CN117865857A - Sulfonic acid monomer, preparation method and application thereof, copolymer and application thereof and drilling fluid - Google Patents
Sulfonic acid monomer, preparation method and application thereof, copolymer and application thereof and drilling fluid Download PDFInfo
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- CN117865857A CN117865857A CN202211237190.XA CN202211237190A CN117865857A CN 117865857 A CN117865857 A CN 117865857A CN 202211237190 A CN202211237190 A CN 202211237190A CN 117865857 A CN117865857 A CN 117865857A
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- sulfonic acid
- acid monomer
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- 239000000178 monomer Substances 0.000 title claims abstract description 118
- 239000012530 fluid Substances 0.000 title claims abstract description 37
- 238000005553 drilling Methods 0.000 title claims abstract description 36
- 229920001577 copolymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title abstract description 83
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 43
- 239000010936 titanium Substances 0.000 claims description 41
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 34
- -1 alkenyl compound Chemical class 0.000 claims description 28
- 239000000654 additive Substances 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 14
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 14
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- 229910010082 LiAlH Inorganic materials 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 9
- 150000003839 salts Chemical class 0.000 abstract description 13
- 230000037048 polymerization activity Effects 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 52
- 239000000706 filtrate Substances 0.000 description 44
- 238000006116 polymerization reaction Methods 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000012043 crude product Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- 238000007334 copolymerization reaction Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000002002 slurry Substances 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 150000001993 dienes Chemical group 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- XKCABFSZWJTJFC-UHFFFAOYSA-N C=CC(C)=C.[Na] Chemical compound C=CC(C)=C.[Na] XKCABFSZWJTJFC-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 8
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000013505 freshwater Substances 0.000 description 7
- 239000012267 brine Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 2
- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical compound CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910000281 calcium bentonite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZAMCMCQRTZKGDX-SNAWJCMRSA-N (e)-3-methylpent-3-en-2-one Chemical compound C\C=C(/C)C(C)=O ZAMCMCQRTZKGDX-SNAWJCMRSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- IUWWYLSYWMLZSR-UHFFFAOYSA-N 2-(2-methylpropanoyl)benzenesulfonic acid Chemical compound CC(C)C(=O)C1=CC=CC=C1S(O)(=O)=O IUWWYLSYWMLZSR-UHFFFAOYSA-N 0.000 description 1
- PDFIEHRTRXPBNH-UHFFFAOYSA-N 2-methyl-2-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)OC(=O)C=C PDFIEHRTRXPBNH-UHFFFAOYSA-N 0.000 description 1
- QXHRQZNDMYRDPA-UHFFFAOYSA-N 3,4-dimethylpentan-2-one Chemical compound CC(C)C(C)C(C)=O QXHRQZNDMYRDPA-UHFFFAOYSA-N 0.000 description 1
- ZAMCMCQRTZKGDX-UHFFFAOYSA-N 3-methylpent-3-en-2-one Natural products CC=C(C)C(C)=O ZAMCMCQRTZKGDX-UHFFFAOYSA-N 0.000 description 1
- LRZLUWUMEKLURJ-UHFFFAOYSA-N 4-(2,2-dimethylpropanoyl)benzenesulfonic acid Chemical compound CC(C)(C)C(=O)C1=CC=C(S(O)(=O)=O)C=C1 LRZLUWUMEKLURJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UYLUJGRCKKSWHS-UHFFFAOYSA-N prop-1-en-1-one Chemical compound CC=C=O UYLUJGRCKKSWHS-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- ADPUQRRLAAPXGT-UHFFFAOYSA-M sodium;2-formylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=O ADPUQRRLAAPXGT-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Abstract
The invention relates to the field of oilfield aids, and discloses a sulfonic acid monomer, a preparation method and application thereof, a copolymer and application thereof and drilling fluid. The sulfonic acid monomer has a structure shown in a formula (I-1),therein, R, R 0 、R 1 、R 2 、R 3 Each independently is H or C 1 ‑C 6 An alkyl group; r is R 1 、R 2 、R 3 、R 4 And R is 5 At least one of them is SO 3 H、SO 3 Na or SO 3 K, the remainder each independently being H or C 1 ‑C 6 An alkyl group; t is a natural number from 0 to 9. The sulfonic acid monomer has higher polymerization activity, and the polymer prepared by the sulfonic acid monomer has good temperature resistance and salt resistance.
Description
Technical Field
The invention relates to the field of petroleum aids, in particular to a sulfonic acid monomer, a preparation method and application thereof, a copolymer and application thereof and drilling fluid.
Background
The oilfield additive is a fine chemical product and is widely used in the fields of exploration and development of oil and gas fields in petroleum industry, exploitation and transportation of oil gas and the like. Along with the increase of oil development types, the demands of oilfield aids are also rising, the oil yield and the oil quality of the oilfield are greatly improved in China, and a large amount of oilfield aids are needed in the process.
In oilfield chemical additives, the high-molecular polymer obtained by copolymerization of alkenyl monomers is a widely applied chemical, and particularly in drilling engineering, the performance of a plurality of chemical working fluids (such as drilling fluid, cement slurry, fracturing fluid and the like) is more dependent on the temperature resistance and salt resistance and is more outstanding in consideration of stratum environments with high temperature, high pressure and high mineralization. Among many synthetic polymer materials, sulfonate copolymers containing 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 2-acryloyloxy-2-methylpropanesulfonic Acid (AOPS), sodium Methallylsulfonate (SMAS), and sodium styrenesulfonate (SSS) have been studied intensively, and particularly, sulfonate copolymers using AMPS as a reaction monomer have been studied and applied to the greatest extent. AMPS contains salt-sensitive-SO 3 The group endows the copolymer prepared by using AMPS with good temperature resistance and salt resistance. However, the copolymerization reaction in which AMPS participates is generally slow, and more industrial use is made of sodium isoprene sulfonate, which is a sulfonic acid monomer having a conjugated diene structure. The monomer has high copolymerization activity, the copolymerization reaction time is generally not more than 1h, and the monomer can be subjected to explosive polymerization with alkenyl monomer even under the condition of extremely low initiator content.
