CN117866012A - Polymer monomer and preparation method thereof, copolymer and preparation method and application thereof, and drilling fluid - Google Patents
Polymer monomer and preparation method thereof, copolymer and preparation method and application thereof, and drilling fluid Download PDFInfo
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- CN117866012A CN117866012A CN202211237902.8A CN202211237902A CN117866012A CN 117866012 A CN117866012 A CN 117866012A CN 202211237902 A CN202211237902 A CN 202211237902A CN 117866012 A CN117866012 A CN 117866012A
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- Prior art keywords
- monomer
- copolymer
- solution
- polymer
- azo
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- 239000000178 monomer Substances 0.000 title claims abstract description 169
- 229920000642 polymer Polymers 0.000 title claims abstract description 161
- 229920001577 copolymer Polymers 0.000 title claims abstract description 95
- 238000005553 drilling Methods 0.000 title claims abstract description 39
- 239000012530 fluid Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 13
- 239000003208 petroleum Substances 0.000 claims abstract description 13
- 125000003368 amide group Chemical group 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- -1 bisacrylamide compound Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000004005 microsphere Substances 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 229920000136 polysorbate Polymers 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000001409 amidines Chemical class 0.000 claims description 7
- ZMLXKXHICXTSDM-UHFFFAOYSA-N n-[1,2-dihydroxy-2-(prop-2-enoylamino)ethyl]prop-2-enamide Chemical compound C=CC(=O)NC(O)C(O)NC(=O)C=C ZMLXKXHICXTSDM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- PNYLLBWMOUAQHV-UHFFFAOYSA-N acetonitrile;triphenylphosphane Chemical group CC#N.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 PNYLLBWMOUAQHV-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 3
- HDMXIELEUKTYFR-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC HDMXIELEUKTYFR-UHFFFAOYSA-N 0.000 claims description 3
- AXZHOFSSTJKWJE-UHFFFAOYSA-N bismuth;trifluoromethanesulfonic acid Chemical compound [Bi].OS(=O)(=O)C(F)(F)F AXZHOFSSTJKWJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- GWGBNENHEGYJSN-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O GWGBNENHEGYJSN-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- KOCDJSLUDZGVJX-UHFFFAOYSA-N indium;trifluoromethanesulfonic acid Chemical compound [In].OS(=O)(=O)C(F)(F)F KOCDJSLUDZGVJX-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 2
- 229950008882 polysorbate Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- HWUPLUNLNUHIQZ-UHFFFAOYSA-N copper;trifluoromethanesulfonic acid Chemical compound [Cu].OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F HWUPLUNLNUHIQZ-UHFFFAOYSA-N 0.000 claims 2
- CFSYYJNGCPTQRE-UHFFFAOYSA-N calcium;trifluoromethanesulfonic acid Chemical compound [Ca].OS(=O)(=O)C(F)(F)F CFSYYJNGCPTQRE-UHFFFAOYSA-N 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- 230000002522 swelling effect Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 103
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 75
- 238000003756 stirring Methods 0.000 description 60
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 239000007787 solid Substances 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- 238000000967 suction filtration Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 26
- 229910000019 calcium carbonate Inorganic materials 0.000 description 25
- 239000002245 particle Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 15
- 239000010419 fine particle Substances 0.000 description 15
- 238000000227 grinding Methods 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 230000000903 blocking effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 230000035699 permeability Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011435 rock Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000440 bentonite Substances 0.000 description 8
- 229910000278 bentonite Inorganic materials 0.000 description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000002981 blocking agent Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 4
- 230000009545 invasion Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 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
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 235000011078 sorbitan tristearate Nutrition 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 2
- FYYOTZLMLLTWAP-UHFFFAOYSA-N 3,3-dimethylpent-4-enoic acid Chemical compound C=CC(C)(C)CC(O)=O FYYOTZLMLLTWAP-UHFFFAOYSA-N 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- 239000012153 distilled water Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 239000001798 (E)-2,4-dimethylpent-2-enoic acid Substances 0.000 description 1
- 239000001373 (E)-2-methylpent-2-enoic acid Substances 0.000 description 1
- BGUAPYRHJPWVEM-UHFFFAOYSA-N 2,2-dimethyl-4-pentenoic acid Chemical compound OC(=O)C(C)(C)CC=C BGUAPYRHJPWVEM-UHFFFAOYSA-N 0.000 description 1
- DMHLGGQHOSTMJG-UHFFFAOYSA-N 2,4-Dimethyl-2-pentenoic acid Chemical compound CC(C)C=C(C)C(O)=O DMHLGGQHOSTMJG-UHFFFAOYSA-N 0.000 description 1
- JJYWRQLLQAKNAD-UHFFFAOYSA-N 2-Methyl-2-pentenoic acid Natural products CCC=C(C)C(O)=O JJYWRQLLQAKNAD-UHFFFAOYSA-N 0.000 description 1
- JJYWRQLLQAKNAD-PLNGDYQASA-N 2-methyl-2-pentenoic acid Chemical compound CC\C=C(\C)C(O)=O JJYWRQLLQAKNAD-PLNGDYQASA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- KVUDZUPUUSUAAJ-UHFFFAOYSA-N bis(chloromethyl) carbonate Chemical compound ClCOC(=O)OCCl KVUDZUPUUSUAAJ-UHFFFAOYSA-N 0.000 description 1
- HIYUMYXSGIKHHE-UHFFFAOYSA-M bismuth trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F HIYUMYXSGIKHHE-UHFFFAOYSA-M 0.000 description 1
- PUQLFUHLKNBKQQ-UHFFFAOYSA-L calcium;trifluoromethanesulfonate Chemical compound [Ca+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PUQLFUHLKNBKQQ-UHFFFAOYSA-L 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- KZNPIUNERUJTFX-UHFFFAOYSA-N n-(2-hydroxybutyl)prop-2-enamide Chemical compound CCC(O)CNC(=O)C=C KZNPIUNERUJTFX-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- UIUWNILCHFBLEQ-UHFFFAOYSA-N pent-3-enoic acid Chemical compound CC=CCC(O)=O UIUWNILCHFBLEQ-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
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- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to the field of petroleum aids, in particular to a polymer monomer and a preparation method thereof, a copolymer and a preparation method and application thereof, and drilling fluid. The polymer monomer is selected from triphenylphosphine derivatives containing amide bonds, carbon-carbon double bonds, phosphorus-carbon double bonds and alkyl groups. According to the invention, a novel polymer monomer is synthesized, the monomer contains an amide bond, a carbon-carbon double bond, a phosphorus-carbon double bond and an alkyl group, and an amide group is introduced into the molecule, so that a hydration group can be provided for the prepared polymer, and the water absorption swelling property of the polymer is improved; the triphenylphosphine group is introduced to provide a hydrophobic group for the prepared polymer, so that the rigidity of a polymer molecular chain is enhanced, and the temperature resistance and salt resistance of the polymer molecule are enhanced.
Description
Technical Field
The invention relates to the field of petroleum aids, in particular to a polymer monomer and a preparation method thereof, a copolymer and a preparation method and application thereof, and drilling fluid.
Background
The well wall instability mainly refers to underground complex conditions such as well collapse, diameter shrinkage, stratum fracture and the like in the well drilling process. Well collapse is prone to occur when certain formations are drilled that encounter a bedding fracture, strong earth stress, pore pressure anomalies, long distance shale, large dip angles, and may experience wellbore skewing. The main factors causing the instability of the well wall can be summarized as physical and chemical factors, engineering technical factors and mechanical factors. In terms of the influence of drilling fluid on the stability of a well wall, the change of the structural strength and the mechanical stability of the well wall caused by the invasion of drilling fluid filtrate into a shale stratum is a main reason for the instability of the well wall, so that the difference of the plugging performance of the drilling fluid is directly related to the advantages and disadvantages of the collapse prevention performance of the drilling fluid. Under the action of pressure difference, plugging particles in the drilling fluid enter micropores of the stratum so as to form a sealing layer near a well bore, the sealing effect is good, the lower the permeability of rock of the sealing layer is, the slower the speed of transferring well bore pressure to a distant stratum is, the slower the speed of changing the mechanical balance of rock of the stratum is, the longer the collapse period of the well wall is, and the well wall tends to be stable. Currently, plugging materials used in drilling fluids mainly include rigid plugging agents and flexible plugging agents. The rigid plugging agent, such as superfine calcium carbonate, nano-micron silicon dioxide and the like, can enter into the hole seams with smaller particle sizes under the action of pressure difference to realize plugging, and has poor plugging effect on micro-cracks with nano-micron level.
It is therefore desirable to develop a flexible blocking agent.
Disclosure of Invention
The invention aims to solve the problems of layer-encountering micro-cracks, abnormal pore pressure, brittle mudstone and igneous rock instability in drilling when the plugging agent is used in drilling fluid in the prior art, and provides a polymer monomer, a preparation method thereof, a copolymer, a preparation method thereof and application thereof, and the drilling fluid.
In order to achieve the above object, the first aspect of the present invention provides a polymer monomer selected from triphenylphosphine derivatives having an amide bond, a carbon-carbon double bond, a phosphorus-carbon double bond, and an alkyl group.
