifier with the formula amount into a reaction container, and uniformly stirring in the atmosphere of nitrogen or inert gas to obtain an oil phase and emulsifier mixed solution;
Step (2), preparing an aqueous phase:
dissolving the monomer A, the monomer B, the monomer C and the monomer D in water, and uniformly mixing to obtain a water phase, wherein:
The monomer A is selected from one of acrylamide, (methyl) acrylamide, N-hydroxypropyl (methyl) acrylamide and N-isopropyl (methyl) acrylamide;
The monomer B is at least one selected from (methyl) acrylic acid, maleic anhydride, fumaric acid and itaconic acid;
The monomer C is selected from one of 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-methylbutyric acid, vinylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium, 2-acrylamide-2-methylbutyric acid sodium, vinylsulfonic acid sodium, styrenesulfonic acid sodium and vinylphosphonic acid sodium;
The monomer D is a monomer D 1, which has the following structure:
monomer D 1, or
The monomer D has the following structure:
wherein:
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
Step (3), carrying out polymerization reaction to prepare polymer emulsion:
(31) Dropwise adding the water phase obtained in the step (2) into the mixed solution of the oil phase obtained in the step (1) and the emulsifier to form a reaction solution;
(32) And (3) dropwise adding an oxidation-reduction initiator, a water-soluble thermal initiator and an oil-soluble thermal initiator into the reaction liquid obtained in the step (31) under the condition of nitrogen atmosphere or inert atmosphere for polymerization reaction, and then preserving heat for a period of time to obtain the polymer emulsion.
Further, in the step (2), the weight ratio of the monomer A, the monomer B, the monomer C and the monomer D is (75-90): (1-5): (5-20): (0.25-1).
Further, the polymerization reaction in step (32) is carried out at a temperature of 10 to 20℃for at least 3 hours, preferably 3 to 6 hours;
The incubation time is at least 14 hours, preferably 14 to 18 hours.
Further, the oxidation-reduction initiator in the step (32) is formed by mixing an oxidant and a reducing agent according to a weight ratio of 1:6-1:8, wherein:
the oxidant is at least one selected from ammonium persulfate, potassium persulfate, hydrogen peroxide, organic hydrogen peroxide and dimethylbenzene acyl peroxide;
The reducing agent is at least one selected from sodium sulfite, ferrous sulfate, sodium thiosulfate or fatty amine (octylamine).
Still further, the organic hydroperoxide is at least one of tert-butyl hydroperoxide, cumene hydroperoxide, methylcyclohexane hydroperoxide.
Further, the addition amount of the oxidation-reduction initiator is 0.01-0.08% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the water-soluble thermal initiator is 0.01-0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the oil-soluble thermal initiator is 0.01-0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D.
Further, the water-soluble thermal initiator in the step (32) is one of water-soluble azo diiso Ding Mi hydrochloride, azo diisobutyl amidine hydrochloride, water-soluble sodium persulfate and hydrogen peroxide.
Further, the oil-soluble thermal initiator in the step (32) is one of oil-soluble azobisisobutyronitrile, benzoyl peroxide and diacetyl peroxide.
Further, in the step (1), the stirring speed is 250-350 RPM, and the temperature of the whole system is controlled at 28-35 ℃ during stirring.
Further, the weight ratio of the total mass of the monomer A, the monomer B, the monomer C and the monomer D to water in the step (2) is (20.5-40.25): (13.25-36.25).
Further, EDTA disodium salt is added into the water phase in the step (2), and the addition amount of the EDTA disodium salt is 0.01-0.1% of the total mass of the monomer A, the monomer B, the monomer C and the monomer D.
For the third object of the present invention:
The application of the polymer emulsion in preparing oilfield fracturing fluid.
Further, the polymer emulsion of any one of the above is used for preparing the oilfield fracturing fluid again to serve as a thickening agent.
For the fourth object of the present invention:
The strong suspension fracturing fluid comprises 0.6-3 parts by weight of any one of the polymer emulsions.
Further, the composition also comprises 0.3 to 0.5 weight parts of star ligand cross-linking agent, 0.1 to 0.3 weight parts of anti-swelling agent and 90 to 100 weight parts of water, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is one selected from H, methyl and ethyl;
m is one of chromium, aluminum, titanium, boron and zirconium;
The anti-swelling agent is 0.1 to 0.5 percent of aqueous solution of choline chloride with mass concentration or 0.1 to 0.5 percent of aqueous solution of benzyl trimethyl ammonium chloride with mass concentration.
Further comprises 0.1 to 0.3 weight part of cleanup additive, the cleanup additive is an anionic surfactant or a nonionic surfactant.
Further, the organic acid catalyst also comprises 0.01 to 0.2 weight part of cosolvent, wherein the cosolvent is betaine cosolvent and/or MOA-9 cosolvent.
In one embodiment:
A polymer emulsion comprising a polymer (I), wherein:
The polymer (I) has rigid units
Further, the structural formula of the polymer (I) is as follows:
wherein: x is y is 20:1;
(x+y) m is 1:0.005;
(x+y): n is 1:0.05.
Still further, the polymer emulsion is composed of the following components:
30 parts by weight of an oil phase of a continuous phase;
50 parts by weight of a disperse phase aqueous phase containing the polymer (I);
2 parts by weight of an emulsifier.
Still further, the oil phase is selected from white oils.
Still further, the emulsifier is selected from the group consisting of fatty alcohol-polyoxyethylene ethers.
Still further, the fatty alcohol-polyoxyethylene ether is a flat O series (peregal O) fatty alcohol-polyoxyethylene ether;
the polyoxyethylene alkylphenol ether is OP series polyoxyethylene alkylphenol ether;
the nonylphenol polyoxyethylene ether is TX series nonylphenol polyoxyethylene ether;
The polyether surfactant is Pluronic surfactant;
The polyol surfactant is Span series polyol surfactant.
Still further, the content of polymer (I) in the aqueous phase is 25% by weight based on the total weight of the polymer emulsion.
For the second object of the invention:
the preparation method of the polymer emulsion comprises the following steps:
step (1), preparing an oil phase and emulsifier mixed solution:
Adding the oil phase with the formula amount and the emulsifier with the formula amount into a reaction container, and uniformly stirring in the atmosphere of nitrogen to obtain an oil phase and emulsifier mixed solution;
Step (2), preparing an aqueous phase:
dissolving the monomer A, the monomer B, the monomer C and the monomer D in water, and uniformly mixing to obtain a water phase, wherein:
The monomer A is selected from acrylamide;
the monomer B is selected from (methyl) acrylic acid;
The monomer C is selected from 2-acrylamide-2-methylpropanesulfonic acid;
The monomer D is a monomer D 1, which has the following structure:
Step (3), carrying out polymerization reaction to prepare polymer emulsion:
(31) Dropwise adding the water phase obtained in the step (2) into the mixed solution of the oil phase obtained in the step (1) and the emulsifier to form a reaction solution;
(32) And (3) dropwise adding an oxidation-reduction initiator, a water-soluble thermal initiator and an oil-soluble thermal initiator into the reaction liquid obtained in the step (31) in nitrogen atmosphere for polymerization reaction, and then preserving heat for a period of time to obtain the polymer emulsion.