However, the polymerization activity of the monomer is low and the temperature and salt resistance of the polymer obtained by polymerization is not ideal, so that it is needed to provide a sulfonic acid monomer with high polymerization activity, and the polymer obtained by polymerization of the sulfonic acid monomer has good temperature and salt resistance.
Disclosure of Invention
The invention aims to solve the problems of low polymerization activity and poor temperature and salt resistance of an obtained polymer in production and practical application of a sulfonic acid monomer in the prior art, and provides a sulfonic acid monomer, a preparation method and application thereof, a copolymer, application and drilling fluid.
In order to achieve the above object, a first aspect of the present invention provides a sulfonic acid monomer having a structure represented by formula (I-1),
therein, R, R 0 、R 1 、R 2 、R 3 Each independently is H or C 1 -C 6 An alkyl group; r is R 1 、R 2 、R 3 、R 4 And R is 5 At least one of them is SO 3 H、SO 3 Na or SO 3 K, the remainder each independently being H or C 1 -C 6 An alkyl group; t is a natural number from 0 to 9.
The second aspect of the invention provides a method for preparing the sulfonic acid monomer, which comprises the following steps: in the presence of a catalyst, carrying out a synthetic reaction on an alkenyl compound shown in a formula (II-1) and a phenyl compound shown in a formula (II-2) to obtain a sulfonic acid monomer shown in the formula (I-1),
therein, R, R 1 、R 2 、R 3 、R 0 、R 1 、R 2 、R 3 、R 4 And R is 5 And t is defined as the aboveShould be identical.
In a third aspect, the present invention provides a sulfonic acid monomer prepared by the preparation method provided by the present invention.
The fourth aspect of the invention provides an application of the sulfonic acid monomer provided by the invention in an oilfield additive.
In a fifth aspect, the present invention provides a copolymer comprising structural units derived from the sulfonic acid monomers provided herein.
The sixth aspect of the invention provides the use of the copolymer provided by the invention as a fluid loss additive, a tackifier, a viscosity reducer, a cutting agent and an inhibitor.
In a seventh aspect, the present invention provides a drilling fluid comprising the copolymer provided herein.
The beneficial effects of the invention are as follows:
(1) The benzene ring structure is introduced into the sulfonic acid monomer, so that the monomer not only improves the water solubility of polymer molecules, but also has weaker sensitivity to metal ions; and the introduced benzene ring structure endows the monomer with stronger rigidity. In addition, the steric hindrance effect of the benzene ring structure also reduces the thermal motion degree of the molecular chain under the high temperature condition. Comparing the high temperature and high pressure Fluid Loss (FL) measured in the brine-based slurry and in the fresh water-based slurry HTHP ) It is known that when the copolymer obtained by taking the sulfonic acid monomer provided by the invention as a raw material is used as a fluid loss additive in drilling fluid, the fluid loss reducing capability and the temperature and salt resistance are better than those of sodium isoprene sulfonate. According to the invention, the sulfonic acid monomer is simultaneously introduced with the sulfonic acid group and the benzene ring structure, and the sulfonic acid group and the benzene ring structure are mutually matched and act synergistically, so that the temperature resistance and salt resistance of the polymer molecule are obviously improved.
(2) The sulfonic acid monomer provided by the invention also contains a conjugated diene structure, and can synergistically contain a sulfonic acid group and a benzene ring structure, so that the polymerization activity of the monomer is enhanced, and the polymerization speed is improved. The fluid loss additive further obtained by taking the sulfonic acid monomer as the raw material has FL after the polymerization reaction time reaches 0.5h HTHP The value of (2) no longer changes with the extension of the polymerization time, indicating that the monomer had completed polymerization within 0.5hThe reaction has higher polymerization activity, and the polymerization activity is equivalent to that of sodium isoprene sulfonate.
Drawings
FIG. 1 shows the magnetic resonance spectrum of the sulfonic acid monomer obtained in example 1 1 H NMR) map;
FIG. 2 shows the magnetic resonance spectrum of the sulfonic acid monomer obtained in example 2 1 H NMR) map.
Detailed Description
The following describes embodiments of the present invention in detail with reference to fig. 1-2. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a sulfonic acid monomer, wherein the sulfonic acid monomer has a structure represented by formula (I-1),
therein, R, R 0 、R 1 、R 2 、R 3 Each independently is H or C 1 -C 6 An alkyl group; r is R 1 、R 2 、R 3 、R 4 And R is 5 At least one of them is SO 3 H、SO 3 Na or SO 3 K, the remainder each independently being H or C 1 -C 6 An alkyl group; t is a natural number from 0 to 9.
According to the invention, preferably R, R 1 、R 2 、R 3 Each independently is H or CH 3 ，R 0 H, CH of a shape of H, CH 3 、C 2 H 5 、CH(CH 3 ) 2 Or C (CH) 3 ) 3 ；R 1 、R 2 、R 3 、R 4 And R is 5 At least one of them is SO 3 H、SO 3 Na or SO 3 K, the rest is H; t is a natural number from 0 to 6; more preferably, t is 0, 1 or 2.
According to a particular embodiment of the invention, the monomer is selected from the compounds shown below:
the second aspect of the invention provides a preparation method of the sulfonic acid monomer, wherein the method comprises the following steps: in the presence of a catalyst, carrying out a synthetic reaction on an alkenyl compound shown in a formula (II-1) and a phenyl compound shown in a formula (II-2) to obtain a sulfonic acid monomer shown in the formula (I-1),
therein, R, R 1 、R 2 、R 3 、R 0 、R 1 、R 2 、R 3 、R 4 And R is 5 And t is correspondingly the same as the definition above.
The catalyst used in the preparation method provided by the invention can be used for promoting the coupling of carbonyl into alkene, and can be at least one of low-valence titanium, low-valence tungsten, low-valence molybdenum, low-valence zirconium, low-valence vanadium and low-valence niobium.
The low-valent titanium, low-valent tungsten, low-valent molybdenum, low-valent zirconium, low-valent vanadium and low-valent niobium used in the catalyst of the invention can be substances obtained by taking the preparation of low-valent titanium as an example by methods known in the art.
