CN106366204A - Comb-type polysaccharides compound, preparation method of same, application of same as coating agent, and water-based drilling fluid and application thereof - Google Patents
Comb-type polysaccharides compound, preparation method of same, application of same as coating agent, and water-based drilling fluid and application thereof Download PDFInfo
- Publication number
- CN106366204A CN106366204A CN201610729963.4A CN201610729963A CN106366204A CN 106366204 A CN106366204 A CN 106366204A CN 201610729963 A CN201610729963 A CN 201610729963A CN 106366204 A CN106366204 A CN 106366204A
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- China
- Prior art keywords
- compound
- polysaccharide
- formula
- weight
- polysaccharide compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 157
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 157
- -1 polysaccharides compound Chemical class 0.000 title claims abstract description 157
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 238000005553 drilling Methods 0.000 title claims abstract description 51
- 239000012530 fluid Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 88
- 229920002472 Starch Polymers 0.000 claims abstract description 23
- 235000019698 starch Nutrition 0.000 claims abstract description 22
- 239000008107 starch Substances 0.000 claims abstract description 21
- 229920002678 cellulose Polymers 0.000 claims abstract description 13
- 239000001913 cellulose Substances 0.000 claims abstract description 13
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 9
- 239000000230 xanthan gum Substances 0.000 claims abstract description 8
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 8
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 8
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical class C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- 238000007334 copolymerization reaction Methods 0.000 claims description 22
- 238000006277 sulfonation reaction Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000003125 aqueous solvent Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 150000004676 glycans Chemical class 0.000 claims description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 238000010276 construction Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 15
- 150000003839 salts Chemical class 0.000 abstract description 15
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910000278 bentonite Inorganic materials 0.000 description 7
- 229940092782 bentonite Drugs 0.000 description 7
- 239000000440 bentonite Substances 0.000 description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 7
- 229920002401 polyacrylamide Polymers 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000006184 cosolvent Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
- 229910052601 baryte Inorganic materials 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 229940080314 sodium bentonite Drugs 0.000 description 2
- 229910000280 sodium bentonite Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- NQQRXZOPZBKCNF-NSCUHMNNSA-N (e)-but-2-enamide Chemical compound C\C=C\C(N)=O NQQRXZOPZBKCNF-NSCUHMNNSA-N 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- LPNSCOVIJFIXTJ-UHFFFAOYSA-N 2-methylidenebutanamide Chemical compound CCC(=C)C(N)=O LPNSCOVIJFIXTJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-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
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 240000004922 Vigna radiata Species 0.000 description 1
- 235000010721 Vigna radiata var radiata Nutrition 0.000 description 1
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B13/00—Preparation of cellulose ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明涉及石油工业的钻井领域，具体地，涉及一种梳型多糖类化合物及其制备方法和作为包被剂的应用及水基钻井液及其应用。所述梳型多糖类化合物的主链由磺化多糖类化合物提供，所述梳型多糖类化合物的侧链由下式(1)所示的化合物和式(2)所示的化合物提供，其中，所述磺化多糖类化合物为磺化的淀粉、磺化的纤维素类化合物或磺化的黄原胶。本发明提供的梳型多糖类化合物，通过主链的磺化多糖类化合物和侧链的丙烯酸类和丙烯酰胺类单元的协同作用，能够在钻井液中作为包被剂时发挥良好的包被性能，且还具有优良的抗温性能和抗盐性能。 The invention relates to the field of drilling in the petroleum industry, in particular to a comb-shaped polysaccharide compound and its preparation method, its application as a coating agent, water-based drilling fluid and its application. The main chain of the comb-shaped polysaccharide compound is provided by a sulfonated polysaccharide compound, and the side chain of the comb-shaped polysaccharide compound is composed of a compound shown in the following formula (1) and a compound shown in formula (2) Provided, wherein, the sulfonated polysaccharide compound is sulfonated starch, sulfonated cellulose compound or sulfonated xanthan gum. The comb-shaped polysaccharide compound provided by the present invention, through the synergistic effect of the sulfonated polysaccharide compound of the main chain and the acrylic acid and acrylamide units of the side chain, can play a good coating when used as a coating agent in drilling fluid. It also has excellent temperature resistance and salt resistance.
Description
技术领域technical field
本发明涉及石油工业的钻井领域，具体地，涉及一种梳型多糖类化合物及其制备方法和作为包被剂的应用及水基钻井液及其应用。The invention relates to the field of drilling in the petroleum industry, in particular to a comb-shaped polysaccharide compound and its preparation method, its application as a coating agent, water-based drilling fluid and its application.
背景技术Background technique
包被剂是水基钻井液处理剂中非常重要的一种处理剂，它不仅可以通过吸附作用包被岩屑，防止岩屑分散，利于固控过程中岩屑的排除，同时包被剂对泥页岩等有强抑制作用，阻止其水化膨胀，有利于井壁稳定。此外，在盐水钻井液体系中，包被剂也会起到部分提切、润滑作用，具有多功能性。The coating agent is a very important treatment agent in the water-based drilling fluid treatment agent. It can not only coat cuttings by adsorption, prevent the dispersion of cuttings, and facilitate the removal of cuttings during the solid control process. Mud shale has a strong inhibitory effect, preventing its hydration expansion, which is beneficial to the stability of the borehole wall. In addition, in the brine drilling fluid system, the coating agent can also partially lift and lubricate, and has multiple functions.
高分子量聚丙烯酰胺类聚合物作为常用的包被剂，包被、抑制性突出，但一直存在着抗温、抗盐性不足等缺陷。由于高分子量聚丙烯酰胺分子链为柔性长链，其在高剪切作用下极易降解，导致其分子量降低，从而失去包被性能。将耐温耐盐单体如N-乙烯基吡咯烷酮、2-丙烯酰胺基-2-甲基丙磺酸接枝到聚丙烯酰胺上是较为常用的聚丙烯酰胺类包被剂的改性方法，但引入这些单体后聚合物的分子量会大幅度降低，导致其包被性能下降。High-molecular-weight polyacrylamide polymers, as commonly used coating agents, have outstanding coating and inhibition properties, but have always had defects such as insufficient temperature resistance and salt resistance. Since the molecular chain of high molecular weight polyacrylamide is a flexible long chain, it is easily degraded under high shear, resulting in a decrease in its molecular weight, thereby losing its coating performance. Grafting temperature-resistant and salt-resistant monomers such as N-vinylpyrrolidone and 2-acrylamido-2-methylpropanesulfonic acid onto polyacrylamide is a commonly used modification method for polyacrylamide coating agents. However, the molecular weight of the polymer will be greatly reduced after the introduction of these monomers, resulting in a decrease in its coating performance.
发明内容Contents of the invention
本发明的目的在于针对现有的包被剂难以兼具较好的包被性能、抗温性能和抗盐性能的缺陷，提供了一种具有优良的包被性能、抗温性能和抗盐性能的梳型多糖类化合物及其制备方法和作为包被剂的应用及水基钻井液及其应用。The object of the present invention is to provide a coating agent with excellent coating performance, temperature resistance and salt resistance, aiming at the defect that the existing coating agent is difficult to have good coating performance, temperature resistance and salt resistance. The comb polysaccharide compound and its preparation method and its application as a coating agent and water-based drilling fluid and its application.
为了实现上述目的，本发明提供一种梳型多糖类化合物，所述梳型多糖类化合物的主链由磺化多糖类化合物提供，所述梳型多糖类化合物的侧链由下式(1)所示的化合物和式(2)所示的化合物提供，其中，所述磺化多糖类化合物为磺化的淀粉、磺化的纤维素类化合物或磺化的黄原胶：In order to achieve the above object, the present invention provides a comb-shaped polysaccharide compound, the main chain of the comb-shaped polysaccharide compound is provided by a sulfonated polysaccharide compound, and the side chain of the comb-shaped polysaccharide compound is provided by the following The compound shown in formula (1) and the compound shown in formula (2) are provided, wherein, the sulfonated polysaccharide compound is sulfonated starch, sulfonated cellulose compound or sulfonated xanthan gum:
式(1)式(2) Formula 1) Formula (2)
其中，R1、R1'、R2和R2'各自独立地选自H和C1-C6的烷基。Wherein, R 1 , R 1 ′, R 2 and R 2 ′ are each independently selected from H and C1-C6 alkyl groups.