Further, in the step (2), the weight ratio of the monomer A, the monomer B, the monomer C and the monomer D is 75:1:5:0.25.
Further, the polymerization reaction in the step (32) is carried out at 10℃for 6 hours;
The incubation time was 18 hours.
Further, the oxidation-reduction initiator in the step (32) is formed by mixing an oxidant and a reducing agent according to a weight ratio of 1:6, wherein:
the oxidant is ammonium persulfate;
The reducing agent is sodium sulfite.
Further, the addition amount of the oxidation-reduction initiator is 0.01% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the water-soluble thermal initiator is 0.01 percent of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the oil-soluble thermal initiator is 0.01% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D.
Further, the water-soluble thermal initiator in step (32) is water-soluble azobisiso Ding Mi-hydrochloride.
Further, the oil-soluble thermal initiator in step (32) is oil-soluble azobisisobutyronitrile.
Further, in the step (1), the stirring rate was 250RPM, and the temperature of the whole system was controlled at 28℃during stirring.
Further, the weight ratio of the total mass of monomer a, monomer B, monomer C and monomer D to water in step (2) was 20.5:13.25.
Further, EDTA disodium salt is added to the aqueous phase in the amount of 0.01% of the total mass of the monomers A, B, C and D in the step (2).
For the third object of the present invention:
The application of the polymer emulsion in preparing oilfield fracturing fluid.
Further, the polymer emulsion of any one of the above is used for preparing the oilfield fracturing fluid again to serve as a thickening agent.
For the fourth object of the present invention:
A strong suspension fracturing fluid comprising 0.6 parts by weight of any one of the polymer emulsions described above.
Further, it further comprises 0.3 parts by weight of a star ligand cross-linking agent, 0.1 parts by weight of an anti-swelling agent, and 90 parts by weight of water, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is H;
M is chromium;
The anti-swelling agent is a choline chloride aqueous solution with the mass concentration of 0.1 percent.
Further, 0.1 part by weight of a cleanup additive, which is an anionic surfactant, is also included.
Further, the aqueous solution further comprises 0.01 part by weight of a cosolvent, wherein the cosolvent is a betaine cosolvent.
In another embodiment, the polymer emulsion comprises a polymer (II), wherein:
The polymer (II) has rigid units Wherein:
r 1 is methyl;
R 2 is methyl;
r 3 is methyl.
Further, the structural formula of the polymer (II) is as follows:
Wherein:
x is y is 20:1;
(x+y) m is 1:0.05;
(x+y) n is 1:0.0025;
r 1 is methyl;
R 2 is methyl;
r 3 is methyl.
Still further, the polymer emulsion is composed of the following components:
50 parts by weight of an oil phase of a continuous phase;
60 parts by weight of a disperse phase aqueous phase containing polymer (II);
5 parts by weight of an emulsifier.
Still further, the oil phase is selected from kerosene. Still further, the emulsifier is selected from polyoxyethylene alkylphenol ethers.
Still further, the fatty alcohol-polyoxyethylene ether is AEO series fatty alcohol-polyoxyethylene ether; the polyoxyethylene alkylphenol ether is OP series polyoxyethylene alkylphenol ether;
the nonylphenol polyoxyethylene ether is TX series nonylphenol polyoxyethylene ether;
The polyether surfactant is Pluronic surfactant;
the polyol surfactant is Tween series polyol surfactant.
Still further, the content of the polymer (II) in the aqueous phase is 35% by weight based on the total weight of the polymer emulsion. In other embodiments: a polymer emulsion comprising a polymer (ii), wherein:
The polymer (II) has rigid units Wherein:
r 1 is n-propyl;
R 2 is n-propyl;
R 3 is n-propyl.
Further, the structural formula of the polymer (II) is as follows:
Wherein:
Y is a ratio of 30:1;
(x+y) m is a ratio of 1:0.1;
(x+y) n is a ratio of 1:0.01;
R 1 is n-propyl; ;
R 2 is n-propyl; ;
R 3 is n-propyl; .
Still further, the polymer emulsion is composed of the following components:
40 parts by weight of an oil phase of a continuous phase;
55 parts by weight of a disperse phase aqueous phase containing polymer (II);
3 parts by weight of an emulsifier.
Still further, the oil phase is selected from diesel.
Still further, the emulsifier is selected from the group consisting of nonylphenol polyoxyethylene ether.
Still further, the fatty alcohol-polyoxyethylene ether is a flat O series (peregal O) fatty alcohol-polyoxyethylene ether;
the polyoxyethylene alkylphenol ether is OP series polyoxyethylene alkylphenol ether;
the nonylphenol polyoxyethylene ether is TX series nonylphenol polyoxyethylene ether;
The polyether surfactant is Pluronic surfactant;
The polyol surfactant is Span series polyol surfactant.
Still further, the content of the polymer (II) in the aqueous phase is 30% by weight based on the total weight of the polymer emulsion.
For the second object of the invention:
the preparation method of the polymer emulsion comprises the following steps:
step (1), preparing an oil phase and emulsifier mixed solution:
Adding the oil phase with the formula amount and the emulsifier with the formula amount into a reaction container, and uniformly stirring in the atmosphere of helium gas to obtain an oil phase and emulsifier mixed solution;
Step (2), preparing an aqueous phase:
dissolving the monomer A, the monomer B, the monomer C and the monomer D in water, and uniformly mixing to obtain a water phase, wherein:
The monomer A is (methyl) acrylamide;
the monomer B is maleic anhydride;
the monomer C is 2-acrylamide-2-methylbutanoic acid;
The monomer D has the following structure:
r 1 is methyl;
R 2 is methyl;
r 3 is methyl;
Step (3), carrying out polymerization reaction to prepare polymer emulsion:
(31) Dropwise adding the water phase obtained in the step (2) into the mixed solution of the oil phase obtained in the step (1) and the emulsifier to form a reaction solution;
(32) And (3) dropwise adding an oxidation-reduction initiator, a water-soluble thermal initiator and an oil-soluble thermal initiator into the reaction liquid obtained in the step (31) under the condition of nitrogen atmosphere or inert atmosphere for polymerization reaction, and then preserving heat for a period of time to obtain the polymer emulsion.
Further, in the step (2), the weight ratio of the monomer A, the monomer B, the monomer C to the monomer D is 90:5:20:1.
Further, the polymerization reaction in the step (32) is carried out at 20℃for 3 hours;
the incubation time was 14 hours.
Further, the oxidation-reduction initiator in the step (32) is formed by mixing an oxidant and a reducing agent according to a weight ratio of 1:8, wherein:
The oxidant is potassium persulfate;
The reducing agent is ferrous sulfate.
Further, the addition amount of the oxidation-reduction initiator is 0.08% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the water-soluble thermal initiator is 0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
the addition amount of the oil-soluble thermal initiator is 0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D.