According to a preferred embodiment of the invention, the catalyst is a low-valent titanium.
According to a preferred embodiment of the present invention, a method for producing, for example, low-priced titanium comprises: and dissolving the titanium-containing reagent and the reducing agent in the solvent A for reduction reaction.
Preferably, the preparation method of the low-valence titanium further comprises the following steps: the reduction reaction is carried out under a protective atmosphere, wherein the protective atmosphere is nitrogen and/or argon.
According to the invention, the titanium-containing reagent is selected from at least one of titanium trichloride, titanium tetrachloride or commercial titanium powder; the reducing agent is selected from K, li, na, zn +CuCl and LiAlH 4 The valence state of the low-valence titanium, at least one of Mg, mg+hg, li+hg and chlorosilane, generally varies depending on the reducing activity of the reducing agent and the ratio of the reducing agent to the amounts of titanium trichloride, titanium tetrachloride and commercial titanium powders.
According to the invention, solvent A is Tetrahydrofuran (THF) and/or Dimethyl Ether (DEM).
According to a preferred embodiment of the invention, the titanium-containing reagent is titanium tetrachloride; the reducing agent is Zn and CuCl; solvent A is one of Tetrahydrofuran (THF) and dimethyl ether (DME).
Preferably, the concentration of titanium tetrachloride in the solvent A is 0.2-0.7mmol/mL, the concentration of Zn in the solvent A is 0.3-0.8mmol/mL, and the concentration of CuCl in the solvent A is 0.02-0.06mmol/mL.
According to an embodiment of the present invention, the method for preparing low-valence titanium further specifically comprises: adding activated Zn, cuCl and solvent A into a reactor, cooling, stirring, and adding TiCl 4 The reduction reaction is performed in a reflux manner to obtain low-valence titanium.
According to a preferred embodiment of the invention, when the solvent a is THF, the temperature of the reflux is 66 ℃ to 72 ℃ and it is necessary to cool again after the reflux; when the solvent A is DME, the reflux is carried out without increasing the temperature, i.e. at the cooling temperature of the preceding step.
Preferably, the Zn has a particle size of at least 200 mesh, more preferably 200-600 mesh.
Preferably, the temperature of the cooling is-10 ℃ to 0 ℃, and the time of the reflux is 2-4h.
According to a preferred embodiment of the present invention, the molar ratio of alkenyl compound to phenyl compound in the synthesis reaction is 1: (1.2-1.6).
According to one embodiment of the invention, the preparation method of the sulfonic acid monomer comprises the following steps: the alkenyl compound and the phenyl compound are dissolved in solvent B prior to the synthesis reaction.
According to a specific embodiment of the present invention, the preparation method of the sulfonic acid monomer includes: the alkenyl compound and the phenyl compound are dissolved in the solvent B and then mixed into the low-valence titanium reagent, and the synthesis reaction is performed in a reflux manner under stirring.
Preferably, the solvent B is the same as the solvent a in a volume ratio of 1: (2.5-5).
Preferably, the concentration of the alkenyl compound in the solvent B is 0.2-0.5mmol/mL.
Preferably, the temperature of the synthesis reaction is-10 ℃ to 0 ℃ or 66 ℃ to 72 ℃; the synthesis reaction time is 2-8h; more preferably 3-6 hours. Wherein, when solvent B is THF, the temperature of the synthesis reaction is, correspondingly, 66 ℃ to 72 ℃; when solvent B is DME, the temperature of the synthesis reaction is correspondingly-10 ℃ to 0 ℃.
The preparation method of the monomer provided by the invention can also comprise quenching reaction after the synthesis reaction is performed to a certain extent. Because of the excess reactants present in the synthesis reaction, when the reaction proceeds to some extent, the desired product is already obtained and the excess reactants, if present, continue to react further to form undesired products. The principle of quenching is to react with another compound that is more reactive with the excess compound, thereby removing it from the system.
In order to avoid the occurrence of impurities in the product, the present invention preferably performs the quenching reaction after the synthesis reaction has proceeded to a certain extent, i.e., the alkenyl compound has reacted completely, the present invention is not particularly limited, and conventional quenching reagents such as alkali metal cyanide, amide, borane, potassium carbonate, lithium aluminum hydride and sodium borohydride may be selected. However, in view of the stability of the product and the ease of handling, potassium carbonate (K) 2 CO 3 ) As a quenchAnd (3) a reagent.
According to a preferred embodiment of the invention, the concentration of the potassium carbonate solution is between 5% and 20% by weight, preferably between 8% and 12% by weight, the K 2 CO 3 The volume ratio of the solution to the solvent B is 1: (8-16).
In order to obtain a solid of the monomer, the preparation method of the monomer provided by the invention can further comprise the following steps: filtering after quenching reaction, removing catalyst, and collecting filtrate; drying and removing the solvent.
The present invention is not limited to the filtration method, and conventional filter aids such as diatomaceous earth filter aid, charcoal filter aid, activated carbon filter aid, and perlite filter aid may be added as long as low-valent titanium can be filtered out.
According to a preferred embodiment of the invention, diatomaceous earth is used for filtration.
In order to collect as much product as possible, the invention also preferably provides for rinsing after filtration and collection of the filtrate, the rinsing solvent may be selected from conventional rinsing reagents, preferably with CH 2 Cl 2 And (3) pouring, namely mixing the pouring liquid with the filtrate after pouring to obtain a mixed liquid.
The method of obtaining the monomer solid, including the drying agent used and the method of removing the solvent, is not limited in the present invention, as long as a solid product can be obtained.
According to a preferred embodiment of the present invention, the mixed solution is dried with a desiccant, filtered and distilled under reduced pressure, and the solvent is removed to obtain a pale yellow crude product; the desiccant is preferably an inorganic neutral desiccant, e.g. MgSO 4 Anhydrous Na 2 SO 4 、CaSO 4 、CaCl 2 One or more of the following.
In order to obtain a solid of the monomer with high purity, the preparation method of the sulfonic acid monomer provided by the invention can further comprise the following steps: and (3) purifying the crude product obtained by the synthesis reaction.