本发明还提供了一种梳型多糖类化合物的制备方法，该方法包括：The present invention also provides a kind of preparation method of comb polysaccharide compound, this method comprises:
(1)在含水溶剂中，将多糖类化合物与磺化剂进行磺化反应，得到磺化多糖类化合物；(1) In an aqueous solvent, the polysaccharide compound is subjected to a sulfonation reaction with a sulfonating agent to obtain a sulfonated polysaccharide compound;
(2)在含水溶剂中，在接枝共聚催化剂存在下，将磺化多糖类化合物、式(1)所示的化合物和式(2)所示的化合物进行接枝共聚反应；(2) In an aqueous solvent, in the presence of a graft copolymerization catalyst, the compound shown in the sulfonated polysaccharide compound, the formula (1) and the compound shown in the formula (2) is subjected to a graft copolymerization reaction;
其中，所述多糖类化合物为淀粉、纤维素类化合物和黄原胶中的一种或多种；Wherein, the polysaccharide compound is one or more of starch, cellulose compound and xanthan gum;
式(1)式(2) Formula 1) Formula (2)
其中，R1、R1'、R2和R2'各自独立地选自H和C1-C6的烷基。Wherein, R 1 , R 1 ′, R 2 and R 2 ′ are each independently selected from H and C1-C6 alkyl groups.
本发明还提供了上述方法制得的梳型多糖类化合物。The present invention also provides the comb polysaccharide compound prepared by the above method.
本发明还提供了上述梳型多糖类化合物在钻井液中作为包被剂的应用。The present invention also provides the application of the above-mentioned comb polysaccharide compound as a coating agent in drilling fluid.
本发明还提供一种含有上述梳型多糖类化合物作为包被剂的水基钻井液。The present invention also provides a water-based drilling fluid containing the above-mentioned comb polysaccharide compound as a coating agent.
本发明还提供上述水基钻井液在油气钻井中的应用。The present invention also provides the application of the above-mentioned water-based drilling fluid in oil and gas drilling.
本发明提供的梳型多糖类化合物，通过主链的磺化多糖类化合物和侧链的丙烯酸类和丙烯酰胺类单元的协同作用，能够在钻井液中作为包被剂时发挥良好的包被性能，且还具有优良的抗温性能和抗盐性能。特别是，本发明所得的梳型多糖类化合物溶解性好，更适用于水基钻井液。The comb-shaped polysaccharide compound provided by the present invention, through the synergistic effect of the sulfonated polysaccharide compound of the main chain and the acrylic acid and acrylamide units of the side chain, can play a good role in coating when used as a coating agent in drilling fluid. It also has excellent temperature resistance and salt resistance. In particular, the comb-shaped polysaccharide compound obtained by the invention has good solubility and is more suitable for water-based drilling fluid.
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present invention will be described in detail in the detailed description that follows.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明提供一种梳型多糖类化合物，所述梳型多糖类化合物的主链由磺化多糖类化合物提供，所述梳型多糖类化合物的侧链由下式(1)所示的化合物和式(2)所示的化合物提供，其中，所述磺化多糖类化合物为磺化的淀粉、磺化的纤维素类化合物或磺化的黄原胶：The present invention provides a comb-shaped polysaccharide compound, the main chain of the comb-shaped polysaccharide compound is provided by a sulfonated polysaccharide compound, and the side chain of the comb-shaped polysaccharide compound is represented by the following formula (1): The compound shown and the compound shown in formula (2) provide, wherein, the sulfonated polysaccharide compound is sulfonated starch, sulfonated cellulose compound or sulfonated xanthan gum:
式(1)式(2) Formula 1) Formula (2)
其中，R1、R1'、R2和R2'各自独立地选自H和C1-C6的烷基。Wherein, R 1 , R 1 ′, R 2 and R 2 ′ are each independently selected from H and C1-C6 alkyl groups.
根据本发明，所述梳型多糖类化合物可以认为是在磺化多糖类化合物的主链上接枝上由式(1)所示的化合物和式(2)所示的化合物提供的侧链，该侧链可以是式(1)所示的化合物和式(2)所示的化合物共聚链，也可以是分别是式(1)所示的化合物提供的均聚链和和式(2)所示的化合物的均聚链。所述梳型多糖类化合物在用于钻井液作为包被剂时，通过分子链上的极性基团对岩屑的多点吸附作用，有效地将高度分散的岩屑聚并成为大粒径颗粒并在固控过程中除去，发挥优良的包被作用，同时上述梳型多糖类化合物还能够在保证较好的包被作用下获得优良的抗温和抗盐性能。并且，相比于线性的聚合物包被剂来说，本发明的梳型多糖类化合物不仅能够获得更高的包被性能、抗温性能和抗盐性能，还能够获得更好的水溶性，这样便更加适用于水基钻井液。According to the present invention, the comb-shaped polysaccharide compound can be regarded as grafting on the main chain of the sulfonated polysaccharide compound the side compound provided by the compound represented by formula (1) and the compound represented by formula (2). chain, the side chain can be the compound shown in the formula (1) and the compound copolymerized chain shown in the formula (2), also can be respectively the homopoly chain provided by the compound shown in the formula (1) and the formula (2) ) is a homopolymeric chain of the compound shown. When the comb-shaped polysaccharide compound is used as a coating agent in drilling fluid, the highly dispersed cuttings are effectively aggregated into large-grained cuttings through the multi-point adsorption of the polar groups on the molecular chain. Large particles are removed during the solid control process to exert an excellent coating effect. At the same time, the above-mentioned comb-shaped polysaccharides can also obtain excellent temperature and salt resistance properties while ensuring a better coating effect. Moreover, compared with the linear polymer coating agent, the comb polysaccharide compound of the present invention can not only obtain higher coating performance, temperature resistance performance and salt resistance performance, but also can obtain better water solubility , which is more suitable for water-based drilling fluid.
根据本发明，其中，上述C1-C6的烷基例如可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、正己基等。According to the present invention, wherein, the above-mentioned C1-C6 alkyl group can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Isopentyl, n-hexyl, etc.
为了能够更好地发挥所述梳型多糖类化合物作为包被剂的作用，优选情况下，R1、R1'、R2和R2'各自独立地选自H、甲基、乙基、正丙基、异丙基和正丁基。In order to better play the role of the comb polysaccharide compound as a coating agent, preferably, R 1 , R 1 ′, R 2 and R 2 ′ are each independently selected from H, methyl, ethyl , n-propyl, isopropyl and n-butyl.
其中，式(1)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Wherein, the specific example of the compound shown in formula (1) can be one or more of the compounds shown in the following formula, for example:
式(1-1)中：R1和R1'为H(也称作丙烯酰胺)；In formula (1-1): R 1 and R 1 ' are H (also known as acrylamide);
式(1-2)中：R1为甲基，R1'为H(也称作甲基丙烯酰胺)；In formula (1-2): R 1 is methyl, R 1 ' is H (also known as methacrylamide);
式(1-3)中：R1为乙基，R1'为H(也称作乙基丙烯酰胺)；In formula (1-3): R 1 is ethyl, R 1 ' is H (also known as ethylacrylamide);
式(1-4)中：R1为H，R1'为甲基(也称作2-丁烯酰胺)。In formula (1-4): R 1 is H, and R 1 ' is methyl (also known as 2-butenamide).
其中，式(2)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Wherein, the specific example of the compound shown in formula (2) can be for example one or more in the compound shown in the following formula:
式(2-1)中：R2和R2'为H(也称作丙烯酸)；In formula (2-1): R 2 and R 2 ' are H (also known as acrylic acid);
式(2-2)中：R2为甲基，R2'为H(也称作甲基丙烯酸)。In formula (2-2): R 2 is methyl, R 2 ' is H (also called methacrylic acid).
根据本发明，所述磺化多糖类化合物为磺化的淀粉、磺化的纤维素类化合物或磺化的黄原胶。这些磺化的多糖类化合物可以是市售品，也可以采用本发明中下文描述的过程进行制备。可以认为磺化的多糖类化合物是多糖类化合物上形成了一些磺酸基或其它含硫基团的结构，这是本领域的常规认知，本发明在此不再赘述。According to the present invention, the sulfonated polysaccharide compound is sulfonated starch, sulfonated cellulose compound or sulfonated xanthan gum. These sulfonated polysaccharides can be commercially available, or can be prepared by the process described below in the present invention. It can be considered that the sulfonated polysaccharide compound is a structure in which some sulfonic acid groups or other sulfur-containing groups are formed on the polysaccharide compound, which is a common knowledge in the art, and the present invention will not repeat it here.