Further, the water-soluble thermal initiator in step (32) is azobisisobutylamidine hydrochloride.
Further, the oil-soluble thermal initiator in step (32) is benzoyl peroxide.
Further, in the step (1), the stirring rate was 350RPM, and the temperature of the whole system was controlled at 35℃during stirring.
Further, the weight ratio of the total mass of monomer a, monomer B, monomer C and monomer D to water in step (2) was 40.25:36.25.
Further, EDTA disodium salt was added to the aqueous phase in the amount of 0.1% of the total mass of monomer A, monomer B, monomer C and monomer D in step (2).
For the third object of the present invention:
The application of the polymer emulsion in preparing oilfield fracturing fluid.
Further, the polymer emulsion of any one of the above is used for preparing the oilfield fracturing fluid again to serve as a thickening agent.
For the fourth object of the present invention:
A strong suspension fracturing fluid comprising 3 parts by weight of any one of the polymer emulsions described above.
Further, it further comprises 0.5 parts by weight of a star ligand cross-linking agent, 0.3 parts by weight of an anti-swelling agent, and 100 parts by weight of water, wherein:
the star ligand cross-linking agent has the following structural formula:
wherein: r is methyl;
M is aluminum;
The anti-swelling agent is a choline chloride aqueous solution with the mass concentration of 0.5 percent.
Further, 0.3 parts by weight of a cleanup additive, which is a nonionic surfactant, is also included.
Further, 0.2 part by weight of a cosolvent is also included, wherein the cosolvent is MOA-9 cosolvent.
In yet another embodiment:
a polymer emulsion comprising a polymer (ii), wherein:
The polymer (II) has rigid units Wherein:
R 1 is a C20 linear alkyl group;
R 2 is a C20 linear alkyl group;
R 3 is a C20 straight chain alkyl group.
Further, the structural formula of the polymer (II) is as follows:
Wherein:
x: y is a ratio of 40:1;
(x+y) m is a ratio of 1:0.2;
(x+y) a ratio of n 1:0.025;
R 1 is a C20 linear alkyl group;
R 2 is a C20 linear alkyl group;
R 3 is a C20 straight chain alkyl group.
Still further, the polymer emulsion is composed of the following components:
40 parts by weight of an oil phase of a continuous phase;
55 parts by weight of a disperse phase aqueous phase containing polymer (II);
4 parts by weight of an emulsifier.
Still further, the oil phase is diesel. In other embodiments, the oil phase is selected from cyclohexane. In other embodiments, the oil phase is toluene. In other embodiments, the oil phase is a white oil, kerosene mixture of equal mass ratio. In other embodiments, the oil phase is a mixture of white oil, kerosene, diesel, cyclohexane, toluene in equal mass ratios.
Still further, the emulsifier is nonylphenol polyoxyethylene ether. In other embodiments: the emulsifier is a polyether surfactant. In other embodiments: the emulsifier is a polyol surfactant. In other embodiments: the emulsifier is oleamide. In other embodiments: the emulsifier is a mixture of fatty alcohol polyoxyethylene ether, polyoxyethylene alkylphenol ether, nonylphenol polyoxyethylene ether, polyether surfactant, polyol surfactant and oleamide with equal mass ratio, and the fatty alcohol polyoxyethylene ether is a flat O series (peregal O) fatty alcohol polyoxyethylene ether;
the polyoxyethylene alkylphenol ether is OP series polyoxyethylene alkylphenol ether;
the nonylphenol polyoxyethylene ether is TX series nonylphenol polyoxyethylene ether;
The polyether surfactant is Pluronic surfactant;
the polyol surfactant is Tween series polyol surfactant.
Still further, the content of the polymer (II) in the aqueous phase is 28% by weight based on the total weight of the polymer emulsion.
For the second object of the invention:
the preparation method of the polymer emulsion comprises the following steps:
step (1), preparing an oil phase and emulsifier mixed solution:
Adding the oil phase with the formula amount and the emulsifier with the formula amount into a reaction container, and uniformly stirring in an argon atmosphere to obtain an oil phase and emulsifier mixed solution;
Step (2), preparing an aqueous phase:
dissolving the monomer A, the monomer B, the monomer C and the monomer D in water, and uniformly mixing to obtain a water phase;
Step (3), carrying out polymerization reaction to prepare polymer emulsion:
(31) Dropwise adding the water phase obtained in the step (2) into the mixed solution of the oil phase obtained in the step (1) and the emulsifier to form a reaction solution;
(32) And (3) dropwise adding an oxidation-reduction initiator, a water-soluble thermal initiator and an oil-soluble thermal initiator into the reaction liquid obtained in the step (31) under the condition of argon atmosphere for polymerization reaction, and then preserving heat for a period of time to obtain the polymer emulsion.
Further, the monomer A is N-isopropyl (methyl) acrylamide;
The monomer B is fumaric acid; in other embodiments, the monomer B is itaconic acid; in other embodiments, the monomer B is a mixture of (methyl) acrylic acid, maleic anhydride, fumaric acid and itaconic acid with equal mass ratio;
The monomer C is vinyl sulfonic acid; in other embodiments: the monomer C is styrene sulfonic acid. In other embodiments: the monomer C is vinyl phosphonic acid. In other embodiments: the monomer C is 2-acrylamide-2-sodium methylpropanesulfonate. In other embodiments: the monomer C is 2-acrylamide-2-sodium methylbutyrate. In other embodiments: the monomer C is sodium vinylsulfonate. In other embodiments: the monomer C is sodium styrene sulfonate. In other embodiments: the monomer C is sodium vinylphosphonate.
The monomer D has the following structure:
wherein:
r 1 is ethyl;
R 2 is ethyl;
r 3 is ethyl.
Further, in the step (2), the weight ratio of the monomer A, the monomer B, the monomer C and the monomer D is 80:3:12:0.5.
Further, the polymerization reaction in the step (32) is carried out at 15℃for 5 hours;
The incubation time was 16 hours.
Further, the oxidation-reduction initiator in the step (32) is formed by mixing an oxidant and a reducing agent according to a weight ratio of 1:7, wherein:
the oxidant is hydrogen peroxide;
The reducing agent is sodium thiosulfate.
In other embodiments, the redox initiator of step (32) is formed by mixing an oxidizing agent and a reducing agent in a weight ratio of 1:6, wherein: the oxidant is selected from organic hydrogen peroxide; the reducing agent is octyl amine, wherein: the organic hydrogen peroxide is tert-butyl hydroperoxide. In other embodiments, the organic hydroperoxide is cumene hydroperoxide. In other embodiments, the organic hydrogen peroxide is methylcyclohexane hydrogen peroxide. In other embodiments, the organic hydroperoxide is a mixture of tert-butyl hydroperoxide, cumene hydroperoxide, methylcyclohexane hydroperoxide in equal mass ratios.
In other embodiments, the redox initiator of step (32) is formed by mixing an oxidizing agent and a reducing agent in a weight ratio of 1:6, wherein: the oxidant is selected from the group consisting of dimethylbenzoyl peroxide; the reducing agent is selected from sodium sulfite.