According to the invention, recrystallization purification is employed. The method is not limited to the recrystallized solvent, and the method preferably uses methanol or ethanol to recrystallize the crude product to obtain white frosty powder, namely the conjugated diene sulfonic acid monomer, in consideration of the polarity and solubility of the solvent.
In a third aspect, the present invention provides a sulfonic acid monomer prepared by the preparation method provided by the present invention.
The fourth aspect of the invention provides an application of the sulfonic acid monomer provided by the invention in an oilfield additive.
In a fifth aspect, the present invention provides a copolymer comprising structural units derived from the sulfonic acid monomers of the present invention.
The present invention is not particularly limited in the kind of copolymer obtained by polymerizing the sulfonic acid monomer of the present invention alone or copolymerizing with other monomers.
Preferably, the other monomers may be selected from, but are not limited to, one or more of acrylamide, N-isopropylacrylamide, vinylpyrrolidone, acrylic acid, sodium acrylate, acrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid, dimethyldiallylammonium chloride, and gamma-methacryloxypropyl trimethoxysilane. For example, the copolymer may be a terpolymer, and may be a copolymer prepared from monomers of Acrylamide (AM), vinylpyrrolidone (NVP) and the sulfonic acid monomer provided by the present invention in a molar ratio of (1-10): (1-3): (1-3) polymerization. The weight average molecular weight of the copolymer may be 1.5X10 5 -2.5×10 5 g/mol。
The present invention is not particularly limited to the polymerization method, and any of solution polymerization, gas phase polymerization, and bulk polymerization may be used, and according to the embodiment of the present invention, the solution polymerization is preferable, and the present invention is exemplified herein by specific operations, and those skilled in the art should not be construed as limiting the present invention.
The sixth aspect of the invention provides the use of the copolymer provided by the invention as a fluid loss additive, a tackifier, a viscosity reducer, a cutting agent and an inhibitor.
In a seventh aspect, the present invention provides a drilling fluid comprising the copolymer provided herein.
In the present invention, the above-mentioned drilling fluid system is not particularly limited, and may be various drilling fluid systems known in the art, and according to a specific embodiment of the present invention, the drilling fluid of the present invention may be a water-based drilling fluid or a salt-based drilling fluid.
Preferably, additives are also included in the water-based drilling fluid.
Preferably, the additive comprises bentonite, sodium carbonate.
In the present invention, the content of the copolymer in the drilling fluid is not particularly limited, and may be appropriately adjusted according to the formation conditions, and for example, the content of the copolymer may be 0.2wt% to 2.0wt% based on the total amount of the drilling fluid.
In the present invention, the preparation method of the drilling fluid is not particularly limited, and may be a preparation method well known to those skilled in the art, and the present invention is not described herein in detail, but specific operations are exemplified herein, and those skilled in the art should not understand the limitation of the present invention.
Example 1
Under the protection of argon, 16.345g (250 mmol) of activated Zn powder with 200 meshes, 1.98g (20 mmol) of CuCl and 500mL of THF are added into a reactor, cooled to-5 ℃, stirred and 37.9358g (200 mmol) of TiCl are added 4 Heating to 68 ℃ and refluxing for 2.5 hours, and cooling to-5 ℃ again to obtain the low-valence titanium reducing agent.
4.2055g (60 mmol) of methylketene and 18.7347g (90 mmol) of sodium benzaldehyde-2-sulfonate are dissolved in 200mL of THF and mixed into a low-valent titanium reducing agent, the temperature is raised to 68℃with stirring, and the mixture is refluxed for 5 hours. 20mL of K having a concentration of 10.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Adding sufficient Na to the mixture 2 SO 4 Filtering, distilling under reduced pressure, and removing THF to obtain a pale yellow crude product.
Recrystallizing the crude product with methanol to obtain white frosty powder, namely the target product with the yield of 72.5%.
Nuclear magnetic characterization of the product obtained in example 1 [ (CD) 3 ) 2 SO，25℃]Magnetic resonance spectrum 1 H NMR) is shown in fig. 1. According to 1 H NMR analysis canThe target product is known to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, wherein: r is R 1 、R 2 、R 3 、R 0 、R 2 、R 3 、R 4 And R is 5 Is H, R is CH 3 ，R 1 Is SO 3 Na, t=0, as shown in the following formula:
example 2
Under the protection of nitrogen, 15.6912g (240 mmol) of 400-mesh activated Zn powder, 1.584g (16 mmol) of CuCl and 800mL of DME are added into a reactor, the temperature is controlled to-10 ℃, stirring is carried out, and 30.3486g (160 mmol) of TiCl is added 4 And refluxing for 2 hours to obtain the low-valence titanium reducing agent.
7.0091g (100 mmol) of 2-butenal and 37.2242g (120 mmol) of sodium benzaldehyde-2, 4-disulfonate were dissolved in 200mL of DME, mixed into a low-valent titanium reducing agent, and refluxed for 3 hours. 20mL of K having a concentration of 10.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Sufficient MgSO was added to the mixture 4 Filtering, distilling under reduced pressure, and removing DME to obtain pale yellow crude product.
Recrystallizing the crude product with ethanol to obtain white frosty powder, namely the target product with the yield of 76.9%.
Nuclear magnetic characterization of the product obtained in example 2 [ (CD) 3 ) 2 SO，25℃]Magnetic resonance spectrum 1 H NMR) is shown in fig. 2. According to 1 The target product was found to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, as determined by H NMR analysis, wherein: r is R 1 Is CH 3 ，R 2 、R 3 、R、R 0 、R 2 、R 4 And R is 5 Is H, R 1 And R is 3 Is SO 3 Na, t=0, as shown in the following formula:
example 3
Under the protection of nitrogen, 15.6912g (240 mmol) of 600-mesh activated Zn powder, 1.584g (16 mmol) of CuCl and 800mL of DME are added into a reactor, the temperature is controlled to-10 ℃, stirring is carried out, and 30.3486g (160 mmol) of TiCl is added 4 And refluxing for 2 hours to obtain the low-valence titanium reducing agent.