其中，所述磺化的纤维素类化合物为磺化的羧甲基纤维素、磺化的羟甲基纤维素、磺化的羧乙基纤维素、磺化的羟乙基纤维素、磺化的羟丙基纤维素或磺化的羟丙基甲基纤维素。Wherein, the sulfonated cellulose compound is sulfonated carboxymethyl cellulose, sulfonated hydroxymethyl cellulose, sulfonated carboxyethyl cellulose, sulfonated hydroxyethyl cellulose, sulfonated hydroxypropylcellulose or sulfonated hydroxypropylmethylcellulose.
根据本发明，尽管本发明对磺化后的多糖类化合物上的含硫基团(如磺酸基、硫酸酯基、硫醇基等)的含量没有特别的限定，但是为了能够获得更加适用于包被剂的梳型多糖类化合物，优选地，所述磺化多糖类化合物中，含硫基团的含量为20-35重量％，优选为25-30重量％。According to the present invention, although the content of sulfur-containing groups (such as sulfonic acid groups, sulfate ester groups, thiol groups, etc.) on the sulfonated polysaccharide compounds is not particularly limited, in order to obtain more suitable In the comb polysaccharide compound of the coating agent, preferably, in the sulfonated polysaccharide compound, the content of sulfur-containing groups is 20-35% by weight, preferably 25-30% by weight.
根据本发明，所述梳型多糖类化合物的分子量可以在较宽范围内变动，为了能够获得更加适用于包被剂的梳型多糖类化合物，优选地，所述梳型多糖类化合物的重均分子量为9,000,000-15,000,000g/mol，优选为9,500,000-14,500,000g/mol，更优选为10,000,000-13,500,000g/mol，更进一步优选为12,000,000-13,500,000g/mol。According to the present invention, the molecular weight of the comb-shaped polysaccharide compound can vary within a wide range, in order to obtain a comb-shaped polysaccharide compound that is more suitable for coating agents, preferably, the comb-shaped polysaccharide compound The weight average molecular weight is 9,000,000-15,000,000g/mol, preferably 9,500,000-14,500,000g/mol, more preferably 10,000,000-13,500,000g/mol, even more preferably 12,000,000-13,500,000g/mol.
根据本发明，优选地，所述梳型多糖类化合物中，由式(1)所示的化合物和式(2)所示的化合物提供的结构单元的含量为80-95重量％，优选为85-92重量％，更优选为88-92重量％。当提供侧链的式(1)所示的化合物和式(2)所示的化合物的结构单元和提供主链的磺化多糖类化合物的结构单元满足上述重量比下，能够更好地发挥梳型多糖类化合物中各个基团的协同作用，获得水溶性高，且包被性能、抗温性能和抗盐性能更为优良的梳型多糖类化合物。According to the present invention, preferably, in the comb polysaccharide compound, the content of the structural units provided by the compound represented by formula (1) and the compound represented by formula (2) is 80-95% by weight, preferably 85-92% by weight, more preferably 88-92% by weight. When the structural unit of the compound shown in the formula (1) and the formula (2) that provides the side chain and the structural unit of the sulfonated polysaccharide compound that provides the main chain meet the above weight ratio, it can be used better. The synergistic effect of each group in the comb-shaped polysaccharide compound obtains the comb-shaped polysaccharide compound with high water solubility, better coating performance, temperature resistance performance and salt resistance performance.
根据本发明，尽管式(1)所示的化合物和式(2)所示的化合物提供的结构单元的摩尔比可以在较宽范围内变动，但是优选地，式(1)所示的化合物和式(2)所示的化合物提供的结构单元的摩尔比为1：0.2-1，优选为1：0.2-0.5，更优选为1：0.24-0.4(例如1：0.25-0.33)，更进一步优选为1：0.27-0.33。当式(1)所示的化合物和式(2)所示的化合物提供的结构单元的摩尔比在该范围内时，能够获得更有利于与主链配合发挥包被剂性能的侧链，如上所述，可以认为该侧链是式(1)所示的化合物提供的均聚链和式(2)所示的化合物的均聚链，但是更优选是式(1)所示的化合物和式(2)所示的化合物形成的共聚链，特别是无规线性共聚链。该数个侧链接枝在磺化多糖类化合物上，形成梳型结构，也即形成本发明的梳型多糖类化合物。According to the present invention, although the molar ratio of the structural units provided by the compound shown in formula (1) and the compound shown in formula (2) can vary within a wide range, preferably, the compound shown in formula (1) and The molar ratio of the structural units provided by the compound represented by formula (2) is 1:0.2-1, preferably 1:0.2-0.5, more preferably 1:0.24-0.4 (such as 1:0.25-0.33), even more preferably For 1:0.27-0.33. When the molar ratio of the structural units provided by the compound shown in formula (1) and the compound shown in formula (2) is within this range, it is possible to obtain a side chain that is more conducive to coordinating with the main chain and exerting the performance of the coating agent, as above Said, it can be considered that the side chain is the homopolymeric chain provided by the compound shown in formula (1) and the homopolymeric chain of the compound shown in formula (2), but more preferably the compound shown in formula (1) and the homopolymeric chain of formula Copolymer chains formed by the compounds shown in (2), especially random linear copolymer chains. The several side chains are grafted on the sulfonated polysaccharide compound to form a comb structure, that is, the comb-shaped polysaccharide compound of the present invention.
本发明还提供了一种梳型多糖类化合物的制备方法，该方法包括：The present invention also provides a kind of preparation method of comb polysaccharide compound, this method comprises:
(1)在含水溶剂中，将多糖类化合物与磺化剂进行磺化反应，得到磺化多糖类化合物；(1) In an aqueous solvent, the polysaccharide compound is subjected to a sulfonation reaction with a sulfonating agent to obtain a sulfonated polysaccharide compound;
(2)在含水溶剂中，在接枝共聚催化剂存在下，将磺化多糖类化合物、式(1)所示的化合物和式(2)所示的化合物进行接枝共聚反应；(2) In an aqueous solvent, in the presence of a graft copolymerization catalyst, the compound shown in the sulfonated polysaccharide compound, the formula (1) and the compound shown in the formula (2) is subjected to a graft copolymerization reaction;
其中，所述多糖类化合物为淀粉、纤维素类化合物和黄原胶中的一种或多种；Wherein, the polysaccharide compound is one or more of starch, cellulose compound and xanthan gum;
式(1)式(2) Formula 1) Formula (2)
其中，R1、R1'、R2和R2'各自独立地选自H和C1-C6的烷基。Wherein, R 1 , R 1 ′, R 2 and R 2 ′ are each independently selected from H and C1-C6 alkyl groups.
其中，式(1)所示的化合物和式(2)所示的化合物及其基团如上文中所描述的，在此不再赘述。Wherein, the compound represented by formula (1) and the compound represented by formula (2) and their groups are as described above, and will not be repeated here.
根据本发明，步骤(1)中将通过所述磺化反应提供上文中所描述的磺化多糖类化合物，因此，所述多糖类化合物可以根据所需的磺化多糖类化合物进行选择，即为淀粉、纤维素类化合物和黄原胶中的一种或多种。According to the present invention, the sulfonated polysaccharide compound described above will be provided through the sulfonation reaction in step (1), therefore, the polysaccharide compound can be selected according to the desired sulfonated polysaccharide compound , that is, one or more of starch, cellulose compound and xanthan gum.
根据本发明，所述淀粉的数均分子量通常为2万-200万，其可以为本领域常规的各种天然淀粉，例如土豆淀粉、绿豆淀粉、红薯淀粉、小麦淀粉等中的一种或多种。其中，所述淀粉任选含有其在酸中的分解产物，例如可以含有糊精、麦芽糖及其更低分子量的葡萄糖中的一种或多种。According to the present invention, the number average molecular weight of the starch is generally 20,000-2 million, which can be various natural starches conventional in the art, such as one or more of potato starch, mung bean starch, sweet potato starch, wheat starch, etc. kind. Wherein, the starch may optionally contain its decomposition products in acid, for example, may contain one or more of dextrin, maltose and lower molecular weight glucose.