In other embodiments, the redox initiator of step (32) is formed by mixing an oxidizing agent and a reducing agent in a weight ratio of 1:8, wherein: the oxidant is a mixture of ammonium persulfate, potassium persulfate, hydrogen peroxide, organic hydrogen peroxide and dimethylbenzene acyl peroxide in equal mass ratio, and the organic hydrogen peroxide is tert-butyl hydrogen peroxide; the reducing agent is a mixture of sodium sulfite, ferrous sulfate, sodium thiosulfate and octylamine.
Further, the addition amount of the oxidation-reduction initiator is 0.05% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D.
The addition amount of the water-soluble thermal initiator is 0.1% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
the addition amount of the oil-soluble thermal initiator is 0.1% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D.
Further, the water-soluble thermal initiator in step (32) is water-soluble sodium persulfate. In other embodiments, the water-soluble thermal initiator in step (32) is hydrogen peroxide.
Further, the oil-soluble thermal initiator in step (32) is diacetyl peroxide.
Further, in the step (1), the stirring rate was 300RPM, and the temperature of the whole system was controlled at 30℃during stirring.
Further, the weight ratio of the total mass of monomer a, monomer B, monomer C and monomer D to water in step (2) is 30:25.
Further, EDTA disodium salt was added to the aqueous phase in the amount of 0.05% by mass of the total mass of monomer A, monomer B, monomer C and monomer D in step (2).
For the third object of the present invention:
The application of the polymer emulsion in preparing oilfield fracturing fluid.
Further, the polymer emulsion of any one of the above is used for preparing the oilfield fracturing fluid again to serve as a thickening agent.
For the fourth object of the present invention:
a strong suspension fracturing fluid comprising 2 parts by weight of any one of the polymer emulsions described above.
Further, it further comprises 0.4 parts by weight of a star ligand cross-linking agent, 0.2 parts by weight of an anti-swelling agent, and 95 parts by weight of water, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is ethyl;
m is titanium;
the anti-swelling agent is a choline chloride aqueous solution with the mass concentration of 0.3 percent.
In other embodiments, 0.4 parts by weight of a star ligand crosslinker, 0.2 parts by weight of an anti-swelling agent, and 95 parts by weight of water are also included, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is ethyl;
M is boron;
the anti-swelling agent is benzyl trimethyl ammonium chloride aqueous solution with the mass concentration of 0.1 percent.
In other embodiments, 0.4 parts by weight of a star ligand crosslinker, 0.2 parts by weight of an anti-swelling agent, and 95 parts by weight of water are also included, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is H;
M is zirconium;
the anti-swelling agent is benzyl trimethyl ammonium chloride aqueous solution with the mass concentration of 0.5 percent.
In other embodiments, 0.4 parts by weight of a star ligand crosslinker, 0.2 parts by weight of an anti-swelling agent, and 95 parts by weight of water are also included, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is ethyl;
M is titanium
The anti-swelling agent is benzyl trimethyl ammonium chloride aqueous solution with the mass concentration of 0.2 percent.
Further, 0.2 parts by weight of a cleanup additive, which is an anionic surfactant, is also included.
Further, the organic acid catalyst further comprises 0.1 part by weight of cosolvent, wherein the cosolvent is a mixture of betaine cosolvent and MOA-9 cosolvent in equal mass ratio.
Example 1:
The polymer emulsion consists of the following components:
30 parts by weight of a continuous phase oil phase;
60 parts by weight of a disperse phase aqueous phase containing the polymer (I);
3 parts by weight of an emulsifier.
Still further, the oil phase is white oil.
Still further, the emulsifier is selected from a mixture of fatty alcohol polyoxyethylene ether and a polyol surfactant, and the mass ratio of the emulsifier to the polyol surfactant is 1:1.
Still further, the fatty alcohol-polyoxyethylene ether is peregal O-10;
the polyol surfactant is a Spa80 polyol surfactant.
Still further, the content of polymer (I) or the content of polymer (II) in the aqueous phase is 32.25% based on the total weight of the polymer emulsion.
The preparation method of the polymer emulsion comprises the following steps:
step (1): preparing an oil phase and emulsifier mixed solution:
Adding a mixed emulsifier consisting of 30 parts by weight of a white oil phase, 2 parts by weight of peregal O-10 and 1 part by weight of span80 into a reactor, and carrying out constant-temperature stirring on the reactor with a mechanical stirring device, a nitrogen inlet, a constant-pressure funnel and a thermometer at the temperature of 28 ℃ and the speed of 250rpm to obtain a uniform mixed solution;
step (2): preparation of the aqueous phase
Acrylamide monomer A, (methyl) acrylic acid monomer B, 2-acrylamido-2-methylpropanesulfonic acid C and monomer D 1 are mixed according to the weight ratio of 75:4:5:0.25 is dissolved in water and evenly mixed to form a water phase, wherein:
the total weight of the monomers is 30 parts by weight, and the weight of the water is 30 parts by weight;
simultaneously adding EDTA disodium salt in an amount of 0.1 percent (0.3 parts by weight) based on the total weight of the monomers into the aqueous phase;
step (3): carrying out polymerization reaction
Transferring the water phase obtained in the step (2) into a constant pressure funnel of the reactor, and dropwise adding the water phase into the uniform mixed solution prepared in the step (1) under strong stirring (300 rpm); then, under the condition of nitrogen atmosphere, dropwise adding 0.01% of oxidation-reduction initiator based on the total weight of the monomer A, the monomer B, the monomer C and the monomer D, wherein the oxidation-reduction initiator consists of oxidant tert-butyl hydroperoxide and reducer sodium bisulphite according to the weight ratio of 1:8, and carrying out polymerization reaction for 3 hours at the temperature of 10 ℃; then preserving the heat for 14 hours to obtain white emulsion polymer emulsion, which is abbreviated as: HAPAM.
For the fourth object of the present invention:
The strong suspension fracturing fluid consists of the following substances:
1.2 parts by weight of the above polymer emulsion;
0.3 parts by weight of a star ligand cross-linking agent;
0.3 parts by weight of an anti-swelling agent;
0.1 parts by weight of a cleanup additive which is an anionic surfactant;
0.01 part by weight of a cosolvent, wherein the cosolvent is a betaine cosolvent, and the cosolvent comprises the following components in parts by weight:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is selected from H;
M is chromium;
the anti-swelling agent is a choline chloride aqueous solution with the mass concentration of 0.3 percent.
The preparation of the strong suspension fracturing fluid comprises the following steps:
Adding 0.01 part by weight of cosolvent into 98 parts by weight of water, dissolving 1.2 parts by weight of polymer emulsion, adding 0.3 part by weight of star ligand cross-linking agent, 0.3 part by weight of anti-swelling agent and 0.1 part by weight of cleanup additive after 20s, and uniformly mixing to obtain strong suspension fracturing fluid, which is called SWJX-1 for short.