In a second aspect, the present invention provides a process for the preparation of a polymer monomer, the process comprising:
1) Mixing a bisacrylamide compound with a solvent to obtain a solution I;
2) Mixing triphenylphosphine alkyl amide compounds with the solution I to obtain a solution II;
3) The catalyst is contacted with the solution II to react, so as to obtain a solution III;
4) And removing the solvent from the solution III, and drying to obtain a polymer monomer.
In a third aspect, the present invention provides a polymer monomer prepared by the preparation method of the present invention.
In a fourth aspect, the present invention provides a copolymer comprising: structural unit c derived from the polymer monomer of the present invention, structural unit a represented by formula (2), structural unit b represented by formula (3):
wherein R is 1 、R 3 Each independently selected from H or C 1 -C 6 Alkyl of R 2 Selected from amide groups, R 4 Selected from carboxylic acid groups; wherein,structural unit c: structural unit a: the molar ratio of the structural units b is (2-7): (20-60): (15-35), the weight-average molecular weight of the copolymer was 4.25X10 4 -5×10 4 g/mol；
In a fifth aspect, the present invention provides a method for producing a copolymer, comprising the steps of:
(1) Mixing an emulsifying agent with an organic solvent to obtain a solution A;
(2) Mixing a monomer (1) shown in a formula (5), a monomer (2) shown in a formula (6), a polymer monomer and water to obtain a solution B;
(3) The solution A, the initiator and the solution B are contacted for copolymerization reaction to obtain a copolymer;
wherein the polymer monomer is the polymer monomer disclosed by the invention;
wherein R is 1 、R 2 、R 3 、R 4 The definition of (c) is correspondingly the same as in the fourth aspect of the invention.
In a sixth aspect, the present invention provides a copolymer produced by the production method of the present invention.
In a seventh aspect, the present invention provides the use of a copolymer according to the invention as a polymeric microsphere plugging agent in the field of petroleum aids.
In an eighth aspect, the present invention provides a drilling fluid comprising a copolymer according to the present invention.
Compared with the prior art, the invention has the advantages that:
the invention synthesizes a new polymer monomer, which contains amide bond, carbon-carbon double bond, phosphorus-carbon double bond and alkyl, and introduces amide group into the molecule, which can provide hydration group for the prepared polymer, and is beneficial to improving the water absorption swelling property of the polymer; the triphenylphosphine group is introduced to provide a hydrophobic group for the prepared polymer, so that the rigidity of a polymer molecular chain is enhanced, and the temperature resistance and salt resistance of the polymer molecule are enhanced.
The copolymer prepared by the invention can be used for the application of polymer microsphere plugging agents in drilling fluid, the particle size of the copolymer is distributed at 25-80nm, a continuous and compact pressure-bearing plugging layer is formed around a well wall, the pressure transmission speed is reduced, the invasion of filtrate is prevented, and the well wall stability of easily-unstable well walls such as hard brittle mudstone, igneous rock and the like is improved.
Drawings
FIG. 1 is a nuclear magnetic characterization of polymer monomer-1;
FIG. 2 is a nuclear magnetic characterization of polymer monomer-2;
FIG. 3 is a nuclear magnetic characterization of polymer monomer-3;
FIG. 4 is a scanning electron microscope image of copolymer-1;
FIG. 5 is a graph of the laser particle size distribution of copolymer-1.
Detailed Description
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.
In a first aspect the present invention provides a polymer monomer selected from triphenylphosphine derivatives containing an amide bond, a carbon-carbon double bond, a phosphorus-carbon double bond and an alkyl group.
The invention synthesizes a new polymer monomer, which contains amide bond, carbon-carbon double bond, phosphorus-carbon double bond and alkyl, and introduces amide group into the molecule, which can provide hydration group for the prepared polymer, and is beneficial to improving the water absorption swelling property of the polymer; the triphenylphosphine group is introduced to provide a hydrophobic group for the prepared polymer, so that the rigidity of a polymer molecular chain is enhanced, and the temperature resistance and salt resistance of the polymer molecule are enhanced.
According to a preferred embodiment of the invention, the polymer monomer contains 2 triphenylphosphine groups, 4 amide bonds, 2 carbon-carbon double bonds, 2 phosphorus-carbon double bonds, m+n methylene groups and 2 methine groups.
According to a preferred embodiment of the present invention, the polymer monomer has a structure represented by formula (1):
wherein m is a natural number from 0 to 6, preferably a natural number from 0 to 4, more preferably 0,1,2; n is a natural number of 0 to 6, preferably a natural number of 0 to 4, more preferably 0,1,2. By adopting the above preference, the introduction of an amide group, a rigid group phenyl group, into the molecule is advantageous in enhancing the water swelling property and the temperature and salt resistance of the polymer prepared by using the monomer, and in addition, the monomer contains 2 carbon-carbon double bonds, which can simultaneously provide double bond addition to form the polymer, providing the possibility that the obtained polymer has a crosslinked bulk structure.
In a second aspect, the present invention provides a process for the preparation of a polymer monomer, the process comprising:
1) Mixing a bisacrylamide compound with a solvent to obtain a solution I;
2) Mixing triphenylphosphine alkyl nitrile compound with the solution I to obtain a solution II;
3) The catalyst is contacted with the solution II to react, so as to obtain a solution III;
4) And removing the solvent from the solution III, and drying to obtain a polymer monomer.
The polymer monomer prepared by the method contains amide groups and rigid group phenyl groups, which is beneficial to enhancing the water swelling property and the temperature and salt resistance of the polymer prepared by the monomer. In addition, the provided monomer contains 2 carbon-carbon double bonds, can simultaneously provide double bonds for addition to form a polymer, and provides a possible cross-linked body type structure of the obtained polymer.
In the present invention, the inert atmosphere is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the reaction in step 3) is preferably performed in a nitrogen atmosphere.
According to a preferred embodiment of the invention, the concentration of the dipropylamide compound is from 3% to 8% by weight.
According to a preferred embodiment of the present invention, the molar ratio of said dipropylamide compound to said triphenylphosphine alkylnitrile compound is (2.6-3.2): 1.
according to a preferred embodiment of the present invention, the catalyst is used in an amount of 0.05wt% to 12wt%, preferably 1wt% to 10wt%, more preferably 4wt% to 8wt% of the triphenylphosphine alkylnitrile.
In the present invention, the solvent may be selected from a wide range of common solvents, and according to a preferred embodiment of the present invention, the solvent is selected from at least one of water, acetone, butanone, chloroform, dichloromethane, 1' -dichloroethane, 1, 2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, diethyl ether, acetonitrile, ethyl acetate, benzene, toluene, meta-xylene, cyclohexane, ethylene glycol dimethyl ether, nitromethane, 1, 4-dioxane, pyridine, morpholine, N ' -dimethylformamide, N ' -dimethylacetamide and dimethylsulfoxide, preferably from at least one of toluene, 1, 4-dioxane, N ' -dimethylformamide, N ' -dimethylacetamide and dimethylsulfoxide, more preferably from N, N ' -dimethylformamide and/or N, N ' -dimethylacetamide.
In the present invention, the catalyst may be used in the present invention in a wide variety of optional forms, and according to a preferred embodiment of the present invention, the catalyst is selected from at least one of sulfuric acid, phthalimide, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, bismuth trifluoromethanesulfonic acid, calcium trifluoromethanesulfonate, copper trifluoromethanesulfonate, indium trifluoromethanesulfonic acid, bis-trifluoromethanesulfonyl imide, boron trifluoride diethyl ether, perfluorosulfonic acid resin, 2, 4-dinitrobenzenesulfonic acid, dodecylphosphotungstic acid, acid salts of cesium phosphotungstic acid, cesium sulfate, ceric sulfate, phosphorus pentoxide, iodine, cuprous chloride, cuprous bromide, cuprous iodide, copper chloride, cobalt chloride, zinc chloride, and ferric chloride hexahydrate, preferably at least one of boron trifluoride, bismuth trifluoromethanesulfonate, and copper trifluoromethanesulfonate.
According to a preferred embodiment of the present invention, the bisacrylamide compound is selected from the group consisting of N, N '- (1, 2-dihydroxyethylene) bisacrylamide, and N, N' - (1, 2-dihydroxypropylethylene) bisacrylamide.
According to a preferred embodiment of the present invention, the dipropylamide compound has the structural formulaWherein n is a natural number of 0 to 6, preferably a natural number of 0 to 4, more preferably 0,1,2.
According to a preferred embodiment of the invention, the triphenylphosphine alkylnitrile is selected from (triphenylphosphine) acetonitrile, (triphenylphosphine) propionitrile or (triphenylphosphine) butyronitrile.
According to a preferred embodiment of the present invention, the reaction conditions include: the temperature is 80-160 ℃, preferably 100-120 ℃; the time is 6-48 hours, preferably 8-36 hours, more preferably 16-28 hours.
According to a preferred embodiment of the present invention, the first desolventizing agent is removed by distillation under reduced pressure.
According to a particularly preferred embodiment of the present invention, the first solvent-removed product is washed with at least one solvent selected from the group consisting of methanol and acetone.
According to a particularly preferred embodiment of the invention, the first drying temperature is 25 ℃.
In the present invention, there is no particular limitation on the first vacuum pressure as long as the object of the present invention can be achieved, and according to a particularly preferred embodiment of the present invention, the vacuum pressure is-0.1 to 0MPa.