7.0091g (100 mmol) of methacrolein and 27.3914g (120 mmol) of 4- (4-sulfophenyl) -2-butanone were dissolved in 200mL of DME, mixed into a low-valent titanium reducing agent, and refluxed for 3 hours. 20mL of K having a concentration of 10.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Sufficient MgSO was added to the mixture 4 Filtering, distilling under reduced pressure, and removing DME to obtain pale yellow crude product.
Recrystallizing the crude product with methanol to obtain white frosty powder, which is the target product with a yield of 71.4%.
Nuclear magnetic characterization of the product obtained in example 3 [ (CD) 3 ) 2 SO，25℃]. According to 1 The target product was found to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, as determined by H NMR analysis, wherein: r is R 1 And R is 0 Is CH 3 ，R 2 、R 3 、R、R 1 、R 2 、R 4 And R is 5 Is H, R 3 Is SO 3 H, t=2, as shown in the following formula:
example 4
Under the protection of nitrogen, 19.614g (300 mmol) of 500-mesh activated Zn powder, 2.97g (30 mmol) of CuCl and 500mL of THF are added into a reactor, cooled to-10 ℃, stirred, and 47.4198g (250 mmol) of TiCl are added 4 Heating to 72 ℃ and refluxing for 2 hours, and cooling to-10 ℃ again to obtain the low-valence titanium reducing agent.
2.103g (25 mmol) of 3-methyl-2-butenal and 11.7717g (40 mmol) of 3, 5-disulfonic acid phenylacetone are dissolved in 125mL of THF and mixed into the low-valent titanium reducing agent, and the temperature is raised to 72℃with stirring and the mixture is refluxed for 3 hours. 15mL of K having a concentration of 12.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Adding sufficient CaCl to the mixture 2 Filtering, distilling under reduced pressure, and removing THF to obtain a pale yellow crude product.
Recrystallizing the crude product with methanol to obtain white frosty powder, namely the target product with the yield of 75.6 percent.
Nuclear magnetic characterization of the product obtained in example 4 [ (CD) 3 ) 2 SO，25℃]. According to 1 The target product was found to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, as determined by H NMR analysis, wherein: r is R 1 、R 2 And R is 0 Is CH 3 ，R 3 、R、R 1 、R 3 And R is 5 Is H, R 2 And R is 4 Is SO 3 H, t=1, as shown in the following formula:
example 5
Under the protection of argon, 19.614g (300 mmol) of 400-mesh activated Zn powder, 2.97g (30 mmol) of CuCl and 600mL of THF are added into a reactor, cooled to 0 ℃, stirred and 79.6652g (420 mmol) of TiCl are added 4 Heating to 68 ℃ and refluxing for 4 hours, and cooling to 0 ℃ again to obtain the low-valence titanium reducing agent.
2.6911g (48 mmol) of acrolein and 17.1575g (72 mmol) of potassium acetophenone-2-sulfonate are dissolved in 120mL of THF and mixed into a low-valent titanium reducing agent, the temperature is raised to 68℃with stirring, and the mixture is refluxed for 6 hours. 75mL of K at a concentration of 8.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Adding a sufficient amount of the mixtureNa of (2) 2 SO 4 Filtering, distilling under reduced pressure, and removing THF to obtain a pale yellow crude product.
Recrystallizing the crude product with methanol to obtain white frosty powder, namely the target product with the yield of 78.3 percent.
Nuclear magnetic characterization of the product obtained in example 5 [ (CD) 3 ) 2 SO，25℃]. According to 1 The target product was found to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, as determined by H NMR analysis, wherein: r is R 0 Is CH 3 ，R 1 、R 2 、R 3 、R、R 2 、R 3 、R 4 And R is 5 Is H, R 1 Is SO 3 K, t=0, as shown in the following formula:
example 6
Under the protection of argon, 20.9216g (320 mmol) of 500-mesh activated Zn powder, 2.376g (24 mmol) of CuCl and 800mL of THF are added into a reactor, cooled to-4 ℃, stirred, and 45.523g (240 mmol) of TiCl are added 4 Heating to 70 ℃ and refluxing for 3.5 hours, and cooling to-4 ℃ again to obtain the low-valence titanium reducing agent.
6.2813g (64 mmol) of 4-methyl-3-penten-2-one and 23.2597g (96 mmol) of 2, 2-dimethyl- (4-sulfophenyl) -1-propanone are dissolved in 320mL of THF and mixed into the low-valent titanium reducing agent, the temperature is raised to 70℃with stirring, and the reflux is continued for 5h. 20mL of K having a concentration of 12.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Adding sufficient Na to the mixture 2 SO 4 Filtering, distilling under reduced pressure, and removing THF to obtain a pale yellow crude product.
Recrystallizing the crude product with methanol to obtain white frosty powder, namely the target product with the yield of 72.7 percent.
Nuclear magnetic characterization of the product obtained in example 6 [ (CD) 3 ) 2 SO，25℃]. According to 1 The target product was found to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, as determined by H NMR analysis, wherein: r is R 1 、R 2 And R is CH 3 ，R 3 、R 1 、R 2 、R 4 And R is 5 Is H, R 3 Is SO 3 H，R 0 Is C (CH) 3 ) 3 T=0, as shown in the following formula:
example 7
Under the protection of nitrogen, 52.304g (800 mmol) of activated Zn powder with 200 meshes, 3.96g (40 mmol) of CuCl and 1000mL of DME are added into a reactor, the temperature is controlled to 0 ℃, stirring is carried out, and 75.8716g (400 mmol) of TiCl is added 4 Reflux is carried out for 4 hours, and the low-valence titanium reducing agent is obtained.
12.6681g (125 mmol) of 3-methyl-3-penten-2-one and 39.9459g (175 mmol) of 2-methyl-1- (2-sulfophenyl) -1-propanone were dissolved in 250mL of DME and mixed into a low-valent titanium reducing agent and refluxed for 4 hours. 25mL of K at a concentration of 10.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Adding a sufficient amount of CaSO to the mixture 4 Filtering, distilling under reduced pressure, and removing DME to obtain pale yellow crude product.
Recrystallizing the crude product with methanol to obtain white frosty powder, namely the target product with the yield of 75.0%.