And (3) placing the strong suspension fracturing fluid SWJX-1 into a Hash Mars III rheometer, setting the temperature to 130 ℃, shearing the strong suspension fracturing fluid at the shearing rate of 170s -1, and shearing the strong suspension fracturing fluid for 120min, wherein the final viscosity is 112 mPa.s.
Characterization of the properties:
1. Viscosity:
The apparent viscosity of the polymer emulsion HAPAM prepared in example 1 was determined at room temperature using a six-speed viscometer according to the determination method described in its instructions for use, to be 100 mPas.
The polymer emulsion prepared in this example was precipitated in acetone at room temperature, washed with acetone 4 times and dried at 50℃to obtain a polymer powder thereof, and the intrinsic viscosity [ eta ] of the polymer in a 0.1% by weight solution in a mixed solution of 0.5mol/l NaCl+0.5mol/l formamide was measured at room temperature using the six-speed viscometer and found to be 1200ml/g.
2. Particle size
FIG. 1 is an electron micrograph of the polymer emulsion (HAPAM) prepared in example 1, and it can be seen from FIG. 1 that the polymer emulsion (HAPAM has a particle size of 10 μm or less, which meets the properties of the emulsion.
3. Degree of polymerization (1 H NMR spectrum)
FIG. 4 is a 1 H NMR spectrum of the polymer emulsion (HAPAM) prepared in example 1. As can be seen from the information shown in fig. 4:
the polymer emulsion (HAPAM) does not contain double bonds, indicating a more complete polymerization reaction.
4. Frictional resistance
FIG. 5 is a schematic diagram of the frictional resistance of the strong suspension fracturing fluid SWJX-1 prepared in example 1. In the fracturing process of the strong suspension fracturing fluid SWJX-1 prepared in the embodiment 1, the friction resistance of 1800m depth measured by a pressure gauge installed at the bottom of the well is 7-8 MPa, namely about 3-4 MPa/km, which is lower than other fracturing fluids.
5. Resistivity reduction
FIG. 6 is a schematic representation of the resistivity of the strong suspension fracturing fluid SWJX-1 prepared in example 1. As can be seen from fig. 6:
At the same application concentration, the result of the strong suspension fracturing fluid SWJX-1 is comparable to that of the foreign product 501K of the same type.
6. Mineralization resistance
The strong suspension fracturing fluid SWJX-1 prepared in example 1 has a rheological curve of continuous shearing for 120min at 160 ℃ for 170s -1 in a Ha Ke rheometer, which can keep the viscosity of more than 100 mPa.s, which indicates that the strong suspension fracturing fluid SWJX-1 has strong mineralization resistance (100000 ppm).
Example 2:
the preparation method of the polymer emulsion comprises the following steps:
step A: preparation of an oil phase and emulsifier mixture
Adding a mixed emulsifier consisting of 38 parts by weight of kerosene oil phase, 4 parts by weight of oleamide and OP-7 into a reactor provided with a mechanical stirring device, a nitrogen inlet, a constant pressure funnel and a thermometer, and stirring at constant temperature under the conditions of 30 ℃ and 320rpm to obtain a uniform mixed solution;
And (B) step (B): preparation of the aqueous phase
The weight ratio of (methyl) acrylamide monomer A, maleic anhydride monomer B, 2-acrylamido-2-methylpropanesulfonic acid C and monomer D 1 is 20:3:5:0.80 is dissolved in water, the weight ratio of the monomer to the weight of the water is 1:1, the total weight of the water phase is 70, and 0.1 percent EDTA disodium salt based on the total weight of the monomers is added at the same time, so that a water phase is obtained;
Step C: carrying out polymerization reaction
Transferring the water phase obtained in the step B) into a constant pressure funnel of the reactor, and dropwise adding the water phase into the uniform mixed solution prepared in the step A) under strong stirring (300 rpm); then, under the condition of nitrogen atmosphere, dropwise adding 0.06% of oxidation-reduction initiator based on the total weight of the monomer A, the monomer B, the monomer C and the monomer D, wherein the oxidation-reduction initiator consists of oxidant potassium persulfate and reducer ferrous sulfate according to the weight ratio of 1:6, and carrying out polymerization reaction for 3.5 hours at the temperature of 2 ℃; then preserving the temperature for 15 hours to obtain the white emulsion fracturing fluid.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 120 mPas by the method described in example 1, and the intrinsic viscosity [ eta ] value was 1080ml/g.
Preparing a strong suspension fracturing fluid:
Adding 0.01 part by weight of cosolvent into 98 parts by weight of water, dissolving 1.2 parts by weight of polymer emulsion, adding 0.3 part by weight of star ligand cross-linking agent, 0.3 part by weight of anti-swelling agent and 0.1 part by weight of cleanup additive after 20s, uniformly mixing, and then placing into a Hash Mars III rheometer, wherein the temperature is set to 130 ℃, the shearing rate is set to 170s -1, the shearing time is set to 120min, and the final viscosity is 87 mPa.s.
Example 3:
the preparation method of the polymer emulsion comprises the following steps:
step A: preparation of an oil phase and emulsifier mixture
Adding 60 parts by weight of diesel oil phase and 3 parts by weight of mixed emulsifier composed of TX-10 and span80 into a reactor provided with a mechanical stirring device, a nitrogen inlet, a constant pressure funnel and a thermometer, and stirring at constant temperature under the conditions of 35 ℃ and 280rpm to obtain uniform mixed solution;
And (B) step (B): preparation of the aqueous phase
N-hydroxypropyl (methyl) acrylamide monomer A, fumaric acid monomer B, 2-acrylamido-2-methylpropanesulfonic acid C and monomer D 1 are mixed according to the weight ratio of 90:7:15:0.40 of EDTA disodium salt is dissolved in water, the weight ratio of the monomers to the weight of the water is 1:1, the total weight of the water phase is 70, and 0.1 percent of EDTA disodium salt based on the total weight of the monomers is added at the same time, so that a water phase is obtained;
Step C: carrying out polymerization reaction
Transferring the water phase obtained in the step B) into a constant pressure funnel of the reactor, and dropwise adding the water phase into the uniform mixed solution prepared in the step A) under strong stirring (300 rpm); then, dropwise adding 0.02% of oxidation-reduction initiator based on the total weight of the monomer A, the monomer B, the monomer C and the monomer D under the condition of nitrogen atmosphere, wherein the oxidation-reduction initiator consists of oxidant hydrogen peroxide and reducer octyl amine according to the weight ratio of 1:8, and carrying out polymerization reaction for 5.5 hours at the temperature of 5 ℃; then preserving the temperature for 17 hours to obtain the white emulsion fracturing fluid.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 108 mPas by the method described in example 1, and the intrinsic viscosity [ eta ] value was 1030ml/g.
Preparing a strong suspension fracturing fluid:
Adding 0.01 part by weight of cosolvent into 98 parts by weight of water, dissolving 1.2 parts by weight of polymer emulsion, adding 0.3 part by weight of star ligand cross-linking agent, 0.3 part by weight of anti-swelling agent and 0.1 part by weight of cleanup additive after 20s, uniformly mixing, and then placing into a Hash Mars III rheometer, wherein the temperature is set to 130 ℃, the shearing rate is set to 170s -1, the shearing time is set to 120min, and the final viscosity is 90 mPas.