In a third aspect, the present invention provides a polymer monomer prepared by the preparation method of the present invention.
The polymer monomer prepared by the invention can be applied to a drilling fluid plugging agent, so that the plugging agent has good dispersibility, thermal stability, salt resistance and viscoelasticity, and can be applied to the well walls of easily-well-wall unstable formations such as hard brittle mudstones, igneous rocks and the like.
In a fourth aspect, the present invention provides a copolymer comprising: structural unit c derived from the polymer monomer of the present invention, structural unit a represented by formula (2), structural unit b represented by formula (3):
wherein R is 1 、R 3 Each independently selected from H or C 1 -C 6 Alkyl of R 2 Selected from amide groups, R 4 Selected from carboxylic acid groups; wherein the structural unit c: structural unit a: the molar ratio of the structural units b is (2-7): (20-60): (15-35), the weight-average molecular weight of the copolymer was 4.25X10 4 -5×10 4 g/mol。
In the present invention, the structural units a, b and c included in the copolymer are repeating units formed in the molecular chain of the copolymer by addition polymerization of an olefin carbon-carbon double bond contained in a monomer corresponding to each of the above structural units.
The copolymer disclosed by the invention can be used for a drilling fluid plugging agent, and the copolymer molecule has amide groups, rigid groups phenyl groups and phosphorus atoms, so that the plugging agent has good dispersibility, thermal stability, salt resistance and viscoelasticity, and can be suitable for the well walls of easily-unstable well walls such as hard brittle mudstones, igneous rocks and the like.
According to a preferred embodiment of the present invention, the structural unit c has a structure represented by formula (4),
wherein m is a natural number from 0 to 6, preferably a natural number from 0 to 4, more preferably 0,1,2; n is a natural number of 0 to 6, preferably a natural number of 0 to 4, more preferably 0,1,2. By adopting the preference, 2 carbon-carbon double bonds in the structural unit c shown in the formula (4) provide a basis for crosslinking of molecular chain segments, so that the obtained polymer can form an interpenetrating three-dimensional network structure on a microscopic scale, and form polymer polymers with fixed appearance structures, namely gel particles, in a liquid phaseAnd (5) granulating.
According to a preferred embodiment of the invention, R 1 Selected from H, CH 3 Or C 2 H 5 。
According to a preferred embodiment of the invention, R 2 Selected from the group consisting ofThe radicals indicated or->A group of the formula, wherein R a And R is b Each independently selected from H, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkyl alcohol or C of (C) 1 -C 8 Is preferably selected from the group consisting of H, CH 3 、CH 2 CH 3 、/>CH 2 OH、CH 2 CH 2 OH、/> By adopting the preferable scheme, the amide group is introduced into the molecule, so that the high temperature resistance of the plugging agent can be enhanced.
According to a preferred embodiment of the invention, R c Selected from H or C 1 -C 6 Alkyl groups of (2), preferably H, CH 3 、CH 2 CH 3 Or (b)R d Selected from CH 3 、CH 2 CH 3 Or->
According to a preferred embodiment of the present invention, wherein R 3 Selected from H, CH 3 Or C 2 H 5 。
According to a preferred embodiment of the invention, R 4 Selected from the group consisting ofThe radicals or radicals shownA group shown in the specification, wherein A is at least one selected from H, na, K, rb or Cs, preferably at least one selected from H, na and K; r is a natural number from 0 to 6, s is a natural number from 0 to 6, t is a natural number from 0 to 6, R is selected from H or CH 3 . By adopting the foregoing preferred embodiment, the water-swelling property of the blocking agent is improved by introducing a carboxylic acid group into the molecule.
According to a preferred embodiment of the invention r is a natural number from 0 to 2, s is a natural number from 0 to 4, and t is a natural number from 0 to 2.
According to a preferred embodiment of the invention, the copolymer preferably has a particle size distribution of 25-80nm.
In a fifth aspect, the present invention provides a method for producing a copolymer, comprising the steps of:
(1) Mixing an emulsifying agent with an organic solvent to obtain a solution A;
(2) Mixing a monomer (1) shown in a formula (5), a monomer (2) shown in a formula (6), a polymer monomer and water to obtain a solution B;
(3) The solution A, the initiator and the solution B are contacted for copolymerization reaction to obtain a copolymer;
wherein the polymer monomer is the polymer monomer disclosed by the invention; wherein R is 1 、R 2 、R 3 、R 4 The definition of (c) is correspondingly the same as in the fourth aspect of the invention.
The copolymer obtained by the method can be used for a drilling fluid plugging agent, and the copolymer molecule has amide groups, phenyl groups and carboxylic acid groups, so that the plugging agent has good dispersibility, thermal stability, salt resistance and viscoelasticity, and can be suitable for the well walls of hard brittle mudstones, igneous rocks and other easily-unstable well walls.
In the present invention, the inert atmosphere is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the reaction in step (3) is preferably performed in a nitrogen atmosphere.
In the present invention, the organic solvent may be selected from white oil, liquid paraffin, cyclohexane, isooctane, benzene, toluene, xylene, diesel oil, kerosene, methyl nylon, petroleum ether, butanone, isoparaffin, preferably white oil, cyclohexane, isooctane, benzene, toluene, petroleum ether.
In the present invention, the emulsifier may be selected from a wide range of common types, and according to a preferred embodiment of the present invention, the emulsifier is selected from one or more of cationic surfactant, anionic surfactant, amphoteric surfactant, nonionic surfactant, preferably polysorbate nonionic surfactant, more preferably sodium bis (2-ethylhexyl) succinate sulfonate (AOT).
According to a preferred embodiment of the present invention, the nonionic surfactant has an HLB in the range of 0 to 10, preferably 3 to 9.
According to a preferred embodiment of the present invention, the reaction temperature in step (3) is 30 to 150 ℃, preferably 40 to 100 ℃.
According to a preferred embodiment of the invention, the step (3) reaction time is 2-56 hours, preferably 6-48 hours, more preferably 12-36 hours.
According to a preferred embodiment of the present invention, the solution B obtained in the step (2) is charged into a separating funnel and added dropwise to the mixed solution of the solution A and the initiator at a rate of 10 to 100mL/h, preferably 20 to 60mL/h.
According to a preferred embodiment of the invention, the solution B has to be adjusted to a pH of 7-8.5 with NaOH or KOH.
According to a particularly preferred embodiment of the present invention, the second solvent removal is to pour the product into at least one solvent selected from the group consisting of methanol, ethanol, water and acetone for precipitation and filtration. By adopting the above preferences, the adhesion of the copolymer is improved, thereby improving the heat resistance and viscoelasticity of the blocking agent.
According to a particularly preferred embodiment of the present invention, the second solvent-removed product is washed with at least one solvent selected from the group consisting of methanol and acetone. By adopting the above preferences, the adhesion of the copolymer is improved, thereby improving the heat resistance and viscoelasticity of the blocking agent.
According to a particularly preferred embodiment of the invention, the second drying temperature is 35 ℃. By adopting the above preferences, the adhesion of the copolymer is improved, thereby improving the heat resistance and viscoelasticity of the blocking agent.
In the present invention, the second vacuum pressure is not particularly limited as long as the object of the present invention can be achieved, and according to a particularly preferred embodiment of the present invention, the second vacuum pressure is-0.1 MPa to 0MPa (gauge pressure). By adopting the above preferences, the adhesion of the copolymer is improved, thereby improving the heat resistance and viscoelasticity of the blocking agent.
In the present invention, the types of the initiator are wide in optional range, and common types can be used in the present invention, and according to a preferred embodiment of the present invention, the initiator is selected from a water-soluble initiator, a water-soluble redox system initiator, or an azo compound initiator; wherein the water-soluble redox system initiator is selected from K 2 S 2 O 8 And/or (NH) 4 ) 2 S 2 O 8 The azo compound initiator is selected from azo diiso Ding Mi hydrochloride, azo-iso Ding Qingji formamide, azo diisobutyronitrile, benzoyl peroxide, azo-dicarboxyethyl-2-isobutyl amidine hydrate, azo-dimethyl-N-2-hydroxybutyl acrylamide, azo dicyclohexyl carbonitrile, azo diisovaleronitrile, azo diisoheptonitrile, azo dicyanovaleric acid, azo diisobutyl amidine hydrochloride, azo diisopropylimidazoline, azo di-N-butyl acrylamide, azo di-N-butyl formamide, azo di-N-butyl formamide, azoAt least one of N-hydroxy isobutyl amidine hydrate, azo-bis-N, N '-cyclobutylisobutyl amidine hydrate, dimethyl azo-bis-isobutyrate, 2' -azo-bis (N-cyclohexylisobutyl amidine) hydrochloride.
According to a preferred embodiment of the invention, the concentration of the emulsifier is from 10% to 60% by weight, preferably from 20% to 40% by weight, based on the total amount of the solution A.
According to a preferred embodiment of the invention, the water is 1-2.5 times the mass of the organic solvent.
According to a preferred embodiment of the present invention, the molar ratio of the monomer (1), the monomer (2) and the polymer monomer is (20-60): (15-35): (2-9).