其中，所述纤维素类化合物为羧甲基纤维素、羟甲基纤维素、羧乙基纤维素、羟乙基纤维素、羟丙基纤维素和羟丙基甲基纤维素中的一种或多种。应当理解的是所述多糖类化合物通常为线性的大分子，可以认为以下所得的磺化后的多糖类化合物也是线性的大分子结构。Wherein, the cellulose compound is one of carboxymethyl cellulose, hydroxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose or more. It should be understood that the polysaccharide compound is generally a linear macromolecule, and it can be considered that the sulfonated polysaccharide compound obtained below is also a linear macromolecular structure.
根据本发明，所述多糖类化合物的分子量可以根据所需的磺化多糖类化合物进行选择，例如为了制备重均分子量为9,000,000-15,000,000g/mol(优选为9,500,000-14,500,000g/mol，更优选为10,000,000-13,500,000g/mol，更进一步优选为12,000,000-13,500,000g/mol)的梳型多糖类化合物，优选地，所述多糖类化合物的重均分子量为100,000-2,000,000g/mol，优选为150,000-1,000,000g/mol，例如为700,000-1,000,000g/mol。According to the present invention, the molecular weight of the polysaccharide compound can be selected according to the desired sulfonated polysaccharide compound, for example, in order to prepare Preferably 10,000,000-13,500,000g/mol, more preferably 12,000,000-13,500,000g/mol) comb polysaccharide compound, preferably, the weight average molecular weight of the polysaccharide compound is 100,000-2,000,000g/mol, preferably 150,000-1,000,000 g/mol, for example 700,000-1,000,000 g/mol.
根据本发明，所述含水溶剂可以是单独的水，也可以是混溶有一些不影响本发明的反应的溶剂(例如为甲醇、乙醇、乙二醇、丙醇、异丙醇等中的一种或多种)的水的混合物，当然优选为水。为了能够制备适用于本发明所需的磺化多糖类化合物，优选地，步骤(1)中，相对于100重量份的所述多糖类化合物，含水溶剂的用量为1000-5000重量份，优选为2000-4000重量份。According to the present invention, described aqueous solvent can be independent water, also can be miscible with some solvents that do not affect the reaction of the present invention (such as one of methanol, ethanol, ethylene glycol, propanol, isopropanol, etc. One or more) of water mixture, of course, preferably water. In order to be able to prepare the sulfonated polysaccharide compound suitable for the present invention, preferably, in step (1), relative to 100 parts by weight of the polysaccharide compound, the amount of the aqueous solvent used is 1000-5000 parts by weight, Preferably it is 2000-4000 parts by weight.
根据本发明，对所述磺化剂并无特别的限定，只要能够得到本发明的磺化多糖类化合物即可，可以采用本领域常规的各种磺化剂，优选地，所述磺化剂为氯磺酸、三氧化硫、1,3-丙磺酸内酯和浓硫酸(浓度例如为90重量％以上，特别是98重量％的浓硫酸)中的一种或多种。所述磺化剂的用量可以在较宽范围内变动，为了能够制得含硫基团的含量为20-35重量％(优选为25-30重量％)的磺化多糖类化合物，优选情况下，相对于100重量份的所述多糖类化合物，所述磺化剂的用量为20-40重量份，优选为25-35重量份，例如为28-30重量份。According to the present invention, the sulfonating agent is not particularly limited, as long as the sulfonated polysaccharide compound of the present invention can be obtained, various conventional sulfonating agents in the field can be used. Preferably, the sulfonating agent The agent is one or more of chlorosulfonic acid, sulfur trioxide, 1,3-propane sultone and concentrated sulfuric acid (concentrated sulfuric acid with a concentration of 90% by weight or more, especially 98% by weight). The amount of the sulfonating agent can be changed within a wide range, in order to obtain a sulfonated polysaccharide compound with a sulfur-containing group content of 20-35% by weight (preferably 25-30% by weight), preferably In general, relative to 100 parts by weight of the polysaccharide compound, the amount of the sulfonating agent used is 20-40 parts by weight, preferably 25-35 parts by weight, such as 28-30 parts by weight.
根据本发明，优选情况下，所述磺化反应的条件包括：温度为50-70℃(优选为55-65℃)，时间为8-20h(优选为10-12h)。According to the present invention, preferably, the conditions of the sulfonation reaction include: a temperature of 50-70°C (preferably 55-65°C), and a time of 8-20h (preferably 10-12h).
根据本发明，为了促进所述多糖类化合物在含水溶剂中的溶解性，上述磺化反应还在助溶剂存在下进行，所述助溶剂例如可以为甲酸、乙酸、乙二酸和丙二酸中的一种或多种。其中，优选地，相对于100重量份的所述多糖类化合物，所述助溶剂的用量为8-20重量份，优选为10-15重量份。According to the present invention, in order to promote the solubility of the polysaccharide compound in the aqueous solvent, the above-mentioned sulfonation reaction is also carried out in the presence of a cosolvent, and the cosolvent can be, for example, formic acid, acetic acid, oxalic acid and malonic acid one or more of. Wherein, preferably, relative to 100 parts by weight of the polysaccharide compound, the amount of the co-solvent is 8-20 parts by weight, preferably 10-15 parts by weight.
根据本发明，上述步骤(1)可以采用先将所述多糖类化合物和含水溶剂混合，而后引入磺化剂和任选的助溶剂混合并进行所述磺化反应的方式。According to the present invention, the above-mentioned step (1) can adopt the method of firstly mixing the polysaccharide compound and the aqueous solvent, and then introducing a sulfonating agent and an optional co-solvent to mix and carry out the sulfonation reaction.
根据本发明，尽管步骤(1)所得的磺化反应的产物不经过任何进一步的处理即可用于步骤(2)中，但是为了能够更有利于所述接枝共聚反应的进行，该步骤(1)还包括将所述磺化反应的产物进行固液分离(例如采用抽滤的方式)并干燥所得固相，从而得到磺化多糖类化合物的过程。According to the present invention, although the product of the sulfonation reaction obtained in step (1) can be used in step (2) without any further treatment, in order to be more conducive to the carrying out of the graft copolymerization reaction, the step (1 ) also includes the process of subjecting the product of the sulfonation reaction to solid-liquid separation (for example, by means of suction filtration) and drying the obtained solid phase, thereby obtaining the sulfonated polysaccharide compound.
根据本发明，步骤(2)中通过将磺化多糖类化合物、式(1)所示的化合物和式(2)所示的化合物进行接枝共聚反应，即可在磺化多糖类化合物上接枝上式(1)所示的化合物和式(2)所示的化合物形成的聚合物侧链，可以认为这里的磺化多糖类化合物在此并未发生自身聚合反应，仅是在步骤(1)所得的磺化多糖类化合物基础上，以该磺化多糖类化合物为主链再通过步骤(2)的接枝共聚反应接枝上式(1)所示的化合物和式(2)所示的化合物形成的聚合物侧链。尽管所述式(1)所示的化合物和式(2)所示的化合物的用量可以根据所需的梳型多糖类化合物上的侧链情况进行适当地选择，优选情况下，相对于100重量份的所述磺化多糖类化合物，式(1)所示的化合物和式(2)所示的化合物的总用量为500-1500重量份，优选为800-1000重量份，更优选为850-950重量份。为了能够获得能够与主链更好地配合的侧链，优选地，式(1)所示的化合物和式(2)所示的化合物的用量的摩尔比为1：0.2-1，优选为1：0.2-0.5，更优选为1：0.24-0.4(例如1：0.25-0.33)，更进一步优选为1：0.27-0.33。According to the present invention, in step (2), by performing graft copolymerization reaction on the sulfonated polysaccharide compound, the compound represented by the formula (1) and the compound represented by the formula (2), the sulfonated polysaccharide compound can be The polymer side chain formed by grafting the compound shown in formula (1) and the compound shown in formula (2) above, it can be considered that the sulfonated polysaccharide compound does not undergo self-polymerization here, only in On the basis of the sulfonated polysaccharide compound obtained in step (1), the compound shown in formula (1) and formula The polymer side chain formed by the compound shown in (2). Although the amount of the compound shown in the formula (1) and the compound shown in the formula (2) can be properly selected according to the side chain situation on the desired comb polysaccharide compound, preferably, relative to 100 The total amount of the sulfonated polysaccharide compound in parts by weight, the compound shown in formula (1) and the compound shown in formula (2) is 500-1500 parts by weight, preferably 800-1000 parts by weight, more preferably 850-950 parts by weight. In order to obtain a side chain that can better coordinate with the main chain, preferably, the molar ratio of the compound shown in formula (1) and the compound shown in formula (2) is 1:0.2-1, preferably 1 : 0.2-0.5, more preferably 1: 0.24-0.4 (eg 1: 0.25-0.33), still more preferably 1: 0.27-0.33.