Nuclear magnetic characterization of the product obtained in example 7 [ (CD) 3 ) 2 SO，25℃]. According to 1 The target product was found to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, as determined by H NMR analysis, wherein: r is R 1 、R 3 And R is CH 3 ，R 2 、R 2 、R 3 、R 4 And R is 5 Is H, R 1 Is SO 3 H，R 0 Is CH (CH) 3 ) 2 T=0, as shown in the following formula:
example 8
Under the protection of argon, 19.614g (300 mmol) of 600-mesh activated Zn powder, 4.455g (45 mmol) of CuCl and 750mL of DME are added into a reactor, the temperature is controlled to minus 6 ℃, stirring is carried out, and 30.3486g (160 mmol) of TiCl is added 4 Reflux is carried out for 4 hours, and the low-valence titanium reducing agent is obtained.
10.0955g (90 mmol) of 3, 4-dimethyl-2-pentanone and 36.1028g (112 mmol) of 1- (2, 4-disulfonic acid phenyl) -3-pentanone are dissolved in 300mL of DME, mixed into a low-valent titanium reducing agent and refluxed for 3h. 30mL of K at a concentration of 10.0wt% was added 2 CO 3 The solution was filtered through celite and the filtrate was collected and taken up with CH 2 Cl 2 And (3) showering, wherein the showering liquid is mixed with the filtrate to obtain a mixed liquid. Adding sufficient CaCl to the mixture 2 Filtering, distilling under reduced pressure, and removing DME to obtain pale yellow crude product.
Recrystallizing the crude product with ethanol to obtain white frosty powder, namely the target product with the yield of 73.8%.
Nuclear magnetic characterization of the product obtained in example 8 [ (CD) 3 ) 2 SO，25℃]. According to 1 The target product was found to be a conjugated diene sulfonic acid monomer having a structure represented by the formula (I-1) of the present invention, as determined by H NMR analysis, wherein: r is R 1 、R 2 、R 3 And R is CH 3 ，R 2 、R 4 And R is 5 Is H, R 1 And R is 3 Is SO 3 H，R 0 Is C 2 H 5 T=2, as shown in the following formula:
example 9
The procedure of example 8 was followed except that the molar amount of 1- (2, 4-disulfonic acid phenyl) -3-pentanone was 160mmol. Other conditions were the same as in example 8, and the yield of the target product was 45.8%.
Subjecting the obtained product to nuclear magnetic characterization [ (CD) 3 ) 2 SO，25℃]According to 1 The structure of the target product was found to be the same as in example 8 by H NMR analysis.
Example 10
The procedure of example 8 was followed except that the temperature was controlled to 5 ℃. Other conditions were the same as in example 8, and the yield of the target product was 40.1%.
Subjecting the obtained product to nuclear magnetic characterization [ (CD) 3 ) 2 SO，25℃]According to 1 The structure of the target product was found to be the same as in example 8 by H NMR analysis.
Example 11
The procedure of example 6 was followed, except that the temperature rise in the step of producing low-valent titanium was 80 ℃. Other conditions were the same as in example 6, and the yield of the target product was 24.6%.
Subjecting the obtained product to nuclear magnetic characterization [ (CD) 3 ) 2 SO，25℃]According to 1 The structure of the target product was found to be the same as in example 6 by H NMR analysis.
Example 12
The procedure of example 6 was followed except that the reflux time in the step of preparing low-valent titanium was 1h. Other conditions were the same as in example 6, and the yield of the target product was 34.8%.
Subjecting the obtained product to nuclear magnetic characterization [ (CD) 3 ) 2 SO，25℃]According to 1 The structure of the target product was found to be the same as in example 6 by H NMR analysis.
Example 13
The procedure of example 6 was followed except that the particle size of the activated Zn powder in the step of preparing low-valent titanium was 100 mesh. Other conditions were the same as in example 6, and the yield of the target product was 23.7%.
Subjecting the obtained product to nuclear magnetic characterization [ (CD) 3 ) 2 SO，25℃]According to 1 The structure of the target product was found to be the same as in example 6 by H NMR analysis.
PREPARATION EXAMPLES 1 to 18
This preparation is intended to illustrate the preparation of the copolymers of the invention.
400mL of distilled water was added to the reactor, followed by sequential additionAM, vinylpyrrolidone (NVP), sulfonic acid monomer (molar ratio: 3:1:1) 60g, adjust the pH of the solution to 8.0 with 10wt% NaOH, warm to 45 ℃, add 0.2g (NH) under nitrogen protection 4 ) 2 S 2 O 8 The copolymerization reaction is then started.
Taking out the copolymer products obtained after reaching the set different copolymerization reaction time, vacuum drying at 60 ℃ to constant weight, then putting the product into 350mL absolute ethyl alcohol to soak for 2h, precipitating, filtering, flushing the product with acetone for 3 times, extracting the product with a Soxhlet extractor for 4h by taking glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, taking out the product, vacuum drying at 25 ℃ to constant weight, thus obtaining the copolymer 1-18 with the weight average molecular weight of 1.5x10 5 -2.5×10 5 g/mol。
Wherein the sulfonic acid monomers of preparation examples 1 to 13 are the conjugated diene sulfonic acid monomers prepared in examples 1 to 13, respectively; the sulfonic acid monomers of preparations 14-18 were sodium isoprene sulfonate, AMPS, AOPS, SSS and SMAS, respectively.
Test example 1 evaluation of temperature resistance of fluid loss agent product
1. Preparation of drilling fluid
Fresh water based slurry: 400mL of tap water was added to the high-stirring cup, and 16.0g of calcium bentonite and 0.8g of Na were quantitatively added under continuous stirring 2 CO 3 . Stirring for 20min, stopping at least twice, scraping off bentonite adhered to the container wall, and maintaining in a sealed container for 24h.
8g of the copolymer obtained by achieving different set copolymerization reaction times in preparation examples 1-18 was weighed and used as a filtrate reducer, and added into 400mL of the fresh water base slurry, respectively, and the mixture was sufficiently stirred and maintained under sealed conditions for 24 hours, so as to obtain drilling fluids 1-18, wherein each drilling fluid was a copolymer obtained by having different copolymerization reaction times, as shown in Table 1.