Example 4:
the preparation method of the polymer emulsion comprises the following steps:
step A: preparation of an oil phase and emulsifier mixture
Adding 42 parts by weight of solvent oil phase and 7 parts by weight of TX-4 emulsifier into a reactor provided with a mechanical stirring device, a nitrogen inlet, a constant pressure funnel and a thermometer, and stirring at constant temperature under the conditions of 32 ℃ and 350rpm to obtain a uniform mixed solution;
And (B) step (B): preparation of the aqueous phase
N-isopropyl (methyl) acrylamide monomer A, itaconic acid monomer B, 2-acrylamido-2-methylpropanesulfonic acid C and monomer D 1 are mixed according to the weight ratio of 90:25:10:0.60 of EDTA disodium salt is dissolved in water, the weight ratio of the monomers to the weight of the water is 1:1, the total weight of the water phase is 70, and 0.1 percent of EDTA disodium salt based on the total weight of the monomers is added at the same time, so that a water phase is obtained;
Step C: carrying out polymerization reaction
Transferring the water phase obtained in the step B) into a constant pressure funnel of the reactor, and dropwise adding the water phase into the uniform mixed solution prepared in the step A) under strong stirring (300 rpm); then, dropwise adding 0.04% of oxidation-reduction initiator based on the total weight of the monomer A, the monomer B, the monomer C and the monomer D under the condition of nitrogen atmosphere, wherein the oxidation-reduction initiator consists of oxidant tert-butyl hydroperoxide and reducer octylamine according to the weight ratio of 1:6, and carrying out polymerization reaction for 6.0 hours at the temperature of 8 ℃; then preserving heat for 16 hours to obtain the white emulsion fracturing fluid.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 115 mPas and the intrinsic viscosity [. Eta. ] value was 900ml/g by the measurement method described in example 1.
Preparing a strong suspension fracturing fluid:
Adding 0.01 part by weight of cosolvent into 98 parts by weight of water, dissolving 1.2 parts by weight of polymer emulsion, adding 0.3 part by weight of star ligand cross-linking agent, 0.3 part by weight of anti-swelling agent and 0.1 part by weight of cleanup additive after 20s, uniformly mixing, putting into a Hash Mars III rheometer, setting the temperature to 130 ℃, and shearing at 170s -1 for 120min, wherein the final viscosity is 10 mPas, and no cross-linking occurs.
Example 5:
the preparation method of the polymer emulsion comprises the following steps:
step A: preparation of an oil phase and emulsifier mixture
Adding 50 parts by weight of toluene oil phase and 3 parts by weight of a mixed emulsifier consisting of Pluronic RPE3110 and TX-10 into a reactor provided with a mechanical stirring device, a nitrogen inlet, a constant pressure funnel and a thermometer, and stirring at constant temperature under the conditions of 32 ℃ and 320rpm to obtain a uniform mixed solution;
And (B) step (B): preparation of the aqueous phase
(Meth) acrylamide monomer A, acrylic acid B, 2-acrylamido-2-methylpropanesulfonic acid sodium monomer C and monomer D 1 are mixed according to the weight ratio of 86:46:10.0:1.0 in water, wherein the weight ratio of the monomers to the weight of water is 1:1, the total weight of the aqueous phase is 70, and 0.1 percent EDTA disodium salt based on the total weight of the monomers is added at the same time, so that an aqueous phase is obtained;
Step C: carrying out polymerization reaction
Transferring the water phase obtained in the step B) into a constant pressure funnel of the reactor, and dropwise adding the water phase into the uniform mixed solution prepared in the step A) under strong stirring (300 rpm); then, under the condition of nitrogen atmosphere, dropwise adding 0.05 percent of oxidation-reduction initiator based on the total weight of the monomer A, the monomer B, the monomer C and the monomer D, wherein the oxidation-reduction initiator consists of oxidant, namely, dimethylbenzene peroxide and reducing agent, namely, sodium bisulfite according to the weight ratio of 1:8, and carrying out polymerization reaction for 4.0 hours at the temperature of 8 ℃; then preserving the temperature for 18 hours to obtain the white emulsion fracturing fluid.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 96 mPas and the intrinsic viscosity [. Eta. ] value of 1150ml/g by the measurement method described in example 1.
Preparing a strong suspension fracturing fluid:
Adding 0.01 part by weight of cosolvent into 98 parts by weight of water, dissolving 1.2 parts by weight of polymer emulsion, adding 0.3 part by weight of star ligand cross-linking agent, 0.3 part by weight of anti-swelling agent and 0.1 part by weight of cleanup additive after 20s, uniformly mixing, and then placing into a Hash Mars III rheometer, wherein the temperature is set to 130 ℃, the shearing rate is set to 170s -1, the shearing time is set to 120min, and the final viscosity is 75 mPa.s.
Example 6:
the preparation method of the polymer emulsion comprises the following steps:
step A: preparation of an oil phase and emulsifier mixture
Adding 56 parts by weight of an oil phase consisting of white oil and solvent oil according to a weight ratio of 1:1 and 3 parts by weight of an emulsifier consisting of Span80 and Tween80 according to a weight ratio of 1:5 into a reactor provided with a mechanical stirring device, a nitrogen inlet, a constant pressure funnel and a thermometer, and stirring at a constant temperature of 30 ℃ and 260rpm to obtain a uniform mixed solution;
And (B) step (B): preparation of the aqueous phase
N-isopropyl (methyl) acrylamide monomer A, acrylic acid monomer B, sodium styrene sulfonate monomer C and monomer D 1 are mixed according to the weight ratio of 75:5:15:0.90 of EDTA disodium salt is dissolved in water, the weight ratio of the monomers to the weight of the water is 1:1, the total weight of the water phase is 70, and 0.1 percent of EDTA disodium salt based on the total weight of the monomers is added at the same time, so that a water phase is obtained;
Step C: carrying out polymerization reaction
Transferring the water phase obtained in the step B) into a constant pressure funnel of the reactor, and dropwise adding the water phase into the uniform mixed solution prepared in the step A) under strong stirring (300 rpm); then, under the condition of nitrogen atmosphere, dropwise adding 0.08 percent of oxidation-reduction initiator based on the total weight of the monomer A, the monomer B, the monomer C and the monomer D, wherein the oxidation-reduction initiator consists of oxidant potassium persulfate and reducer ferrous sulfate according to the weight ratio of 1:6, and carrying out polymerization reaction for 4.6 hours at the temperature of 10 ℃; then preserving the temperature for 15 hours to obtain the white emulsion fracturing fluid.
The apparent viscosity of the fracturing fluid prepared in this example was determined by the method described in example 1 to be 97 mPas and the intrinsic viscosity [ eta ] value of the fracturing fluid was 1210ml/g.