According to a preferred embodiment of the invention, the concentration of the total amount of monomer (1), monomer (2) and polymer monomer in the solution B is between 10% and 50% by weight, preferably between 15% and 30% by weight.
According to a preferred embodiment of the invention, the initiator is present in an amount of 0.02% to 4% by weight, preferably 0.05% to 3% by weight, more preferably 0.2% to 2% by weight, based on the total mass of the monomers.
In a sixth aspect, the present invention provides a copolymer produced by the production method of the present invention.
The copolymer obtained by the method can be used for a drilling fluid plugging agent, and the copolymer molecule has amide groups, phenyl groups and carboxylic acid groups, so that the plugging agent has good dispersibility, thermal stability, salt resistance and viscoelasticity, and can be suitable for the well walls of hard brittle mudstones, igneous rocks and other easily-unstable well walls.
In a seventh aspect, the present invention provides the use of a copolymer according to the invention as a polymeric microsphere plugging agent in the field of petroleum aids.
The copolymer prepared by the invention can be used for the application of polymer microsphere plugging agents in drilling fluid, the particle size of the copolymer is distributed at 25-80nm, a continuous and compact pressure-bearing plugging layer is formed around a well wall, the pressure transmission speed is reduced, the invasion of filtrate is prevented, and the well wall stability of easily-unstable well walls such as hard brittle mudstone, igneous rock and the like is improved.
In an eighth aspect, the present invention provides a drilling fluid comprising a copolymer according to the present invention.
The drilling fluid contains the copolymer, the particle size of which is distributed at 25-80nm, has good dispersibility, thermal stability, salt resistance and viscoelasticity, and can effectively block nano-micron scale pores, thereby being beneficial to forming a continuous and compact pressure-bearing blocking layer around a well wall, reducing the pressure transmission speed, preventing the invasion of filtrate and providing the stability of the well wall. Preferably, the drilling fluid may be a water-based drilling fluid, a water-in-oil drilling fluid, a synthetic-based drilling fluid, and an alcohol-based drilling fluid, and the drilling fluid may further contain conventional drilling fluid treatment agents including a drilling fluid inhibitor, a flow pattern regulator, a plugging agent, a fluid loss additive, a lubricant, a reservoir protecting agent, etc., and the copolymer may be contained in the drilling fluid in an amount of 0.2wt% to 2.0wt%.
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are provided for the purpose of illustration only and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials used in the examples were commercially available unless otherwise specified.
1 H NMR test method or apparatus (CD) 3 ) 2 SO is used as solvent, and Bruker Avance III HD MHz nuclear magnetic resonance spectrometer is used for nuclear magnetic resonance of the product at room temperature 1 H NMR) spectra and scan measurements were taken.
Plugging performance test:
will be at a fixed permeability (360 x 10 -2 mD), 800 mesh superfine calcium carbonate, 1500 mesh superfine calcium carbonate, 2000 mesh superfine calcium carbonate, 2500 mesh superfine calcium carbonate, 3000 mesh superfine calcium carbonate, 4000 mesh superfine calcium carbonate, 5000 mesh superfine calcium carbonate, 6000 mesh superfine calcium carbonate and the polymer microspheres prepared in examples 8-28, comparative example 1 were measured as plugging materials (experimental slurry formulation: 0.5% bentonite (executive standard: GB/T5005) +0.05% highly viscous carboxymethylThe average flow of the sodium salt of base cellulose (execution standard: Q/SH 0038-2007) +1.0% of plugging materials) in the simulated nano-micron stratum is combined with a Darcy formula to calculate the permeability of the simulated stratum before and after plugging, so that the plugging rate of different plugging materials on the simulated stratum is obtained.
Particle size distribution test
The polymer microspheres prepared in the example were prepared by adding 0.05g of the polymer microspheres prepared in the example to 200mL of distilled water, stirring at 600r/min for 20min, measuring the particle size distribution of the polymer microspheres prepared in the example in filtrate by using a Mastersizer 3000E-type laser particle size analyzer, and observing the dispersion morphology of the polymer microspheres in water by using a JSM-7200F-type electron Field Emission Scanning Electron Microscope (FESEM).
Compatibility test
The polymer microsphere and 6000-mesh superfine calcium carbonate are compounded, namely the formula of drilling fluid experimental slurry is 0.5 percent bentonite (execution standard: GB/T5005) +0.05 percent high-viscosity carboxymethyl cellulose sodium salt (execution standard: Q/SH 0038-2007) +0.5 percent polymer microsphere+0.5 percent 6000-mesh superfine calcium carbonate, and the plugging rate of the formula is verified.
Temperature resistance test
Firstly, aging drilling fluid experimental slurry (formula: 0.5% bentonite (execution standard: GB/T5005) +0.05% high viscosity carboxymethyl cellulose sodium salt (execution standard: Q/SH 0038-2007) +1.0% plugging material) at 150deg.C for 16h, then fixing permeability (360×10) -2 mD), respectively measuring the average flow of the polymer microspheres prepared in examples 8-14 and comparative example 1 as plugging materials in the simulated nano-micron stratum, and calculating the permeability of the simulated stratum before and after plugging by combining a darcy formula, thereby obtaining the plugging rate of different plugging materials on the simulated stratum.
Salt resistance test
Preparing drilling fluid experimental slurry (formula: 0.5% bentonite (execution standard: GB/T5005) +0.05% high viscosity carboxymethyl cellulose sodium salt (execution standard: Q/SH 0038-2007) +10% NaCl+1.0% plugging material), and then fixing the permeability (360×10) -2 mD) simulated nano-micron formations were simulated, examples 8-14, pairs were measured, respectivelyThe polymer prepared in the proportion 1 is used as the average flow of the plugging material in the simulated nano-micron stratum, and the Darcy formula is combined to calculate the permeability of the simulated stratum before and after plugging, so that the plugging rate of different plugging materials on the simulated stratum is obtained.
Example 1
Preparation of Polymer monomers
20.0194g (0.1 mol) of N, N '- (1, 2-dihydroxyethylene) bisacrylamide and 240g of N, N' -dimethylacetamide were charged into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, and after stirring thoroughly until dissolved, 96.3252g (0.32 mol) of (triphenylphosphine) acetonitrile was added thereto and stirred thoroughly. After nitrogen was introduced for 30 minutes, the temperature was raised to 100℃and after 4.63g of copper triflate was added, the reaction was continued for 16 hours with stirring.
After the reaction is finished, N' -dimethylacetamide is removed by reduced pressure distillation, the obtained products are respectively stirred and washed by methanol and acetone, and then are dried in vacuum until the weight is constant, thus obtaining polymer monomers, and nuclear magnetic characterization [ (CD) is carried out 3 ) 2 SO，25℃]The results are shown in FIG. 1. According to 1 H NMR and elemental analysis test results correspond to formula (2) wherein the two secondary amines have hydrogens at about the chemical shift of about 8.5ppm and about 8.3ppm, and the benzene ring has hydrogens at about 7.6 ppm. It was found that the polymer monomer-1 represented by the formula (1) was obtained, wherein m=0, n=0,
example 2
Preparation of Polymer monomers
20.0194g (0.1 mol) of N, N '- (1, 2-dihydroxyethylene) bisacrylamide and 240g of N, N' -dimethylacetamide were charged into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, and after stirring thoroughly until dissolved, 100.9139g (0.32 mol) of (triphenylphosphine) propionitrile was added thereto and stirred thoroughly. After nitrogen was introduced for 30 minutes, the temperature was raised to 117℃and after 8g of bismuth triflate was added, the reaction was continued for 18 hours with stirring.
After the reaction is finished, N' -dimethylacetamide is removed by reduced pressure distillation, the obtained products are respectively stirred and washed by methanol and acetone, and then are dried in vacuum until the weight is constant, thus obtaining polymer monomers, and nuclear magnetic characterization [ (CD) is carried out 3 ) 2 SO，25℃]The results are shown in FIG. 2. According to 1 H NMR and elemental analysis test results correspond to formula (2) wherein the two secondary amines have hydrogens at about 8.5ppm and about 8.3ppm chemical shifts, the benzene rings have hydrogens at about 7.6ppm chemical shifts, and the methylene has hydrogens at about 2.2ppm chemical shifts. It was found that the polymer monomer-2 represented by the formula (2) was obtained, wherein m=1, n=0,
Example 3
Preparation of Polymer monomers
20.0194g (0.1 mol) of N, N '- (1, 2-dihydroxyethylene) bisacrylamide and 240g of N, N' -dimethylacetamide were charged into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, and after stirring thoroughly until dissolved, 101.5424g (0.32 mol) of (triphenylphosphine) butyronitrile was added thereto and stirred thoroughly. After nitrogen was introduced for 30 minutes, the temperature was raised to 102℃and 5.66g of boron trifluoride etherate was added thereto, followed by continuing the reaction with stirring for 22 hours.