2. The testing method comprises the following steps:
ZB/TE13004-90 is adopted: drilling fluid testing procedure.
Drilling fluids 1-18 (each drilling fluid is copolymer obtained by 8g of different copolymerization reaction time) are respectively stirred at high speed for 5min and then are filled inAging at 150deg.C for 16 hr in a high temperature aging tank, and measuring drilling fluid high temperature and high pressure Filtration Loss (FL) with a high temperature and high pressure filtration loss instrument HTHP ) The test results are shown in Table 1.
TABLE 1 FL of different experimental slurries HTHP (mL)
As can be seen from Table 1, the filtrate reducer obtained by using the sulfonic acid monomers of the present invention prepared in examples 1 to 13 as a raw material, after the copolymerization time reached 0.5h, had FL of drilling fluid containing the same HTHP The values of (2) are not changed with the extension of the polymerization time in the synthesis of the filtrate reducer, which indicates that the sulfonic acid monomers prepared in examples 1-13 have completed polymerization with AM and NVP within 0.5h, indicating that the monomers have good reactivity and rapid polymerization capability. In comparison with the filtrate reducer obtained from the sulfonic acid monomer of the present invention prepared in examples 1 to 13 using the same polymerization time, the drilling fluid 14 contains the filtrate reducer obtained from sodium isoprene sulfonate as a raw material, and the FL of the monomer is obtained when the polymerization time of the monomer is also about 0.5 hours HTHP Slightly larger. In contrast, the filtrate reducer obtained by further copolymerizing AMPS, AOPS, SSS and SMAS as sulfonic acid monomers has a FL as the polymerization time increases HTHP The values of (2) gradually decrease, indicating that AMPS, AOPS, SSS and SMAS did not complete the polymerization with AM and NVP over a longer polymerization time. The test results show that the sulfonic acid monomer prepared in the embodiments 1-13 has higher polymerization activity, and the filtrate reduction effect of the filtrate reducer obtained by further copolymerization is superior to that of the filtrate reducer obtained by taking sodium isoprene sulfonate as a raw material. In addition, the sulfonic acid monomers prepared in examples 9 to 10 had the same structure as the sulfonic acid monomer prepared in example 8, and the yield of the sulfonic acid monomer was lowered, so that the fluid loss additive obtained by further copolymerizing the sulfonic acid monomers prepared in examples 9 to 10 as a raw material was further copolymerized with the fluid loss additive FL obtained by further copolymerizing the sulfonic acid monomer prepared in example 8 as a raw material HTHP The same applies. Similarly, the sulfonic acid monomers prepared in examples 11 to 13 had the same structure as the sulfonic acid monomer prepared in example 6, and the yield of the sulfonic acid monomer was lowered, so that the fluid loss additive obtained by further copolymerizing the sulfonic acid monomers prepared in examples 11 to 13 as a raw material was FL of the fluid loss additive obtained by further copolymerizing the sulfonic acid monomer prepared in example 6 as a raw material HTHP The same applies.
Test example 2 evaluation of salt resistance of fluid loss additive product
1. Preparation of drilling fluid
Brine-based slurry: 400mL of tap water was added to the high-stirring cup, and 40g of NaCl, 16.0g of calcium bentonite and 0.8g of Na were quantitatively added under continuous stirring 2 CO 3 . Stirring for 20min, stopping at least twice, scraping off bentonite adhered to the container wall, and maintaining in a sealed container for 24h.
8g of the copolymer obtained by achieving different set copolymerization times in preparation examples 1 to 18 was weighed as a filtrate reducer, and added to the above 400mL of brine-based slurry, respectively, and the mixture was sufficiently stirred and cured under sealed conditions for 24 hours, to obtain drilling fluids 19 to 36, respectively, each of which was a copolymer obtained by having different copolymerization times, as shown in Table 2.
2. The testing method comprises the following steps:
ZB/TE13004-90 is adopted: drilling fluid testing procedure.
Drilling fluids 19-36 (each of which is a copolymer obtained by 8g of different copolymerization reaction time) are respectively put into a high-temperature aging tank after being stirred at high speed for 5min, are respectively aged at 150 ℃ for 16h, and the high-temperature and high-pressure Filtration Loss (FL) of the drilling fluids is measured by a high-temperature and high-pressure filtration loss instrument HTHP ) The test results are shown in Table 2.
TABLE 2 FL of different experimental slurries HTHP (mL)
As can be seen from Table 2, the filtrate reducer obtained by using the sulfonic acid monomers of the present invention prepared in examples 1 to 13 as raw materials was used in copolymerizationAfter reaching 0.5h, FL of drilling fluid containing the same HTHP The values of (2) are not changed with the extension of the polymerization time in the synthesis of the filtrate reducer, which indicates that the sulfonic acid monomers prepared in examples 1-13 have completed polymerization with AM and NVP within 0.5h, indicating that the monomers have good reactivity and rapid polymerization capability. In comparison with the filtrate reducer obtained from the sulfonic acid monomer of the present invention prepared in examples 1 to 13 using the same polymerization time, the drilling fluid 32 contains the filtrate reducer obtained from sodium isoprene sulfonate, and the FL of the monomer is obtained when the polymerization time is about 0.5h HTHP Slightly larger. In contrast, the filtrate reducer obtained by further copolymerizing AMPS, AOPS, SSS and SMAS as sulfonic acid monomers has a FL as the polymerization time increases HTHP The values of (2) gradually decrease, indicating that AMPS, AOPS, SSS and SMAS did not complete the polymerization with AM and NVP over a longer polymerization time. This is the same as the trend of the performance change measured in fresh water based slurries for different fluid loss additives.
Comparing the measurement results of the filtrate reducer in the fresh water base slurry, and measuring FL of the filtrate reducer obtained by further copolymerizing the sulfonic acid monomers prepared in examples 1-13 of the present invention and sodium isoprene sulfonate as raw materials in the brine base slurry HTHP Slightly higher than in fresh water base pulp, but still in a controllable range, has good salt resistance. For the filtrate reducer obtained by further copolymerizing AMPS, AOPS, SSS and SMAS serving as sulfonic acid monomers, FL when the copolymerization time reaches 8h HTHP Still larger, i.e., longer polymerization times are required to complete the polymerization, indicating that the reactivity and polymerization capacity of the monomer is poor.