根据本发明，步骤(2)中的含水溶剂如上文所述的进行选择，而为了能够制备适用于本发明所需的梳型多糖类化合物，优选地，步骤(2)中，相对于100重量份的所述磺化多糖类化合物，含水溶剂的用量为5000-10000重量份，优选为6000-9000重量份，更优选为6500-8000重量份。According to the present invention, the aqueous solvent in step (2) is selected as described above, and in order to be able to prepare the required comb polysaccharide compound suitable for the present invention, preferably, in step (2), relative to 100 For the sulfonated polysaccharide compound in parts by weight, the amount of aqueous solvent used is 5000-10000 parts by weight, preferably 6000-9000 parts by weight, more preferably 6500-8000 parts by weight.
根据本发明，所述接枝共聚催化剂可以采用本领域常规的用于接枝共聚的催化剂，为了更好地适用于本发明的磺化多糖类化合物、式(1)所示的化合物和式(2)所示的化合物进行的接枝共聚反应，优选情况下，所述接枝共聚催化剂为高价金属化合物和过硫酸盐中的一种或多种。其中，所述高价金属化合物例如可以是四价铈的化合物、二价钴的化合物、五价钒的化合物、三价铁的化合物等中的一种或多种，优选为硝酸铈铵、三氯化铁、四(4-羧基苯基)钴卟啉和乙酰丙酮钒中的一种或多种。优选地，所述过硫酸盐为过硫酸铵、过硫酸钠和过硫酸钾中的一种或多种。所述接枝共聚催化剂的用量可以根据所需的梳型多糖类化合物进行调整，优选地，相对于100重量份的所述磺化多糖类化合物，所述接枝共聚催化剂的用量为0.1-2重量份，优选为0.2-1重量份，更优选为0.2-0.5重量份。According to the present invention, the graft copolymerization catalyst can be a conventional catalyst for graft copolymerization in the art, in order to be better applicable to the sulfonated polysaccharide compound of the present invention, the compound shown in formula (1) and the formula (2) The graft copolymerization reaction carried out by the compound shown in (2), preferably, the graft copolymerization catalyst is one or more of a high-valent metal compound and a persulfate. Wherein, the high-valent metal compound can be, for example, one or more of tetravalent cerium compounds, divalent cobalt compounds, pentavalent vanadium compounds, ferric iron compounds, etc., preferably cerium ammonium nitrate, trichloride One or more of iron oxide, tetrakis(4-carboxyphenyl) cobalt porphyrin and vanadium acetylacetonate. Preferably, the persulfate is one or more of ammonium persulfate, sodium persulfate and potassium persulfate. The amount of the graft copolymerization catalyst can be adjusted according to the desired comb polysaccharide compound, preferably, relative to 100 parts by weight of the sulfonated polysaccharide compound, the amount of the graft copolymerization catalyst is 0.1 -2 parts by weight, preferably 0.2-1 parts by weight, more preferably 0.2-0.5 parts by weight.
根据本发明，优选情况下，步骤(2)中，所述接枝共聚反应的条件包括：温度为10-40℃(优选为20-35℃，例如为25-35℃)，时间为10-30h(优选为16-25h，例如为20-24h)。According to the present invention, preferably, in step (2), the conditions of the graft copolymerization reaction include: the temperature is 10-40°C (preferably 20-35°C, such as 25-35°C), and the time is 10- 30h (preferably 16-25h, eg 20-24h).
根据本发明，为了能够保持催化剂等的活性，该方法还可以包括：使得所述接枝共聚反应在惰性气氛中进行，例如可以向体系中通入氮气、氦气、氖气、氩气等一种或多种并置换其中的气氛(该过程例如可以进行5-300min，主要是除氧)。According to the present invention, in order to be able to maintain the activity of the catalyst, the method may also include: making the graft copolymerization reaction to be carried out in an inert atmosphere, for example, nitrogen, helium, neon, argon, etc. may be introduced into the system. One or more and replace the atmosphere therein (this process, for example, can be carried out for 5-300min, mainly to remove oxygen).
根据本发明，为了能够更为充分地反应，步骤(2)可以采用先将磺化多糖类化合物和含水溶剂混合，而后引入式(1)所示的化合物和式(2)所示的化合物进行混合，并在通入氮气、氦气、氖气、氩气等一种或多种并置换其中的气氛后，引入所述接枝共聚催化剂进行所述接枝共聚反应。According to the present invention, in order to be able to react more fully, step (2) can be used to mix the sulfonated polysaccharide compound and the aqueous solvent first, and then introduce the compound shown in formula (1) and the compound shown in formula (2) Mixing is carried out, and after introducing one or more of nitrogen, helium, neon, argon and the like to replace the atmosphere therein, the graft copolymerization catalyst is introduced to carry out the graft copolymerization reaction.
根据本发明，该方法还可以包括将所述接枝共聚反应的产物进行干燥，从而得到所述梳型多糖类化合物。According to the present invention, the method may further include drying the product of the graft copolymerization reaction, so as to obtain the comb-shaped polysaccharide compound.
本发明还提供了上述方法制得的梳型多糖类化合物。尽管本发明没有特别的限定，但是该梳型多糖类化合物可以认为是上文中所介绍的梳型多糖类化合物中的一种，或者多种梳型多糖类化合物的混合物。当然，应当理解的是，上述方法所制备的梳型多糖类化合物通常是指上述方法未经过提纯的直接产物，尽管这样的产物可能是多种梳型多糖类化合物的混合物，但是本发明也将这样的情况包括在本发明的范围内。The present invention also provides the comb polysaccharide compound prepared by the above method. Although the present invention is not particularly limited, the comb polysaccharide compound can be regarded as one of the comb polysaccharide compounds described above, or a mixture of multiple comb polysaccharide compounds. Certainly, it should be understood that the comb polysaccharide compound prepared by the above method usually refers to the direct product without purification of the above method, although such product may be a mixture of multiple comb polysaccharide compounds, but the present invention Such cases are also included in the scope of the present invention.
本发明还提供了上述梳型多糖类化合物在钻井液中作为包被剂的应用。The present invention also provides the application of the above-mentioned comb polysaccharide compound as a coating agent in drilling fluid.
本发明还提供一种含有上述梳型多糖类化合物作为包被剂的水基钻井液。The present invention also provides a water-based drilling fluid containing the above-mentioned comb polysaccharide compound as a coating agent.
本发明提供的梳型多糖类化合物，通过主链的磺化多糖类化合物和侧链的丙烯酸类和丙烯酰胺类单元的协同作用，能够在钻井液中作为包被剂时发挥良好的包被性能，且还具有优良的抗温性能和抗盐性能。特别是，本发明所得的梳型多糖类化合物溶解性好，更适用于水基钻井液。本发明对该梳型多糖类化合物的含量并无特别的限定，可以根据地层情况进行适当地调整，优选地，相对于100重量份的水基钻井液中的水，所述梳型多糖类化合物的含量为0.2-2重量份，优选为0.3-1.5重量份，例如0.5-1重量份。The comb-shaped polysaccharide compound provided by the present invention, through the synergistic effect of the sulfonated polysaccharide compound of the main chain and the acrylic acid and acrylamide units of the side chain, can play a good role in coating when used as a coating agent in drilling fluid. It also has excellent temperature resistance and salt resistance. In particular, the comb-shaped polysaccharide compound obtained by the invention has good solubility and is more suitable for water-based drilling fluid. The content of the comb polysaccharide compound is not particularly limited in the present invention, and can be appropriately adjusted according to formation conditions. Preferably, relative to the water in 100 parts by weight of water-based drilling fluid, the comb polysaccharide The content of the quasi-compound is 0.2-2 parts by weight, preferably 0.3-1.5 parts by weight, such as 0.5-1 part by weight.
根据本发明，除了水和上述的共聚物以外，所述水基钻井液还可以含有作为水基钻井液的其他添加剂，例如，可以含有膨润土、碱度调节剂和加重剂等中的一种或多种。According to the present invention, in addition to water and the above-mentioned copolymer, the water-based drilling fluid can also contain other additives as water-based drilling fluid, for example, can contain one or more of bentonite, alkalinity regulator and weighting agent, etc. Various.