After the reaction is finished, N' -dimethylacetamide is removed by reduced pressure distillation, the obtained products are respectively stirred and washed by methanol and acetone, and then are dried in vacuum until the weight is constant, thus obtaining polymer monomers, and nuclear magnetic characterization [ (CD) is carried out 3 ) 2 SO，25℃]The results are shown in FIG. 3. According to 1 H NMR and elemental analysis test results correspond to formula (2) wherein the two secondary amines have hydrogens at about 8.5ppm and about 8.3ppm chemical shifts, the benzene rings have hydrogens at about 7.6ppm chemical shifts, and the two methylene groups have hydrogens at about 2.2ppm and about 1.9ppm chemical shifts. It was found that the polymer monomer-3 represented by the formula (3) was obtained, wherein m=2, n=0,
example 4
Synthesis of Polymer monomer:
20.0194g (0.1 mol) of N, N '- (1, 2-dihydroxyethylene) bisacrylamide and 360g of N, N' -dimethylformamide were charged into a reactor equipped with a temperature control apparatus, a reflux condensing apparatus and a constant pressure charging apparatus, and after stirring sufficiently until dissolved, 94.6067g (0.3 mol) of (triphenylphosphine) propionitrile was added. After nitrogen was introduced for 30 minutes, the temperature was raised to 108℃and 6.28g of boron trifluoride etherate was added thereto, followed by continuing the reaction with stirring for 22 hours.
After the reaction is finished, N' -dimethylformamide is removed by reduced pressure distillation, the obtained products are respectively stirred and washed by methanol and acetone, and the polymer monomer-4 is obtained by vacuum drying until the weight is constant, wherein m=1 and n=0,
example 5
Synthesis of Polymer monomer:
20.0194g (0.1 mol) of N, N '- (1, 2-dihydroxyethylene) bisacrylamide and 560g of N, N' -dimethylacetamide were charged into a reactor equipped with a temperature control device, a reflux condensing device and a constant pressure charging device, and after stirring thoroughly until dissolved, 85.64g (0.26 mol) of (triphenylphosphine) butyronitrile was added. After nitrogen was introduced for 30 minutes, the temperature was raised to 120℃and after 5.32g of bismuth triflate was added, the reaction was continued for 28 hours with stirring.
After the reaction is finished, N' -dimethylacetamide is removed by reduced pressure distillation, the obtained products are respectively stirred and washed by methanol and acetone, and the polymer monomer-5 is obtained by vacuum drying to constant weight, wherein m=2 and n=0,
example 6
Preparation of Polymer monomers
22.8248g (0.1 mol) of N, N '- (1, 2-dihydroxyethyl ethylene) bisacrylamide and 400g of N, N' -dimethylformamide were charged into a reactor equipped with a temperature control apparatus, a reflux condensing apparatus and a constant pressure charging apparatus, and after stirring sufficiently until dissolved, 90.3986g (0.3 mol) of (triphenylphosphine) acetonitrile was added thereto and stirred sufficiently. After nitrogen was introduced for 30 minutes, the temperature was raised to 107℃and after 6.24g of bismuth triflate was added, the reaction was continued for 22 hours with stirring.
After the reaction is finished, N' -dimethylformamide is removed by reduced pressure distillation, the obtained product is put into methanol solution to be soaked for 2 hours, suction filtration is carried out, methanol and acetone are respectively used for showering, and the polymer monomer-6 is obtained after vacuum drying to constant weight, wherein m=0 and n=1,
example 7
Preparation of Polymer monomers
25.63g (0.1 mol) of N, N '- (1, 2-dihydroxypropylethylene) bisacrylamide and 600g of N, N' -dimethylacetamide were charged into a reactor equipped with a temperature control apparatus, a reflux condensing apparatus and a constant pressure charging apparatus, and after stirring sufficiently until dissolved, 86.7228g (0.275 mol) of (triphenylphosphine) propionitrile was added thereto and stirred sufficiently. After nitrogen was introduced for 30 minutes, the temperature was raised to 116℃and after 5.16g of copper triflate was added, the reaction was continued for 20 hours with stirring.
After the reaction is finished, N' -dimethylacetamide is removed by reduced pressure distillation, the obtained product is put into ethanol solution to be soaked for 2 hours, suction filtration is carried out, ethanol and acetone are respectively used for showering, and the polymer monomer-7 is obtained by vacuum drying to constant weight. Where m=1, n=2,
example 8
Preparation of the copolymer
280g toluene, 50g Span 65 and 50g T were weighed outwen 40 (hlb=8.85) was added to the reactor and stirred at high speed until clear to give solution a; 101.5344g (0.6 mol) of diacetone acrylamide (monomer of the formula (5)) in which R 1 ＝H，) 19.2257g (0.15 mol) of 3, 3-dimethyl-4-pentenoic acid (monomer represented by the formula (6), wherein R 3 ＝H，/>) 16.057g (0.02 mol) of the polymer monomer-1 prepared in example 1 was added to 600g of water, stirred until completely dissolved to obtain solution B, and the pH of the obtained solution B was adjusted to 8.5 with NaOH and added to a separating funnel for use; />
The reactor was purged with nitrogen and warmed to 72 ℃, 1.2g of 2,2' -azobis (N-cyclohexylisobutyl amidine) hydrochloride was added with continuous stirring, and solution B in the separating funnel was added dropwise to the solution in the reactor at a dropping rate of 50 mL/h. After the reaction is continued for 20 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain the copolymer-1, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 60:15:2.
the copolymer-1 was subjected to a particle size distribution test, the test results of which are shown in FIG. 5, and the particle size of the polymer microspheres can be seen; as shown in FIG. 4, the copolymer-1 has better dispersion property and no obvious agglomeration phenomenon.
Example 9
Preparation of the copolymer
The procedure of example 8 was followed except that the polymer monomer-1 prepared in example 1 was replaced with the same molar amount of the polymer monomer-2 prepared in example 2. A copolymer-2 was obtained in which the molar ratio of the three monomers (monomer represented by formula (5): monomer represented by formula (6): polymer monomer-2) was 60:15:2.
example 10
Preparation of the copolymer
The procedure of example 8 was followed except that the polymer monomer-1 prepared in example 1 was replaced with the same molar amount of the polymer monomer-3 prepared in example 3. A copolymer-3 was obtained in which the molar ratio of the three monomers (monomer represented by formula (5): monomer represented by formula (6): polymer monomer-3) was 60:15:2.
example 11
Preparation of the copolymer
The procedure of example 8 was followed except that the polymer monomer-1 prepared in example 1 was replaced with the same molar amount of the polymer monomer-4 prepared in example 4. A copolymer-4 was obtained in which the molar ratio of the three monomers (monomer represented by formula (5): monomer represented by formula (6): polymer monomer-4) was 60:15:2.
example 12
Preparation of the copolymer
The procedure of example 8 was followed except that the polymer monomer-1 prepared in example 1 was replaced with the same molar amount of the polymer monomer-5 prepared in example 5. A copolymer-5 was obtained in which the molar ratio of the three monomers (monomer represented by formula (5): monomer represented by formula (6): polymer monomer-5) was 60:15:2.
Example 13
Preparation of the copolymer
The procedure of example 8 was followed except that the polymer monomer-1 prepared in example 1 was replaced with the same molar amount of the polymer monomer-6 prepared in example 6. A copolymer-6 was obtained in which the molar ratio of the three monomers (monomer represented by formula (5): monomer represented by formula (6): polymer monomer-6) was 60:15:2.
example 14
Preparation of the copolymer
The procedure of example 8 was followed except that the polymer monomer-1 prepared in example 1 was replaced with the same molar amount of the polymer monomer-7 prepared in example 7. A copolymer-7 was obtained in which the molar ratio of the three monomers (monomer represented by formula (5): monomer represented by formula (6): polymer monomer-7) was 60:15:2.
example 15
Synthesis of copolymer
280g of toluene, 50g of Span 65 and 50g of Tween 40 (HLB=8.85) were weighed into a reactor, and stirred at high speed until clear to obtain a solution A; 101.5344g (0.6 mol) of diacetone acrylamide (monomer of the formula (5)) in which R 1 ＝H，) 19.2257g (0.15 mol) of 3, 3-dimethyl-4-pentenoic acid (monomer represented by the formula (6), wherein R 3 ＝H，/>) 16.057g (0.02 mol) of the polymer monomer-1 prepared in example 1 was added to 600g of water, stirred until completely dissolved to obtain solution B, and the pH of the obtained solution B was adjusted to 8.5 with NaOH and added to a separating funnel for use;
The reactor was purged with nitrogen and warmed to 72 ℃, 1.2g of 2,2' -azobis (N-cyclohexylisobutyl amidine) hydrochloride was added with continuous stirring, and solution B in the separating funnel was added dropwise to the solution in the reactor at a dropping rate of 50 mL/h. After the reaction is continued for 20 hours, the reaction product is poured into ethanol, stirred for 30 minutes, filtered, and the obtained solid is sequentially stirred and washed by methanol and acetone, and filtered. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-8, wherein the mole ratio of three monomers (monomer shown in formula (5): monomer shown in formula (6): polymer monomer-1) in the copolymer is 60:15:2.
