CN116731250B - Preparation method of high-temperature-resistant acid liquid gelatinizing agent - Google Patents
Preparation method of high-temperature-resistant acid liquid gelatinizing agent Download PDFInfo
- Publication number
- CN116731250B CN116731250B CN202310715119.6A CN202310715119A CN116731250B CN 116731250 B CN116731250 B CN 116731250B CN 202310715119 A CN202310715119 A CN 202310715119A CN 116731250 B CN116731250 B CN 116731250B
- Authority
- CN
- China
- Prior art keywords
- stirring
- monomer
- parts
- reaction
- temperature
- 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.)
- Active
Links
- 239000002253 acid Substances 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 70
- 239000003349 gelling agent Substances 0.000 claims abstract description 41
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 19
- -1 pyrimidinyl alcohol Chemical compound 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 86
- 238000003756 stirring Methods 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 26
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229920000858 Cyclodextrin Polymers 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- PNROREDTZJCOHF-UHFFFAOYSA-N 2-(3,5-dichlorophenoxy)acetonitrile Chemical compound ClC1=CC(Cl)=CC(OCC#N)=C1 PNROREDTZJCOHF-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 7
- KAYAKFYASWYOEB-UHFFFAOYSA-N 3-octadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC=CC1CC(=O)OC1=O KAYAKFYASWYOEB-UHFFFAOYSA-N 0.000 claims description 7
- 239000001116 FEMA 4028 Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 7
- 229960004853 betadex Drugs 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 claims description 6
- UHDNUPHSDMOGCR-UHFFFAOYSA-N 3-Formylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=O)=C1 UHDNUPHSDMOGCR-UHFFFAOYSA-N 0.000 claims description 6
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- HPRSBHNFXFTUQL-UHFFFAOYSA-N sodium;ethanolate;hydrochloride Chemical compound [Na+].Cl.CC[O-] HPRSBHNFXFTUQL-UHFFFAOYSA-N 0.000 claims description 3
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 7
- 238000010008 shearing Methods 0.000 abstract description 7
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract description 7
- 125000003368 amide group Chemical group 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 6
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000003921 oil Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 5
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 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 2
- YCIPQJTZJGUXND-UHFFFAOYSA-N Aglaia odorata Alkaloid Natural products C1=CC(OC)=CC=C1C1(C(C=2C(=O)N3CCCC3=NC=22)C=3C=CC=CC=3)C2(O)C2=C(OC)C=C(OC)C=C2O1 YCIPQJTZJGUXND-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 2
- 125000005598 acylhydrazone group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- LAGQCXVIXQYJHO-UHFFFAOYSA-N (4-ethenylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=C(C=C)C=C1 LAGQCXVIXQYJHO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of a high-temperature-resistant acid liquid gelatinizer, which belongs to the technical field of gelatinizer preparation and comprises the following steps: s1, mixing monomers; s2, preparing a high-temperature-resistant acid liquid gelatinizing agent; the heat-resistant tackifying component is added, and contains sulfonic acid groups, carboxyl groups, quaternary ammonium salts, pyrimidinyl alcohol, disulfide bonds, acylhydrazone bonds, amide groups, siloxane groups, benzene rings and imidazole rings, wherein the sulfonic acid groups, carboxyl groups and quaternary ammonium salt groups have good acid resistance, and the pyrimidinyl alcohol, disulfide bonds, acylhydrazone bonds, amide groups, siloxane groups, benzene rings and imidazole ring structures have good high temperature resistance and high temperature resistance, and the structures can be synergistic with polyhydroxy active sites for fixing salt ions in modified beta cyclodextrin through chelation and hydrophobic long-chain alkyl chains for enabling macromolecular chains to associate in and between molecules, so that the high temperature stability, viscosity and shearing resistance of the acid liquid gelling agent are improved.
Description
Technical Field
The invention belongs to the field of preparation of gelling agents, and particularly relates to a preparation method of a high-temperature-resistant acid liquid gelling agent.
Background
The proportion of the low-permeability oil gas resources in China is more than 50%, and the low-permeability oil gas resources become the main exploration and development object in China at present. Because the low permeability reservoir is affected by factors such as large burial depth, high formation temperature (120-160 ℃), high formation water mineralization, strong diagenetic and compaction effects, etc., effective development can be realized usually by means of yield-increasing transformation measures such as fracturing, acidification, acid fracturing, etc. The high-temperature resistant acid liquid gelatinizer system is a key technology for fracturing and reforming a high-humidity low-permeability reservoir.
In the prior art, the acidified gelling agent mainly adopts acrylamide polymer products, such as a copolymer of acrylamide and acryloyloxyethyl trimethyl ammonium chloride, a copolymer of acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, a copolymer of maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid and methacryloyloxyethyl trimethyl ammonium chloride, and the like, and the copolymers have high relative molecular weight, high temperature resistance, salt resistance and shearing resistance, have good retarding performance, and can meet the acidification construction requirements below 150 ℃. However, the acrylamide segment in these copolymers is easily hydrolyzed at high temperature, and the hydrolysis product reacts with high valence ions and the like to form a precipitate. The strong hydration groups in the monomers such as 2-acrylamide-2-methylpropanesulfonic acid, acryloyloxyethyl trimethyl ammonium chloride and the like can improve the water-resistant hydration capability of a polymer molecular chain at high temperature to a certain extent, but the groups have limited functions at higher temperature (such as 180 ℃ and above) and under the action of strong acid, and the high-temperature tackifying effect of the gelling agent is insufficient.