其中，所述膨润土是指以蒙脱石为主要矿物成分的粘土，其具有赋予钻井液粘切力和滤失造壁性的作用，例如可以为钠基膨润土和/或钙基膨润土，优选为钠基膨润土。相对于100重量份的所述钻井液中的水，优选地，所述膨润土的含量为2-4重量份，更优选为3-4重量份。Wherein, the bentonite refers to clay with montmorillonite as the main mineral component, which has the effect of imparting drilling fluid with shear force and fluid loss wall-building properties, such as sodium-based bentonite and/or calcium-based bentonite, preferably Sodium bentonite. Relative to 100 parts by weight of water in the drilling fluid, preferably, the content of the bentonite is 2-4 parts by weight, more preferably 3-4 parts by weight.
其中，所述碱度调节剂具有提高膨润土造浆率、调节钻井液pH值的作用，例如可以为Na2CO3。优选地，相对于100重量份的所述水基钻井液中的水，所述碱度调节剂的含量为0.2-0.4重量份。Wherein, the alkalinity regulator has the function of increasing the slurrying rate of bentonite and adjusting the pH value of the drilling fluid, for example, it may be Na 2 CO 3 . Preferably, relative to 100 parts by weight of water in the water-based drilling fluid, the content of the alkalinity regulator is 0.2-0.4 parts by weight.
其中，所述加重剂的作用为调节钻井液的密度达到所需密度，例如可以为重晶石(例如可以为硫酸钡含量在90重量％以上的重晶石)等。优选地，相对于100重量份的所述钻井液中的水相，所述加重剂的用量为200-300重量份。Wherein, the function of the weighting agent is to adjust the density of the drilling fluid to the required density, for example, it can be barite (for example, it can be barite with barium sulfate content above 90% by weight) and the like. Preferably, relative to 100 parts by weight of the water phase in the drilling fluid, the weighting agent is used in an amount of 200-300 parts by weight.
上述添加剂为的各种物质可以是市售品，也可以根据本领域常规的方法制得，这里不再赘述。The various substances of the above additives can be commercially available, or can be prepared according to conventional methods in the art, and will not be repeated here.
本发明还提供了上述水基钻井液在油气钻井中的应用。The present invention also provides the application of the above-mentioned water-based drilling fluid in oil and gas drilling.
本发明提供的梳型多糖类化合物能够快速地溶于水中，特别适用于水基钻井液，且具有优良的包被性能、抗温性能和抗盐性能。The comb-shaped polysaccharide compound provided by the invention can be quickly dissolved in water, is especially suitable for water-based drilling fluid, and has excellent coating performance, temperature resistance performance and salt resistance performance.
以下将通过实施例对本发明进行详细描述。The present invention will be described in detail below by way of examples.
以下实施例和对比例中：In the following examples and comparative examples:
由式(1)所示的化合物和式(2)所示的化合物提供的结构单元的含量是指以梳型多糖类化合物的总重量为基准，式(1)所示的化合物和式(2)所示的化合物提供的结构单元所占的含量，可以认为是侧链占梳型多糖类化合物的百分重量。The content of the structural unit provided by the compound shown in the formula (1) and the compound shown in the formula (2) refers to the total weight of the comb polysaccharide compound as a basis, the compound shown in the formula (1) and the formula ( 2) The content of the structural units provided by the compounds shown can be considered as the percentage weight of the side chains in the comb polysaccharide compound.
实施例1Example 1
本实施例用于说明本发明的梳型多糖类化合物及其制备方法和包被剂。This example is used to illustrate the comb polysaccharide compound of the present invention, its preparation method and coating agent.
(1)将100g的淀粉(购自萨恩化学技术(上海)有限公司，分子量为1,000,000g/mol)溶于3000g的水中，并加入12g的乙酸和30g的氯磺酸，搅拌均匀后，于60℃下反应12h；将所得产物进行抽滤，并干燥所得固体，从而得到磺化淀粉SS-1。经红外核磁鉴定，该磺化淀粉中含硫基团的含量为28.5重量％；(1) 100g of starch (purchased from Sarn Chemical Technology (Shanghai) Co., Ltd., molecular weight of 1,000,000g/mol) was dissolved in 3000g of water, and 12g of acetic acid and 30g of chlorosulfonic acid were added, after stirring evenly, in React at 60°C for 12 hours; suction filter the obtained product, and dry the obtained solid to obtain sulfonated starch SS-1. According to infrared nuclear magnetic identification, the content of sulfur-containing groups in the sulfonated starch is 28.5% by weight;
(2)将100g的磺化淀粉SS-1溶于7000g的水中，并加入700g的丙烯酰胺和200g的丙烯酸，搅拌均匀后通氮气15min，然后加入0.2g的硝酸铈铵，并于25℃下反应24h，从而将所得产物进行干燥、粉碎，得到梳型多糖类化合物，即为包被剂C1。该梳型多糖类化合物的重均分子量为13,500,000g/mol，其中，经红外核磁鉴定，形成梳型多糖类化合物侧链的丙烯酰胺和丙烯酸提供的结构单元的摩尔比为1：0.27，由丙烯酰胺和丙烯酸提供的结构单元的含量为90重量％。(2) Dissolve 100g of sulfonated starch SS-1 in 7000g of water, add 700g of acrylamide and 200g of acrylic acid, stir well, and pass nitrogen gas for 15min, then add 0.2g of cerium ammonium nitrate, and put it under 25°C After reacting for 24 hours, the obtained product was dried and pulverized to obtain a comb-shaped polysaccharide compound, which is the coating agent C1. The weight-average molecular weight of the comb-shaped polysaccharide compound is 13,500,000 g/mol, wherein, through infrared nuclear magnetic identification, the molar ratio of the structural units provided by acrylamide and acrylic acid forming the side chain of the comb-shaped polysaccharide compound is 1:0.27, The content of structural units provided by acrylamide and acrylic acid was 90% by weight.
实施例2Example 2
本实施例用于说明本发明的梳型多糖类化合物及其制备方法和包被剂。This example is used to illustrate the comb polysaccharide compound of the present invention, its preparation method and coating agent.
(1)将100g的羧甲基纤维素(购自萨恩化学技术(上海)有限公司，分子量为700,000g/mol)溶于2000g的水中，并加入12g的乙酸和30g的氯磺酸，搅拌均匀后，于55℃下反应10h；将所得产物进行抽滤，并干燥所得固体，从而得到磺化羧甲基纤维素SC-1。经红外核磁鉴定，该磺化羧甲基纤维素中含硫基团的含量为29.1重量％；(1) Dissolve 100g of carboxymethylcellulose (purchased from Sarn Chemical Technology (Shanghai) Co., Ltd., molecular weight is 700,000g/mol) in 2000g of water, and add 12g of acetic acid and 30g of chlorosulfonic acid, stir After uniformity, react at 55° C. for 10 h; filter the obtained product with suction, and dry the obtained solid to obtain sulfonated carboxymethylcellulose SC-1. According to infrared NMR identification, the content of sulfur-containing groups in the sulfonated carboxymethyl cellulose is 29.1% by weight;
(2)将100g的磺化羧甲基纤维素SC-1溶于8000g的水中，并加入710g的丙烯酰胺和240g的丙烯酸，搅拌均匀后通氮气20min，然后加入0.5g的过硫酸铵，并于25℃下反应22h，从而将所得产物进行干燥、粉碎，得到梳型多糖类化合物，即为包被剂C2。该梳型多糖类化合物的重均分子量为12,500,000g/mol，其中，经红外核磁鉴定，形成梳型多糖类化合物侧链的丙烯酰胺和丙烯酸提供的结构单元的摩尔比为1：0.3，由丙烯酰胺和丙烯酸提供的结构单元的含量为90.5重量％。(2) 100g of sulfonated carboxymethyl cellulose SC-1 was dissolved in 8000g of water, and 710g of acrylamide and 240g of acrylic acid were added, stirred evenly, followed by nitrogen gas for 20min, then 0.5g of ammonium persulfate was added, and React at 25° C. for 22 hours to dry and pulverize the obtained product to obtain a comb-shaped polysaccharide compound, which is the coating agent C2. The weight-average molecular weight of the comb-shaped polysaccharide compound is 12,500,000 g/mol, wherein, as identified by infrared nuclear magnetic resonance, the molar ratio of the structural units provided by acrylamide and acrylic acid forming the side chain of the comb-shaped polysaccharide compound is 1:0.3, The content of structural units provided by acrylamide and acrylic acid was 90.5% by weight.