example 16
Synthesis of copolymer
400g 5 is weighed # White oil, 75g Span 80 and 25g Tween 61 (hlb=5.63) were added to the reactor and stirred at high speed until clear to give solution a; 20.221g (0.2 mol) of N-methylolacrylamide (monomer of formula (5), wherein R 1 ＝H，) 38.5537g (0.35 mol) of potassium acrylate (monomer represented by the formula (6) wherein R 3 ＝H，) 72.2566g (0.09 mol) of the polymer monomer-1 prepared in example 1 was added to 740g of water, stirred until it was completely dissolved to obtain a solution B, the pH of the obtained solution B was adjusted to 7.5 with NaOH, and added to a separating funnel for use;
The reactor was purged with nitrogen and warmed to 66℃and 0.65g of dimethyl azodiisobutyrate was added with continuous stirring, and solution B in a separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 50 mL/h. After the reaction is continued for 24 hours, stopping heating and stirring, pouring the reaction product into ethanol, stirring for 30 minutes, carrying out suction filtration, sequentially stirring and cleaning the obtained solid by using methanol and acetone, and carrying out suction filtration. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain the copolymer-9, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 20:35:9.
example 17
Synthesis of copolymer
160g cyclohexane and 100g Span 80 (hlb=4.3) were weighed into a reactor and stirred at high speed until clear to obtain solution a; 19.8266g (0.2 mol) of N-vinyl-N' -methylacetamide (monomer represented by formula (5) wherein R 1 ＝H，) 30.1315g (0.35 mol) of 2-butenoic acid (monomer of formula (6) in which R 3 ＝CH 3 ，/>) 16.057g (0.02 mol) of the polymer monomer-1 prepared in example 1 was added to 160g of water, stirred until completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 7 with NaOH and added to a liquid-separating funnel In the bucket for standby;
the reactor was purged with nitrogen and warmed to 57 ℃, 0.132g of azodicarboxylic ethyl-2-isobutyl amidine hydrate was added with continuous stirring, and solution B in a separating funnel was added dropwise to the solution in the reactor at a dropping rate of 60 mL/h. After the reaction is continued for 36 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain the copolymer-10, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 20:35:2.
example 18
Synthesis of copolymer
360g cyclohexane, 95g Span 20 and 5g Tween 20 (hlb=9) were weighed into a reactor and stirred at high speed until clear to obtain solution a; 76.3122g (0.6 mol) of N-vinyl-N' -methylacetamide (monomer represented by formula (5) wherein R 1 ＝H，) 25.2221g (0.35 mol) of 2-butenoic acid (monomer of formula (6) in which R 3 ＝H，/>) And 72.2566g (0.09 mol), the polymer monomer-1 prepared in example 1 was added to 900g of water, stirred until it was completely dissolved to obtain a solution B, and the obtained solution B was added to a separating funnel by adjusting pH to 7.5 with NaOH for use;
Nitrogen was introduced into the reactor and warmed to 44 ℃, 2.6g of azobisiso Ding Mi hydrochloride was added with continuous stirring, and the solution B in the separating funnel was added dropwise to the solution in the reactor at a dropping rate of 20 mL/h. After the reaction is continued for 12 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-11, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 45:25:4.
example 19
Synthesis of copolymer
250g of isooctane, 60g of Span 40 and 40g of Tween 81 (HLB=8.02) are weighed and added into a reactor, and the mixture is stirred at a high speed until the mixture is clarified to obtain a solution A; 38.2977g (0.45 mol) of N-vinylacetamide (monomer represented by formula (5) wherein R 1 ＝H，) 27.018g (0.25 mol) of sodium methacrylate (monomer represented by the formula (6) wherein R 3 ＝CH 3 ，/>) 32.1141g (0.04 mol) of the polymer monomer-1 prepared in example 1 was added to 500g of water, stirred until completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 8 with NaOH and added to a separating funnel for use;
The reactor was purged with nitrogen and warmed to 56℃and 1.05g of azobisisobutylamidine hydrochloride was added with continuous stirring, and solution B in the separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 40 mL/h. After the reaction is continued for 28 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-12, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 45:25:4.
example 20
Synthesis of copolymer
280g of petroleum ether and 100g of AOT are weighed and added into a reactor, and the mixture is stirred at a high speed until the mixture is clarified to obtain solution A; 50.922g (0.3 mol) of N-isopropylacrylamide (monomer of formula (5) wherein R 1 ＝H，) 25.0293g (0.3 mol) of 2-methyl-3-butenoic acid (monomer of formula (6) in which R 3 ＝CH 3 ，/>) 56.1996g (0.07 mol) of the polymer monomer-1 prepared in example 1 was added to 400g of water, stirred until it was completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 8.5 with NaOH and added to a separating funnel for use;
Nitrogen was introduced into the reactor and heated to 61 ℃, 0.8g of azobisisopropylimidazoline was added with continuous stirring, and solution B in the separating funnel was added dropwise to the solution in the reactor at a dropping rate of 35 mL/h. After the reaction is continued for 32 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-13, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 30:30:7.
example 21
Synthesis of copolymer
200g cyclohexane, 85g Span 85 and 15g Tween 21 (hlb=3.53) were weighed into a reactor and stirred at high speed until clear to give solution a; 34.6424g (0.2 mol) of N, N' -bis (2-hydroxyethyl) methacrylamide (monomer of formula (5), wherein R 1 ＝CH 3 ，) 17.1216g (0.15 mol) of 2-methyl-2-pentenoic acid ∈ ->72.2566g (0.09 mol) of the polymer monomer-1 prepared in example 1 was added to 400g of water, stirred until completely dissolved to obtain a solution B, and the obtained solution B was pH-adjusted to 8 with NaOH and added to the solution B The liquid funnel is reserved for standby;
the reactor was purged with nitrogen and warmed to 88℃and 1g of azobicyclohexyl carbonitrile was added with continuous stirring, and solution B in the separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 30 mL/h. After the reaction is continued for 25 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-14, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 20:15:9.
example 22
Synthesis of copolymer
200g of petroleum ether, 90g of Span 65 and 10g of Tween 85 (HLB=3.0) are weighed and added into a reactor, and the mixture is stirred at a high speed until the mixture is clarified to obtain a solution A; 32.2898g (0.25 mol) of N- (2-hydroxypropyl) acrylamide (monomer of formula (5) wherein R 1 ＝H，) 25.6342g (0.2 mol) of 2, 2-dimethyl-4-pentenoic acid (monomer represented by the formula (6), wherein R 3 ＝H，/>) 64.2281g (0.08 mol) of the polymer monomer-1 prepared in example 1 was added to 400g of water, stirred until completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 8 with NaOH and added to a separating funnel for use;
Nitrogen was introduced into the reactor and heated to 67 ℃, 1g of azobisisovaleronitrile was added with continuous stirring, and solution B in the separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 45 mL/h. After the reaction is continued for 22 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-15, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 25:20:8.
example 23
Synthesis of copolymer
200g of toluene and 100g of sodium bis (2-ethylhexyl) succinate sulfonate (AOT) are weighed and added into a reactor, and the mixture is stirred at a high speed until the mixture is clarified to obtain a solution A; 28.783g (0.28 mol) of N-hydroxyethyl acrylamide (monomer represented by formula (5), wherein R 1 ＝H，) 23.0708g (0.18 mol) of 2, 4-dimethyl-2-pentenoic acid64.2281g (0.05 mol) of the polymer monomer-1 prepared in example 1 was added to 360g of water, stirred until completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 8 with NaOH and added to a separating funnel for use;
Nitrogen was introduced into the reactor and heated to 51 ℃, 1g of azobisisoheptonitrile was added with continuous stirring, and the solution B in the separating funnel was added dropwise to the solution in the reactor at a dropping rate of 40 mL/h. After the reaction is continued for 18 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-16, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 28:18:5.
example 24
200g benzene, 100g Span 60 (hlb=4.7) were weighed into a reactor and stirred at high speed until clear to give solution a; 38.2977g (0.45 mol) of methacrylamide (monomer of formula (5), wherein R 1 ＝CH 3 ， ) 20.0234g (0.2 mol) of 3-methyl-2-butenoic acid ∈ ->24.0855g (0.03 mol) of the polymer monomer-1 prepared in example 1 was added to 420g of water, stirred until it was completely dissolved to obtain a solution B, and the obtained solution B was added to a separating funnel by adjusting pH to 8.5 with NaOH for use;
the reactor was purged with nitrogen and warmed to 67 ℃, 1g of azodicarbonyl valeric acid was added with continuous stirring, and solution B in the separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 30 mL/h. After the reaction is continued for 33 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-17, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 45:20:3.
Example 25
Synthesis of copolymer
Weigh 250g 10 # White oil, 80g Span 40 and 20g Tween 60 (hlb=8.34) were added to the reactor and stirred at high speed until clear to give solution a; 44.6099g (0.42 mol) of N, N' -dimethylacrylamide (monomer represented by formula (5)) wherein R 1 ＝H，) 17.218g (0.27 mol) of methacrylic acid (monomer represented by formula (6) wherein R 3 ＝CH 3 ，/>) 24.0855g (0.04 mol) of the polymer monomer-1 prepared in example 1 was added to 350g of water, stirred until completely dissolved to obtain solution B, and the obtained solution B was added to a separating funnel by adjusting pH to 7.5 with NaOH for use;
the reactor was purged with nitrogen and warmed to 86℃and 1.37g of azodimethyl N-2-hydroxybutyl acrylamide was added with continuous stirring, and solution B in a separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 25 mL/h. After the reaction is continued for 33 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-18, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 42:27:4.