Preparing a strong suspension fracturing fluid:
Adding 0.01 part by weight of cosolvent into 98 parts by weight of water, dissolving 1.2 parts by weight of polymer emulsion, adding 0.3 part by weight of star ligand cross-linking agent, 0.3 part by weight of anti-swelling agent and 0.1 part by weight of cleanup additive after 20s, uniformly mixing, and then placing into a Hash Mars III rheometer, wherein the temperature is set to 130 ℃, the shearing rate is set to 170s -1, the shearing time is set to 120min, and the final viscosity is 101 mPa.s.
Example 7:
This example was carried out in the same manner as described in example 1, except that the water-soluble initiator azobisis Ding Mi-in hydrochloride was used in this example.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 110 mPas by the method described in example 1, and the intrinsic viscosity [. Eta. ] value was 1050ml/g.
Preparation of fracturing fluid
The final viscosity was 100 mPas in the same manner as described in example 1.
Example 8:
this example was carried out in the same manner as described in example 2, except that the water-soluble initiator azobisisobutylamidine hydrochloride was used in this example.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 96 mPas and the intrinsic viscosity [ eta ] value was 980ml/g by the measurement method described in example 1.
Preparation of fracturing fluid
The final viscosity was 60 mPas in the same manner as described in example 1.
Example 9:
this example was performed in the same manner as described in example 3, except that this example used sodium persulfate as a water-soluble initiator.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 92 mPas by the method described in example 1, and the intrinsic viscosity [ eta ] value was 958ml/g.
Preparation of fracturing fluid
The final viscosity was 58 mPas in the same manner as described in example 1.
Example 10:
This example was performed in the same manner as described in example 4, except that the example used the oil-soluble initiator azobisisobutyronitrile.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 106 mPas by the method described in example 1, and the intrinsic viscosity [ eta ] value was 1080ml/g.
Preparation of fracturing fluid
The final viscosity was 78 mPas in the same manner as described in example 1.
Example 11:
This example was performed in the same manner as described in example 5, except that the example used an oil-soluble initiator benzoyl peroxide.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 100 mPas by the method described in example 1, and the intrinsic viscosity [. Eta. ] value was 1150ml/g.
Preparation of fracturing fluid
The final viscosity was 65 mPas in the same manner as described in example 1.
Example 12:
This example was performed in the same manner as described in example 6, except that the example used the oil-soluble initiator diacetyl peroxide.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 110 mPas and the intrinsic viscosity [ eta ] value of the fracturing fluid was 1120ml/g by the measurement method described in example 1.
Preparation of fracturing fluid
The final viscosity was 95 mPas in the same manner as described in example 1.
Comparative examples:
the preparation method of the polymer emulsion comprises the following steps:
step A: preparation of an oil phase and emulsifier mixture
Adding a mixed emulsifier consisting of 38 parts by weight of kerosene oil phase, 4 parts by weight of oleamide and OP-7 into a reactor provided with a mechanical stirring device, a nitrogen inlet, a constant pressure funnel and a thermometer, and stirring at constant temperature under the conditions of 30 ℃ and 320rpm to obtain a uniform mixed solution;
And (B) step (B): preparation of the aqueous phase
Mixing (methyl) acrylamide monomer A and maleic anhydride monomer B with the following components in a weight ratio of 20:8 is dissolved in water, the weight ratio of the monomer to the water is 1:1, the total weight of the water phase is 70, and 0.1 percent EDTA disodium salt based on the total weight of the monomers is added at the same time, so that a water phase is obtained;
Step C: carrying out polymerization reaction
Transferring the water phase obtained in the step B) into a constant pressure funnel of the reactor, and dropwise adding the water phase into the uniform mixed solution prepared in the step A) under strong stirring (300 rpm); then, under the condition of nitrogen atmosphere, dropwise adding 0.06% of oxidation-reduction initiator based on the total weight of the monomer A, the monomer B and the oxidant potassium persulfate and the reducer ferrous sulfate according to the weight ratio of 1:6, and carrying out polymerization reaction for 3.5 hours at the temperature of 2 ℃; then preserving the temperature for 15 hours to obtain the white emulsion fracturing fluid.
The apparent viscosity of the fracturing fluid prepared in this example was determined to be 160 mPas by the method described in example 1, and the intrinsic viscosity [. Eta. ] value was 1680ml/g.
Characterization of the properties:
FIG. 2 is a graph of infrared spectra (FT-IR) of the polymer emulsion (HAPAM) prepared in example 1 versus the polymer emulsion (PAM) prepared in comparative example. It can be seen from FIG. 2 that the peak shape becomes broader below 3000cm -1 due to the combination of imide groups in the ring structure with amide groups in acrylamide, which can be demonstrated for D1 monomers. In addition, 2921cm -1 and 2850cm -1 have strong C-H stretching vibration absorption peaks, 760cm -1 is a medium gamma vibration absorption peak in CH 2. This is due to the methyl group in HAMPS.
FIG. 3 is a thermogravimetric analysis (TG) plot of the polymer emulsion (HAPAM) prepared in example 1 versus the polymer emulsion (PAM) prepared in comparative example. From FIG. 3, it is understood that the comparative examples have thermal weights of 269℃and 381℃respectively, and the target polymer is present at 292℃and 402 ℃. The presence of monomer C and monomer D is illustrated to significantly increase the thermal decomposition temperature of the molecular chain, and the presence of monomer C and monomer D is also illustrated.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various modifications may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (32)
1. Polymer emulsion comprising a polymer (I) or a polymer (ii), wherein:
The polymer (I) has rigid units
The polymer (II) has rigid unitsWherein:
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
2. The polymer emulsion of claim 1 wherein the polymer (I) has the formula:
Wherein:
x and y are a ratio of 20:1 to 40:1;
(x+y) m is a ratio of 1:0.005 to 1:0.05;
(x+y): n is a ratio of 1:0.05 to 1:0.2.
3. The polymer emulsion of claim 1 wherein the polymer (ii) has the formula:
Wherein:
x and y are a ratio of 20:1 to 40:1;
(x+y) m is a ratio of 1:0.05 to 1:0.2;
(x+y) n is a ratio of 1:0.0025 to 1:0.025;
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
4. The polymer emulsion of claim 1, wherein the polymer emulsion consists of:
30-50 parts by weight of an oil phase of a continuous phase;
50 to 60 parts by weight of a disperse phase aqueous phase containing the polymer (I) or the polymer (II);
2 to 5 weight portions of emulsifying agent.
5. The polymer emulsion of claim 4 wherein the oil phase is selected from at least one of white oil, kerosene, diesel, cyclohexane, toluene.
6. The polymer emulsion of claim 4 wherein the emulsifier is selected from at least one of the group consisting of fatty alcohol polyoxyethylene ethers, polyoxyethylene alkylphenol ethers, nonylphenol polyoxyethylene ethers, polyether surfactants, polyol surfactants, and oleamides.
7. The polymer emulsion of claim 6 wherein the fatty alcohol-polyoxyethylene ether is one of a flat O-series fatty alcohol-polyoxyethylene ether and an AEO-series fatty alcohol-polyoxyethylene ether;
the polyoxyethylene alkylphenol ether is OP series polyoxyethylene alkylphenol ether;
the nonylphenol polyoxyethylene ether is TX series nonylphenol polyoxyethylene ether;
The polyether surfactant is Pluronic surfactant;
the polyol surfactant is Span series polyol surfactant or Tween series polyol surfactant.