实施例3Example 3
本实施例用于说明本发明的梳型多糖类化合物及其制备方法和包被剂。This example is used to illustrate the comb polysaccharide compound of the present invention, its preparation method and coating agent.
(1)将100g的羟丙基甲基纤维素(购自萨恩化学技术(上海)有限公司，分子量为150,000g/mol)溶于2000g的水中，并加入15g的乙酸和28g的三氧化硫，搅拌均匀后，于55℃下反应10h；将所得产物进行抽滤，并干燥所得固体，从而得到磺化羟丙基甲基纤维素SC-2。经红外核磁鉴定，该磺化羟丙基甲基纤维素中含硫基团的含量为25.6重量％；(1) 100g of hydroxypropyl methylcellulose (purchased from Sann Chemical Technology (Shanghai) Co., Ltd., molecular weight of 150,000g/mol) was dissolved in 2000g of water, and 15g of acetic acid and 28g of sulfur trioxide were added , after stirring evenly, react at 55° C. for 10 h; filter the obtained product with suction, and dry the obtained solid to obtain sulfonated hydroxypropylmethylcellulose SC-2. According to infrared NMR identification, the content of sulfur-containing groups in the sulfonated hydroxypropyl methylcellulose is 25.6% by weight;
(2)将100g的磺化羟丙基甲基纤维素SC-2溶于6500g的水中，并加入720g的甲基丙烯酰胺和230g的甲基丙烯酸，搅拌均匀后通氮气10min，然后加入0.5g的过硫酸铵，并于30℃下反应20h，从而将所得产物进行干燥、粉碎，得到梳型多糖类化合物，即为包被剂C3。该梳型多糖类化合物的重均分子量为12,000,000g/mol，其中，经红外核磁鉴定，形成梳型多糖类化合物侧链的甲基丙烯酰胺和甲基丙烯酸提供的结构单元的摩尔比为1：0.31，由甲基丙烯酰胺和甲基丙烯酸提供的结构单元的含量为90.5重量％。(2) Dissolve 100g of sulfonated hydroxypropylmethyl cellulose SC-2 in 6500g of water, add 720g of methacrylamide and 230g of methacrylic acid, stir well and pass nitrogen gas for 10min, then add 0.5g ammonium persulfate, and reacted at 30°C for 20 hours, so that the obtained product was dried and pulverized to obtain a comb-shaped polysaccharide compound, which is the coating agent C3. The weight-average molecular weight of the comb-shaped polysaccharide compound is 12,000,000g/mol, wherein, through infrared nuclear magnetic identification, the molar ratio of the structural unit provided by the methacrylamide and methacrylic acid forming the side chain of the comb-shaped polysaccharide compound is: 1:0.31, the content of the structural unit provided by methacrylamide and methacrylic acid was 90.5% by weight.
实施例4Example 4
本实施例用于说明本发明的梳型多糖类化合物及其制备方法和包被剂。This example is used to illustrate the comb polysaccharide compound of the present invention, its preparation method and coating agent.
(1)根据实施例1的步骤(1)制备得到磺化淀粉SS-1；(1) Prepare sulfonated starch SS-1 according to the step (1) of Example 1;
(2)根据实施例1的步骤(2)，不同的是，采用的丙烯酰胺的用量为620g，丙烯酸的用量为180g，从而最终得到梳型多糖类化合物，即为包被剂C4。该梳型多糖类化合物的重均分子量为9,500,000g/mol，其中，经红外核磁鉴定，形成梳型多糖类化合物侧链的丙烯酰胺和丙烯酸提供的结构单元的摩尔比为1：0.26，由丙烯酰胺和丙烯酸提供的结构单元的含量为88.9重量％。(2) According to step (2) of Example 1, the difference is that the amount of acrylamide used is 620g, and the amount of acrylic acid used is 180g, so as to finally obtain the comb-shaped polysaccharide compound, which is the coating agent C4. The weight-average molecular weight of the comb-shaped polysaccharide compound is 9,500,000 g/mol, wherein, as identified by infrared nuclear magnetic resonance, the molar ratio of the structural units provided by acrylamide and acrylic acid forming the side chain of the comb-shaped polysaccharide compound is 1:0.26, The content of structural units provided by acrylamide and acrylic acid was 88.9% by weight.
实施例5Example 5
本实施例用于说明本发明的梳型多糖类化合物及其制备方法和包被剂。This example is used to illustrate the comb polysaccharide compound of the present invention, its preparation method and coating agent.
(1)根据实施例1的步骤(1)制备得到磺化淀粉SS-1；(1) Prepare sulfonated starch SS-1 according to the step (1) of Example 1;
(2)根据实施例1的步骤(2)，不同的是，采用的丙烯酰胺的用量为880g，丙烯酸的用量为220g，从而最终得到梳型多糖类化合物，即为包被剂C5。该梳型多糖类化合物的重均分子量为14,500,000g/mol，其中，经红外核磁鉴定，形成梳型多糖类化合物侧链的丙烯酰胺和丙烯酸提供的结构单元的摩尔比为1：0.24，由丙烯酰胺和丙烯酸提供的结构单元的含量为91.7重量％。(2) According to step (2) of Example 1, the difference is that the amount of acrylamide used is 880g, and the amount of acrylic acid used is 220g, so as to finally obtain the comb-shaped polysaccharide compound, which is the coating agent C5. The weight-average molecular weight of the comb-shaped polysaccharide compound is 14,500,000 g/mol, wherein, as identified by infrared nuclear magnetic resonance, the molar ratio of the structural units provided by acrylamide and acrylic acid forming the side chain of the comb-shaped polysaccharide compound is 1:0.24, The content of structural units provided by acrylamide and acrylic acid was 91.7% by weight.
对比例1Comparative example 1
将实施例1的步骤(1)所得的磺化淀粉SS-1作为包被剂DC1。The sulfonated starch SS-1 obtained in step (1) of Example 1 was used as coating agent DC1.
对比例2Comparative example 2
(1)根据实施例1的步骤(1)制备得到磺化淀粉SS-1；(1) Prepare sulfonated starch SS-1 according to the step (1) of Example 1;
(2)根据实施例1的步骤(2)，不同的是，不采用丙烯酸，且将丙烯酰胺的用量增加至900g，从而最终得到梳型多糖类化合物，即为包被剂DC2。该梳型多糖类化合物的重均分子量为14,000,000g/mol，其中，经红外核磁鉴定，该梳型多糖类化合物中的侧链仅由丙烯酰胺提供，且由丙烯酰胺提供的结构单元的含量为90重量％。(2) According to step (2) of Example 1, the difference is that acrylic acid is not used, and the amount of acrylamide is increased to 900 g, so as to finally obtain a comb-shaped polysaccharide compound, which is the coating agent DC2. The weight-average molecular weight of the comb-shaped polysaccharide compound is 14,000,000 g/mol, wherein, as identified by infrared nuclear magnetic resonance, the side chains in the comb-shaped polysaccharide compound are only provided by acrylamide, and the number of structural units provided by acrylamide The content is 90% by weight.
对比例3Comparative example 3
(1)根据实施例1的步骤(1)制备得到磺化淀粉SS-1；(1) Prepare sulfonated starch SS-1 according to the step (1) of Example 1;
(2)根据实施例1的步骤(2)，不同的是，不采用丙烯酰胺，且将丙烯酸的用量增加至900g，从而最终得到梳型多糖类化合物，即为包被剂DC3。该梳型多糖类化合物的重均分子量为4,200,000g/mol，其中，经红外核磁鉴定，该梳型多糖类化合物中的侧链仅由丙烯酸提供，且由丙烯酸提供的结构单元的含量为90重量％。(2) According to step (2) of Example 1, the difference is that acrylamide is not used, and the amount of acrylic acid is increased to 900g, so as to finally obtain a comb-shaped polysaccharide compound, which is the coating agent DC3. The weight-average molecular weight of the comb-shaped polysaccharide compound is 4,200,000g/mol, wherein, through infrared nuclear magnetic identification, the side chain in the comb-shaped polysaccharide compound is only provided by acrylic acid, and the content of structural units provided by acrylic acid is 90% by weight.