Example 26
Synthesis of copolymer
250g toluene, 80g Span 80 and 20g Tween 80 (hlb=6.44) were weighed into a reactor and stirred at high speed until clear to give solution a; 70.607g (0.5 mol) of N, N' -diethylmethacrylamide (monomer represented by the formula (5), wherein R 1 ＝H，) 20.0234g (0.2 mol) of 3-pentenoic acid24.0855g (0.03 mol) of the polymer monomer-1 prepared in example 1 was added to 360g of water, stirred until it was completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 8.5 with NaOH and added to a separating funnel for use;
the reactor was purged with nitrogen and warmed to 72 ℃, 1.2g of azobis N-hydroxy isobutyl amidine hydrate was added with continuous stirring, and solution B in the separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 25 mL/h. After the reaction is continued for 32 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-19, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 50:20:3.
Example 27
Synthesis of copolymer
220g of isooctane and 100g of AOT are weighed and added into a reactor, and the mixture is stirred at a high speed until the mixture is clarified to obtain solution A; 32.2898g (0.25 mol) of N- (2-hydroxypropyl) acrylamide (monomer of formula (5) wherein R 1 ＝H， ) 17.218g (0.3 mol) of 3-butenoic acid (monomer of formula (6) in which R 3 ＝H，) 16.057g (0.02 mol) of the polymer monomer-1 prepared in example 1 was added to 300g of water, stirred until completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 8 with NaOH and added to a separating funnel for use;
the reactor was purged with nitrogen and warmed to 96 ℃, 1.2g of azoi Ding Qingji formamide was added with continuous stirring, and solution B in the separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 20 mL/h. After the reaction is continued for 36 hours, heating and stirring are stopped, the reaction product is poured into ethanol, stirring is carried out for 30 minutes, suction filtration is carried out, the obtained solid is sequentially stirred and washed by methanol and acetone, and suction filtration is carried out. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain the copolymer-20, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 25:30:2.
Example 28
Synthesis of Polymer microspheres
220g cyclohexane, 80g Span 60 and 20g Tween 65 (hlb=5.86) were weighed into a reactor and stirred at high speed until clear to obtain solution a; 19.8262g (0.2 mol) of N-ethylacrylamide (monomer represented by the formula (5)) was weighed out，R 1 ＝H，) 30.0351g (0.3 mol) of 4-propenoic acid (monomer represented by the formula (6) wherein R 3 ＝H，/>) 24.0855g (0.03 mol) of the polymer monomer-1 prepared in example 1 was added to 320g of water, stirred until completely dissolved to obtain a solution B, and the pH of the obtained solution B was adjusted to 8.5 with NaOH and added to a separating funnel for use;
the reactor was purged with nitrogen and warmed to 67 ℃, 0.36g of azobisisovaleronitrile was added with continuous stirring, and solution B in the separatory funnel was added dropwise to the solution in the reactor at a dropping rate of 30 mL/h. After the reaction is continued for 17.5 hours, stopping heating and stirring, pouring the reaction product into ethanol, stirring for 30 minutes, carrying out suction filtration, sequentially stirring and cleaning the obtained solid by using methanol and acetone, and carrying out suction filtration. Finally, drying the solid to constant weight under vacuum at 35 ℃, and grinding the solid into fine particles to obtain a copolymer-21, wherein the mole ratio of three monomers (the monomer shown in the formula (5): the monomer shown in the formula (6): the polymer monomer-1) in the copolymer is 20:30:3.
Comparative example 1
Preparation of the copolymer
The procedure of example 8 was followed except that the polymer monomer-1 prepared in example 1 was replaced with the same molar amount of N, N' -methylenebisacrylamide. A copolymer-22 was obtained in which the molar ratio of the three monomers (monomer represented by the formula (5): monomer represented by the formula (6): N, N' -methylenebisacrylamide) was 60:15:2.
test example 1
Plugging performance test
Will be at a fixed permeability (360 x 10 -2 mD) to simulate nano-micron grade stratum, respectively measuring 800 mesh superfine calcium carbonate, 1500 mesh superfine calcium carbonate, 2000 mesh superfine calcium carbonate, 2500 mesh superfine calcium carbonate, 3000 mesh superfine calcium carbonate, 4000 mesh superfine calcium carbonate, 5000 mesh superfine carbonThe average flow rate of the calcium carbonate, 6000-mesh superfine calcium carbonate and the polymer microspheres prepared in examples 8-28 and comparative example 1 serving as plugging materials (formula: 0.5% bentonite (executive standard: GB/T5005) +0.05% high-viscosity carboxymethyl cellulose sodium salt (executive standard: Q/SH 0038-2007) +1.0% plugging materials) in the simulated nano-micron stratum is calculated by combining with a Darcy formula, so that the plugging rates of different plugging materials on the simulated stratum are obtained, and experimental results are shown in table 1:
TABLE 1 blocking Rate of different blocking materials
/>
As can be seen from Table 1, the polymer microspheres prepared by the method of the invention have better plugging effect on the nano-micron stratum than 800-6000 mesh superfine calcium carbonate and copolymer-22.
Compatibility test
In order to examine the compatibility of the polymer microsphere and the rigid plugging material, the polymer microsphere and 6000-mesh superfine calcium carbonate are compounded, namely, the formula of drilling fluid experimental slurry is 0.5% bentonite (execution standard: GB/T5005) +0.05% high-viscosity carboxymethyl cellulose sodium salt (execution standard: Q/SH 0038-2007) +0.5% polymer microsphere+0.5% 6000-mesh superfine calcium carbonate, and the plugging rate of the formula is verified, and the experimental result is shown in Table 2:
table 2 blocking rate of composite blocking material
As can be seen from Table 2, compared with the case that only 6000-mesh superfine calcium carbonate is used as the plugging material, the copolymer 1-21 prepared in the examples 8-28 is compounded with 6000-mesh superfine calcium carbonate, so that the permeability of a nano-micron stratum can be effectively reduced, the plugging rate is improved, and the synergistic effect of the copolymer 22 prepared in the comparative example 1 and the 6000-mesh superfine calcium carbonate is relatively weak.
Temperature resistance test
To examine the heat resistance of the polymer microspheres, drilling fluid experimental slurry (formulation: 0.5% bentonite (execution standard: GB/T5005) +0.05% high viscosity carboxymethyl cellulose sodium salt (execution standard: Q/SH 0038-2007) +1.0% plugging material) was aged at 150deg.C for 16h, and then at a fixed permeability (360×10) -2 mD), respectively measuring the average flow rate of the polymer microspheres prepared in examples 8-14 and comparative example 1 as plugging materials in the simulated nano-micron stratum, and calculating the permeability of the simulated stratum before and after plugging by combining a darcy formula to obtain the plugging rate of different plugging materials on the simulated stratum, wherein the experimental results are shown in table 3:
TABLE 3 blocking Rate of different blocking materials (150 ℃ C. X16 h)
As can be seen from Table 3, the blocking ratios of the copolymers 1 to 7 prepared in examples 8 to 14 were slightly reduced but were higher than 70% and the blocking ratio of the copolymer 22 prepared in comparative example 1 was less than 50% after aging at 150℃for 16 hours, compared with the case before the high temperature action, indicating that the copolymers prepared in examples 8 to 14 had higher temperature resistance.
Salt resistance test
To examine the temperature resistance of the polymer microspheres, drilling fluid experimental slurries (formulation: 0.5% bentonite (execution standard: GB/T5005) +0.05% high viscosity carboxymethyl cellulose sodium salt (execution standard: Q/SH 0038-2007) +10% NaCl+1.0% plugging material) were prepared, followed by a fixed permeability (360×10) -2 mD), respectively measuring the average flow rate of the copolymer prepared in examples 8-14 and comparative example 1 as a plugging material in the simulated nano-micron stratum, and calculating the permeability of the simulated stratum before and after plugging by combining a darcy formula to obtain different seals The plugging rate of the plugging material on the simulated stratum is shown in table 4:
TABLE 4 blocking Rate of different blocking materials (10% NaCl)
As can be seen from Table 4, the blocking ratios of the copolymers 1 to 7 prepared in examples 8 to 14 were slightly lower than before the addition of NaCl, but were all higher than 70%, while the blocking ratio of the copolymer-22 prepared in comparative example 1 was less than 50%, indicating that the copolymers prepared in examples 8 to 14 had a higher salt resistance.
Particle size distribution test
0.05g of the copolymer prepared in examples 8 to 28 and comparative example 1 was added to 200mL of distilled water, respectively, stirred at 600r/min for 20min, and the particle size distribution of the copolymer prepared in examples 8 to 28 in the filtrate was tested, respectively, using a Mastersizer 3000E type laser particle size analyzer, and the test results are shown in Table 5; the copolymer microspheres prepared in examples 8 to 28 were observed for their dispersion morphology in water using a JSM-7200F electron Field Emission Scanning Electron Microscope (FESEM), and the test results are shown in fig. 4.
TABLE 5 particle size of different plugging materials
As can be seen from Table 5, the copolymer prepared in examples 8 to 28 had a minimum particle diameter of 25nm and a maximum particle diameter of 80nm. The polymer microsphere has smaller particle size, which is beneficial to plugging the nano-micro-pore of stratum rock.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (19)
1. A polymer monomer, characterized in that the polymer monomer is selected from triphenylphosphine derivatives containing an amide bond, a carbon-carbon double bond, a phosphorus-carbon double bond and an alkyl group.