In addition, as the trend of the performance change measured in the fresh water-based slurry was the same, the sulfonic acid monomers prepared in examples 9 to 10 had the same structure as the sulfonic acid monomer prepared in example 8 in the brine-based slurry, and the yield of the sulfonic acid monomer was lowered, and therefore, the fluid loss additive obtained by further copolymerizing the sulfonic acid monomers prepared in examples 9 to 10 as a raw material was FL of the fluid loss additive obtained by further copolymerizing the sulfonic acid monomer prepared in example 8 as a raw material HTHP The same applies. Likewise, prepared in examples 11-13The structure of the prepared sulfonic acid monomer was the same as that of the sulfonic acid monomer prepared in example 6, and the yield of the sulfonic acid monomer was reduced, so that the filtrate reducer obtained by further copolymerizing the sulfonic acid monomers prepared in examples 11 to 13 was used as the raw material, and the FL of the filtrate reducer obtained by further copolymerizing the sulfonic acid monomer prepared in example 6 was used as the raw material HTHP The same applies.
The test results show that the sulfonic acid monomer prepared in the embodiments 1-13 has higher polymerization activity, the filtrate reducer obtained by further copolymerization of the sulfonic acid monomer has better temperature resistance and salt resistance than the filtrate reducer obtained by further copolymerization of sodium isoprene sulfonate, and the filtrate reducer has better filtrate reducing effect than the filtrate reducer obtained by further copolymerization of sodium isoprene sulfonate serving as a raw material.
The preferred embodiments of the present invention have been described in detail above with reference to fig. 1-2, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of individual specific technical features in any suitable way. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition. Such simple variations and combinations are likewise to be regarded as being within the scope of the present disclosure.
Claims (10)
1. A sulfonic acid monomer is characterized in that the sulfonic acid monomer has a structure shown in a formula (I-1),
therein, R, R 0 、R 1 、R 2 、R 3 Each independently is H or C 1 -C 6 An alkyl group; r is R 1 、R 2 、R 3 、R 4 And R is 5 At least one of them is SO 3 H、SO 3 Na or SO 3 K, the remainder each independently being H or C 1 -C 6 An alkyl group; t is a natural number from 0 to 9.
2. The sulfonic acid monomer of claim 1, wherein R, R 1 、R 2 、R 3 Each independently is H or CH 3 ，R 0 H, CH of a shape of H, CH 3 、C 2 H 5 、CH(CH 3 ) 2 Or C (CH) 3 ) 3 ；R 1 、R 2 、R 3 、R 4 And R is 5 At least one of them is SO 3 H、SO 3 Na or SO 3 K, the rest is H; t is a natural number from 0 to 6;
preferably, t is 0, 1 or 2.
3. Sulfonic acid monomer according to claim 1 or 2, characterized in that it is selected from the following compounds:
4. a method for preparing a sulfonic acid monomer, comprising: in the presence of a catalyst, carrying out a synthetic reaction on an alkenyl compound shown in a formula (II-1) and a phenyl compound shown in a formula (II-2) to obtain a sulfonic acid monomer shown in the formula (I-1),
therein, R, R 1 、R 2 、R 3 、R 0 、R 1 、R 2 、R 3 、R 4 、R 5 And t is correspondingly the same as defined in any one of claims 1 to 3.
5. The method according to claim 4, wherein the catalyst is at least one selected from the group consisting of low-valent titanium, low-valent tungsten, low-valent molybdenum, low-valent zirconium, low-valent vanadium, and low-valent niobium; preferably low-valent titanium;
preferably, the preparation method of the low-valence titanium comprises the following steps: dissolving a titanium-containing reagent and a reducing agent in a solvent A for reduction reaction;
preferably, the preparation method of the low-valence titanium further comprises the following steps: the reduction reaction is carried out in a protective atmosphere, wherein the protective atmosphere is nitrogen and/or argon;
preferably, the titanium-containing reagent is selected from at least one of titanium trichloride, titanium tetrachloride and titanium powder; the reducing agent is selected from K, li, na, zn +CuCl and LiAlH 4 At least one of Mg, mg+hg, li+hg and chlorosilane; the solvent A is tetrahydrofuran and/or dimethyl ether;
preferably, the titanium-containing reagent is titanium tetrachloride; the reducing agent is Zn and CuCl;
preferably, the concentration of the titanium tetrachloride in the solvent A is 0.2-0.7mmol/mL, the concentration of the Zn in the solvent A is 0.3-0.8mmol/mL, and the concentration of the CuCl in the solvent A is 0.02-0.06mmol/mL;
preferably, the molar ratio of the alkenyl compound to the phenyl compound in the synthesis reaction is 1: (1.2-1.6);
preferably, the preparation method further comprises: prior to the synthesis reaction, dissolving the alkenyl compound and phenyl compound in solvent B;
preferably, the solvent B is the same as the solvent a, wherein the volume ratio of the solvent B to the solvent a is 1: (2.5-5);
preferably, the concentration of the alkenyl compound in the solvent B is 0.2-0.5mmol/mL;
preferably, the temperature of the synthesis reaction is-10 ℃ to 0 ℃ or 66 ℃ to 72 ℃; the synthesis reaction time is 2-8h; preferably 3-6h.
6. A sulfonic acid monomer produced by the production process according to claim 4 or 5.
7. Use of a sulphonic acid monomer according to any one of claims 1 to 3 and 6 in an oilfield additive.
8. A copolymer comprising structural units derived from the sulfonic acid monomer of any one of claims 1 to 3 and 6;
preferably, the copolymer further contains structural units derived from one or more monomers of acrylamide, N-isopropylacrylamide, vinylpyrrolidone, acrylic acid, sodium acrylate, acrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid, dimethyldiallylammonium chloride and γ -methacryloxypropyl trimethoxysilane.
9. Use of the copolymer of claim 8 as a fluid loss additive, tackifier, viscosity reducer, cutting agent, inhibitor.
10. A drilling fluid comprising the copolymer of claim 8.
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