对比例4Comparative example 4
将购自天润化工公司AB1000牌号的重均分子量为10,600,000g/mol的聚丙烯酰胺作为包被剂DC4。Polyacrylamide with a weight average molecular weight of 10,600,000 g/mol purchased from Tianrun Chemical Company AB1000 was used as coating agent DC4.
测试例1test case 1
本测试例用于说明本发明的钻井液。This test example is used to illustrate the drilling fluid of the present invention.
基础钻井液Y：100重量份的水，3重量份的钠基膨润土(购自潍坊华维膨润土技术研究中心)，0.3重量份的Na2CO3。Basic drilling fluid Y: 100 parts by weight of water, 3 parts by weight of sodium bentonite (purchased from Weifang Huawei Bentonite Technology Research Center), 0.3 parts by weight of Na 2 CO 3 .
在室温(约25℃)下，分别将0.4重量份的上述包被剂C1-C5和DC1-DC4溶解于上述基础钻井液Y中，从而制得钻井液Y1-Y5和钻井液DY1-DY4，其中，上述包被剂C1-C5和DC4的溶解耗时如下表1所示：At room temperature (about 25° C.), 0.4 parts by weight of the above-mentioned coating agents C1-C5 and DC1-DC4 were dissolved in the above-mentioned basic drilling fluid Y, thereby preparing drilling fluids Y1-Y5 and drilling fluids DY1-DY4, Among them, the dissolution time consumption of the above-mentioned coating agents C1-C5 and DC4 is shown in Table 1 below:
表1Table 1
通过表1可以看出，本发明的包被剂C1-C5的溶解时间同比未引入磺化多糖的聚丙烯酰胺包被剂DC4至少降低5min，说明本发明的包被剂具有更快的溶解速度。It can be seen from Table 1 that the dissolution time of the coating agent C1-C5 of the present invention is at least 5 min lower than that of the polyacrylamide coating agent DC4 without introducing sulfonated polysaccharide, indicating that the coating agent of the present invention has a faster dissolution rate .
测试例2test case 2
分别对上述钻井液的流变性能抗温性能进行测试，即分别测量上述钻井液体系在老化前和150℃老化16h后在室温下的表观粘度(AV)、塑性粘度(PV)、动切力(YP)、初终切(G10”/10’)；结果见表2所示，其中：The rheological properties and temperature resistance of the above drilling fluids were tested respectively, that is, the apparent viscosity (AV), plastic viscosity (PV), dynamic shear Force (YP), initial and final cut (G10”/10’); the results are shown in Table 2, where:
表观粘度(AV)是采用范式六速粘度计根据国家标准GB/T29170-2012中规定的方法进行测量的，单位为mPa·s， Apparent viscosity (AV) is measured by a paradigm six-speed viscometer according to the method specified in the national standard GB/T29170-2012, and the unit is mPa s,
塑性粘度(PV)是采用范式六速粘度计根据国家标准GB/T29170-2012中规定的方法进行测量的，单位为mPa·s，PV＝θ600-θ300。The plastic viscosity (PV) is measured by a Paradigm six-speed viscometer according to the method specified in the national standard GB/T29170-2012, the unit is mPa·s, PV=θ 600 -θ 300 .
动切力(YP)是采用范式六速粘度计根据国家标准GB/T29170-2012中规定的方法进行测量的，YP＝0.511×(2×φ300-φ600)，单位为Pa。The dynamic shear force (YP) is measured with a six-speed viscometer according to the method specified in the national standard GB/T29170-2012, YP=0.511×(2×φ300-φ600), the unit is Pa.
初终切(G10”/10’)是根据范式六速粘度计根据国家标准GB/T29170-2012中规定的方法进行测量的，单位为Pa/Pa。The initial and final cut (G10”/10’) is measured with a six-speed viscometer according to the method specified in the national standard GB/T29170-2012, and the unit is Pa/Pa.
表2Table 2
通过表2可以看出，本发明的包被剂具有良好的增粘、提切效果，加入本发明的包被剂的钻井液在表2中的表观粘度、动切力和静切力均有明显增长，且在150℃热滚后，钻井液仍可以维持较好的粘度与切力，说明本发明的包被剂具有良好的抗温性能，综合性能优于对比例。As can be seen from Table 2, the coating agent of the present invention has good viscosity-increasing and shearing effects, and the apparent viscosity, dynamic shear force and static shear force of the drilling fluid added to the coating agent of the present invention in Table 2 are all equal. There is an obvious increase, and after hot rolling at 150°C, the drilling fluid can still maintain a good viscosity and shear force, which shows that the coating agent of the present invention has good temperature resistance, and the comprehensive performance is better than that of the comparative example.
测试例3Test case 3
盐水Y'：100重量份的水，10重量份的NaCl。Salt water Y': 100 parts by weight of water, 10 parts by weight of NaCl.
分别将0.4重量份的上述包被剂C1-C5和DC1-DC4溶解于上述盐水Y'中，从而制得钻井液Y'1-Y'5和钻井液DY'1-DY'4。0.4 parts by weight of the above-mentioned coating agents C1-C5 and DC1-DC4 were respectively dissolved in the above-mentioned brine Y' to prepare drilling fluids Y'1-Y'5 and drilling fluids DY'1-DY'4.
根据测试例2所述的方法，分别测量上述钻井液Y'1-Y'5和钻井液DY'1-DY'4的表观粘度(AV)、塑性粘度(PV)、动切力(YP)、初终切(G10”/10’)；结果见表3所示，其中：According to the method described in test example 2, measure the apparent viscosity (AV), plastic viscosity (PV), dynamic shear force (YP) of above-mentioned drilling fluid Y'1-Y'5 and drilling fluid DY'1-DY'4 respectively. ), initial and final cut (G10”/10’); the results are shown in Table 3, where:
表3table 3
通过表3可以看出，本发明的包被剂C1-C5在盐水中仍具有明显的增粘、提切作用，说明受到盐的影响较小，相比于对比例来说具有更好的抗盐性能。As can be seen from Table 3, the coating agent C1-C5 of the present invention still has obvious viscosity-increasing and cutting effects in salt water, indicating that it is less affected by salt and has better anti-corrosion properties than the comparative examples. salt properties.
测试例4Test case 4
热滚回收率的主要步骤如下：在老化罐加入350mL试液(分别是水，水和以上包被剂的混合液，这里的水采用的是自来水)，称取5-10目泥页岩岩屑50g，在120℃的滚子炉中，滚动分散16h；然后用40目筛将回收岩样在水中筛洗干净，将筛余岩样放入表面皿中，在105℃烘箱中烘干至恒重；称重，由下式计算热滚回收率(结果见表4)：The main steps of hot rolling recovery rate are as follows: add 350mL test solution (respectively water, water and the mixture of the above coating agent, the water here is tap water) into the aging tank, weigh 5-10 mesh shale rock Roll and disperse 50g of crumbs in a roller furnace at 120°C for 16 hours; then use a 40-mesh sieve to wash the recovered rock samples in water, put the remaining rock samples into a watch glass, and dry them in an oven at 105°C until Constant weight; Weigh, calculate the hot roll recovery rate by the following formula (results are shown in Table 4):
S＝M/50×100％S=M/50×100%
式中：S—40目筛后的回收率，％；M—40目筛的筛余量，g。In the formula: S—the recovery rate after 40 mesh sieve, %; M—the sieve residue of 40 mesh sieve, g.
表4Table 4
通过表4可以看出，实施例在0.5％加量下即能有效地发挥包被作用，增加岩屑的滚动回收率，效果优于对比例；将加量提升至1％后，岩屑在实施例水溶液中的滚动回收率可以达到74％，甚至高达81.1％，而线性聚丙烯酰胺包被剂DC4的滚动回收率仅为68％，可见本发明的包被剂具有优良的包被性能。As can be seen from Table 4, the embodiment can effectively exert the coating effect under the addition of 0.5%, and increase the rolling recovery rate of cuttings, and the effect is better than that of the comparative example; after the addition is increased to 1%, the cuttings are The rolling recovery rate in the aqueous solution of the example can reach 74%, even as high as 81.1%, while the rolling recovery rate of the linear polyacrylamide coating agent DC4 is only 68%. It can be seen that the coating agent of the present invention has excellent coating performance.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
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