2. The polymer monomer of claim 1, wherein the polymer monomer contains 2 triphenylphosphine groups, 4 amide bonds, 2 carbon-carbon double bonds, 2 phosphorus-carbon double bonds, m+n methylene groups, and 2 methine groups;
preferably, the polymer monomer has a structure represented by formula (1):
wherein m is a natural number from 0 to 6, preferably a natural number from 0 to 4, more preferably 0,1,2; n is a natural number of 0 to 6, preferably a natural number of 0 to 4, more preferably 0,1,2.
3. A method for preparing a polymer monomer, the method comprising:
1) Mixing a bisacrylamide compound with a solvent to obtain a solution I;
2) Mixing triphenylphosphine alkyl nitrile compound with the solution I to obtain a solution II;
3) The catalyst is contacted with the solution II to react, so as to obtain a solution III;
4) And removing the solvent from the solution III, and drying to obtain a polymer monomer.
4. The preparation method according to claim 3, wherein the concentration of the bisacrylamide compound in the solution I is 3-8 wt%;
preferably, the molar ratio of the bisacrylamide compound to the triphenylphosphine alkyl nitrile compound is (2.6-3.2): 1, a step of;
preferably, the catalyst is used in an amount of 0.05wt% to 12wt%, preferably 1wt% to 10wt%, more preferably 4wt% to 8wt% of the triphenylphosphine alkylnitrile.
5. The production method according to claim 3 or 4, wherein the solvent is at least one selected from the group consisting of water, acetone, butanone, chloroform, methylene chloride, 1-dichloroethane, 1, 2-dichloroethane, methyl ethyl ketone, tetrahydrofuran, petroleum ether, diethyl ether, acetonitrile, ethyl acetate, benzene, toluene, m-xylene, cyclohexane, ethylene glycol dimethyl ether, nitromethane, 1, 4-dioxane, pyridine, morpholine, N '-dimethylformamide, N' -dimethylacetamide and dimethylsulfoxide, preferably at least one selected from the group consisting of toluene, 1, 4-dioxane, N '-dimethylformamide, N' -dimethylacetamide and dimethylsulfoxide, more preferably selected from the group consisting of N, N '-dimethylformamide and/or N, N' -dimethylacetamide.
6. The production method according to any one of claims 3 to 5, wherein the catalyst is at least one selected from sulfuric acid, phthalimide, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, bismuth trifluoromethanesulfonic acid, calcium trifluoromethanesulfonic acid, copper trifluoromethanesulfonic acid, indium trifluoromethanesulfonic acid, bis-trifluoromethanesulfonic imide, boron trifluoride diethyl ether, perfluorosulfonic acid resin, 2, 4-dinitrobenzenesulfonic acid, dodecaphosphotungstic acid, acid salts of cesium phosphotungstic acid, cesium sulfate, ceric sulfate, phosphorus pentoxide, iodine, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cobalt chloride, zinc chloride and ferric chloride hexahydrate, preferably at least one selected from boron trifluoride, bismuth trifluoromethanesulfonic acid and copper trifluoromethanesulfonic acid.
7. The production process according to any one of claims 3 to 6, wherein the bisacrylamide-based compound is selected from the group consisting of N, N '- (1, 2-dihydroxyethylene) bisacrylamide, and N, N' - (1, 2-dihydroxypropylethylene) bisacrylamide;
preferably, the triphenylphosphine alkyl nitrile is selected from (triphenylphosphine) acetonitrile, (triphenylphosphine) propionitrile or (triphenylphosphine) butyronitrile.
8. The production method according to any one of claims 3 to 7, wherein the reaction conditions include: the temperature is 80-160 ℃, preferably 100-120 ℃; the time is 6-48 hours, preferably 8-36 hours, more preferably 16-28 hours.
9. A polymer monomer produced by the production process according to any one of claims 3 to 8.
10. A copolymer, comprising: a structural unit c derived from the polymer monomer according to any one of claims 1 to 2 and 9, a structural unit a represented by formula (2), a structural unit b represented by formula (3):
wherein R is 1 、R 3 Each independently selected from H or C 1 -C 6 Alkyl of R 2 Selected from amide groups, R 4 Selected from carboxylic acid groups;
wherein the structural unit c: structural unit a: the molar ratio of the structural units b is (2-7): (20-60): (15-35), the weight-average molecular weight of the copolymer was 4.25X10 4 -5×10 4 g/mol。
11. The copolymer according to claim 10, wherein the structural unit c has a structure represented by formula (4),
wherein m is a natural number from 0 to 6, preferably a natural number from 0 to 4, more preferably 0,1,2; n is a natural number of 0 to 6, preferably a natural number of 0 to 4, more preferably 0,1,2.
12. According to the weightsThe copolymer of claim 11 or 12, wherein R 1 Selected from H, CH 3 Or C 2 H 5 ；
Preferably, R 2 Selected from the group consisting ofThe radicals indicated or->A group of the formula, wherein R a And R is b Each independently selected from H, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkyl alcohol or C of (C) 1 -C 8 Is preferably selected from the group consisting of H, CH 3 、CH 2 CH 3 、/>CH 2 OH、CH 2 CH 2 OH、/>
R c Selected from H or C 1 -C 6 Alkyl groups of (2), preferably H, CH 3 、CH 2 CH 3 Or (b)
R d Selected from CH 3 、CH 2 CH 3 Or (b)
13. The copolymer according to any one of claims 10 to 12, wherein R 3 Selected from H, CH 3 Or C 2 H 5 ；
Preferably, R 4 Selected from the group consisting ofThe radicals indicated or->A group shown in the specification, wherein A is at least one selected from H, na, K, rb or Cs, preferably at least one selected from H, na and K; s is a natural number from 0 to 6, R is a natural number from 0 to 6, t is a natural number from 0 to 6, R is selected from H or CH 3 ；
Preferably, r is a natural number from 0 to 2, s is a natural number from 0 to 4, and t is a natural number from 0 to 2.
14. A process for the preparation of a copolymer, comprising the steps of:
(1) Mixing an emulsifying agent with an organic solvent to obtain a solution A;
(2) Mixing a monomer (1) shown in a formula (5), a monomer (2) shown in a formula (6), a polymer monomer and water to obtain a solution B;
(3) The solution A, the initiator and the solution B are contacted for copolymerization reaction to obtain a copolymer;
wherein the polymer monomer is the polymer monomer of any one of claims 1-2 and 9;
Wherein R is 1 、R 2 、R 3 、R 4 Is correspondingly the same as the definition as defined in any one of claims 10 to 13.
15. The process according to claim 14, wherein,
the organic solvent is one or more selected from white oil, liquid paraffin, cyclohexane, isooctane, benzene, toluene, xylene, diesel oil, kerosene, methyl nylon, petroleum ether, butanone and isoparaffin, preferably one or more selected from white oil, cyclohexane, isooctane, benzene, toluene and petroleum ether;
preferably, the emulsifier is selected from one or more of cationic surfactant, anionic surfactant, amphoteric surfactant and nonionic surfactant, preferably polysorbate nonionic surfactant, more preferably sodium bis (2-ethylhexyl) succinate sulfonate;
preferably, the initiator is selected from a water-soluble initiator, a water-soluble redox system initiator or an azo compound initiator; wherein the water-soluble redox system initiator is selected from K 2 S 2 O 8 And/or (NH) 4 ) 2 S 2 O 8 The azo compound initiator is at least one selected from azo diiso Ding Mi hydrochloride, azo-iso Ding Qingji formamide, azo-diisobutyronitrile, benzoyl peroxide, azo-dicarboxyethyl-2-isobutyl amidine hydrate, azo-dimethyl N-2-hydroxybutyl acrylamide, azo-dicyclohexyl carbonitrile, azo-diisovaleronitrile, azo-diisoheptonitrile, azo-dicyanovaleric acid, azo-diisobutyl amidine hydrochloride, azo-diisopropylimidazoline, azo-bis-N-hydroxy isobutyl amidine hydrate, azo-bis-N, N '-cyclobutylisobutyl amidine hydrate, azo-diisobutyrate dimethyl ester and 2,2' -azo-bis (N-cyclohexylisobutyl amidine) hydrochloride.
16. The preparation method according to claim 14 or 15, wherein the concentration of the emulsifier is 10wt% to 60wt%, preferably 20wt% to 40wt%, based on the total amount of the solution a;
preferably, the mass of the water is 1-2.5 times that of the organic solvent;
preferably, the molar ratio of monomer (1), monomer (2) and polymer monomer is (20-60): (15-35): (2-9);
preferably, the concentration of the total amount of monomer (1), monomer (2) and polymer monomer in the solution B is 10wt% to 50wt%, preferably 15wt% to 30wt%;
preferably, the initiator is 0.02wt% to 4wt%, preferably 0.05wt% to 3wt%, more preferably 0.2wt% to 2wt% of the total monomer.
17. A copolymer obtainable by the process of any one of claims 14 to 16.
18. Use of a copolymer according to any one of claims 8-13 and 17 as a polymer microsphere plugging agent in the field of petroleum aids.
19. A drilling fluid comprising the copolymer of any one of claims 10-13 and 17.
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