8. The polymer emulsion of claim 4 wherein the polymer (I) or polymer (II) is present in the aqueous phase in an amount of 25% to 35% by weight based on the total weight of the polymer emulsion.
9. The preparation method of the polymer emulsion is characterized by comprising the following steps:
step (1), preparing an oil phase and emulsifier mixed solution:
adding the oil phase with the formula amount and the emulsifier with the formula amount into a reaction container, and uniformly stirring in the atmosphere of nitrogen or inert gas to obtain an oil phase and emulsifier mixed solution;
Step (2), preparing an aqueous phase:
dissolving the monomer A, the monomer B, the monomer C and the monomer D in water, and uniformly mixing to obtain a water phase;
And (3) performing polymerization reaction to prepare polymer emulsion.
10. The method of preparing a polymer emulsion of claim 9 wherein step (3) comprises:
(31) Dropwise adding the water phase obtained in the step (2) into the mixed solution of the oil phase obtained in the step (1) and the emulsifier to form a reaction solution;
(32) And (3) dropwise adding an oxidation-reduction initiator, a water-soluble thermal initiator and an oil-soluble thermal initiator into the reaction liquid obtained in the step (31) under the condition of nitrogen atmosphere or inert atmosphere for polymerization reaction, and then preserving heat for a period of time to obtain the polymer emulsion.
11. The method for preparing a polymer emulsion according to claim 9, wherein the monomer a in the step (2) is one selected from the group consisting of acrylamide, (meth) acrylamide, N-hydroxypropyl (meth) acrylamide and N-isopropyl (meth) acrylamide.
12. The method for preparing a polymer emulsion according to claim 9, wherein the monomer B in the step (2) is at least one selected from (meth) acrylic acid, maleic anhydride, fumaric acid and itaconic acid.
13. The method for preparing a polymer emulsion according to claim 9, wherein the monomer C in the step (2) is selected from one of 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, sodium 2-acrylamido-2-methylpropanesulfonate, sodium 2-acrylamido-2-methylbutanoate, sodium vinylsulfonate, sodium styrenesulfonate, and sodium vinylphosphonate.
14. The method of preparing a polymer emulsion of claim 9 wherein monomer D in step (2) is monomer D 1 having the structure:
monomer D 1, or
The monomer D has the following structure:
wherein:
R 1 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
r 2 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group;
R 3 is a C1-C20 linear alkyl group, preferably a C1-C3 linear alkyl group.
15. The method for preparing a polymer emulsion according to claim 9, wherein the weight ratio of monomer a, monomer B, monomer C and monomer D in step (2) is (75 to 90): (1-5): (5-20): (0.25-1).
16. The process for preparing a polymer emulsion according to claim 10, wherein the polymerization in step (32) in step (2) is carried out at a temperature of 10 ℃ to 20 ℃ for at least 3 hours, preferably 3 to 6 hours;
The incubation time is at least 14 hours, preferably 14 to 18 hours.
17. The method of preparing a polymer emulsion of claim 10 wherein the oxidation-reduction initiator of step (32) of step (2) is formed by mixing an oxidizing agent and a reducing agent in a weight ratio of 1:6 to 1:8.
18. The method for preparing a polymer emulsion according to claim 17, wherein the oxidizing agent is at least one selected from the group consisting of ammonium persulfate, potassium persulfate, hydrogen peroxide, organic hydrogen peroxide, and xylene peroxide;
the reducing agent is at least one selected from sodium sulfite, ferrous sulfate, sodium thiosulfate or fatty amine.
19. The method for producing a polymer emulsion according to claim 18, wherein the organic hydroperoxide is at least one of t-butyl hydroperoxide, cumene hydroperoxide, and methylcyclohexane hydroperoxide.
20. The method for preparing a polymer emulsion according to claim 17, wherein the addition amount of the oxidation-reduction initiator is 0.01% to 0.08% of the sum of the mass of the monomer a, the monomer B, the monomer C and the monomer D;
The addition amount of the water-soluble thermal initiator is 0.01-0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D;
The addition amount of the oil-soluble thermal initiator is 0.01-0.3% of the sum of the mass of the monomer A, the mass of the monomer B, the mass of the monomer C and the mass of the monomer D.
21. The method of preparing a polymer emulsion of claim 10 wherein the water-soluble thermal initiator in step (32) is one of water-soluble azo diiso Ding Mi hydrochloride, azo diisobutylamidine hydrochloride, water-soluble sodium persulfate, hydrogen peroxide.
22. The method of preparing a polymer emulsion of claim 10 wherein the oil-soluble thermal initiator in step (32) is one of oil-soluble azobisisobutyronitrile, benzoyl peroxide, diacetyl peroxide.
23. The method for preparing a polymer emulsion according to claim 9, wherein the stirring rate in the step (1) is 250 to 350RPM, and the temperature of the whole system is controlled to be 28 to 35 ℃ during stirring.
24. The method for producing a polymer emulsion according to claim 9, wherein the weight ratio of the total mass of monomer a, monomer B, monomer C and monomer D to water in step (2) is (20.5 to 40.25): (13.25-36.25).
25. The method for preparing a polymer emulsion according to claim 9, wherein EDTA disodium salt is added to the aqueous phase in an amount of 0.01 to 0.1% based on the total mass of the monomers A, B, C and D in step (2).
26. Use of the polymer emulsion of any one of claims 1-25 in the preparation of an oilfield fracturing fluid.
27. Use of the polymer emulsion of any one of claims 1-25 in the preparation of a fracturing fluid for oilfield applications as a thickener.
28. A strong suspension fracturing fluid comprising 0.6 to 3 parts by weight of the polymer emulsion of any one of claims 1 to 25.
29. The strong suspension fracturing fluid of claim 28, further comprising 0.3 to 0.5 parts by weight of a star ligand cross-linking agent, 0.1 to 0.3 parts by weight of an anti-swelling agent, and 90 to 100 parts by weight of water, wherein:
the star ligand cross-linking agent has the following structural formula:
Wherein: r is one selected from H, methyl and ethyl;
m is one of chromium, aluminum, titanium, boron and zirconium.
30. The strong suspension fracturing fluid of claim 28, wherein said anti-swelling agent is aqueous solution of choline chloride having a mass concentration of 0.1% to 0.5% or aqueous solution of benzyltrimethylammonium chloride having a mass concentration of 0.1% to 0.5%.
31. The strong suspension fracturing fluid of claim 28, further comprising 0.1 to 0.3 parts by weight of a cleanup additive, said cleanup additive being an anionic surfactant or a nonionic surfactant.
32. The strong suspension fracturing fluid of claim 28, further comprising 0.01 to 0.2 parts by weight of a co-solvent, said co-solvent being a betaine-type co-solvent and/or a MOA-9 co-solvent.
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