Disclosure of Invention
The invention aims to solve the following technical problems:
how to improve the high temperature stability, the tackifying performance and the shearing resistance of the acid liquid gelling agent.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a high-temperature-resistant acid liquid gelatinizing agent comprises the following steps:
step S1, mixing monomers, namely stirring and mixing 12-15 parts of acrylic acid, 3-4 parts of methacrylic acid, 1-2 parts of hydroxyethyl acrylate and 5-8 parts of heat-resistant tackifying components for 20-40min to obtain a monomer mixture;
step S2, preparing a high-temperature-resistant acid liquid gelling agent: adding 2-3 parts by weight of a composite emulsifier into 100-110 parts by weight of white oil to obtain an oil phase; dissolving 6-12 parts by weight of the monomer mixture prepared in the step S1 and 6-10 parts by weight of modified beta cyclodextrin in 50 parts by weight of water, stirring and mixing for 15-20min, adding 0.1-0.5 part by weight of an initiator under the protection of inert gas, and regulating the pH value of the solution to 6.9-7.2 to obtain a water phase; adding 30-50 parts by weight of water phase into 50-70 parts by weight of oil phase, emulsifying for 10-15min at 12000-15000r/min, stirring for reacting for 30-50min, adding 2-4 parts by weight of auxiliary initiator, heating to 40-60 ℃, stirring for reacting for 3-5h, and adding 0.6-0.8 part by weight of phase inversion catalyst to obtain the high-temperature resistant acid liquid gelling agent.
Further, the inert gas is at least one selected from nitrogen, ammonia and fluorine.
Further, the composite emulsifier is prepared by mixing a lipophilic emulsifier and a hydrophilic emulsifier according to a mass ratio of 3-5:5-7.
Further, the lipophilic emulsifier is one or more selected from span-20, span-40, span-60 and span-80, and is mixed according to any ratio.
Further, the hydrophilic emulsifier is selected from one or more of Tween-20, tween-40, tween-60 and Tween-80, and is mixed at an arbitrary ratio.
Further, the initiator is one or more of sodium persulfate, ammonium persulfate and potassium persulfate which are mixed according to any ratio.
Further, the co-initiator is a 2-3wt% sodium bisulfite aqueous solution.
Further, the phase transfer catalyst is one or more of cetyl dimethyl benzyl ammonium chloride, cetyl trimethyl sodium bromide, cetyl trimethyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium bromide and stearyl trimethyl ammonium chloride which are mixed according to any ratio.
Further, the preparation method of the modified beta cyclodextrin comprises the following steps:
adding beta cyclodextrin into N, N-dimethylformamide, uniformly stirring at 35 ℃, regulating the pH value to 9 by using a 1M sodium hydroxide solution, then dropwise adding a mixed solution of octadecenylsuccinic anhydride and isopropanol, heating to 85-95 ℃ after the dropwise adding is finished, continuously stirring for reacting for 4-6 hours, regulating the pH value to 6 by using a hydrochloric acid solution, washing 3-5 times by using acetone and deionized water, recrystallizing, and drying at 40 ℃ to obtain modified beta cyclodextrin, wherein the dosage ratio of the beta cyclodextrin, the N, N-dimethylformamide to the mixed solution of the octadecenylsuccinic anhydride and the isopropanol is 3-6g:25-45mL:1-2g, and the dosage ratio of the octadecenylsuccinic anhydride to the isopropanol in the mixed solution of the octadecenylsuccinic anhydride and the isopropanol is 1-2g:10-20mL, cyclodextrin has the characteristic of hydrophilic inner cavity hydrophobic outer wall, can encapsulate hydrophobic molecules, and realizes the aqueous solution polymerization of hydrophobic monomers; the cyclodextrin molecules have various hydroxyl groups with different chemical reactivity, and can form intramolecular hydrogen bonds, so that the cyclodextrin molecules have high activity and certain rigidity, the polymer containing the cyclodextrin structure has certain high temperature resistance, the hydroxyl group at the C6 position in the beta cyclodextrin structure reacts with octadecenyl succinic anhydride, and the viscosity of the beta cyclodextrin is improved by modifying and introducing a hydrocarbon long chain, and meanwhile, unsaturated double bonds are introduced to the outer side of the cyclodextrin, so that the polymer can participate in the subsequent reaction process.
Further, the preparation method of the heat-resistant tackifying component comprises the following steps:
step A1, adding 3-carboxybenzaldehyde, dicyclohexylcarbodiimide and 4-dimethylaminopyridine into N, N-dimethylformamide, stirring uniformly, adding 2-amino-4-hydroxy-6-methylpyrimidine, heating to 45-55 ℃, stirring and reacting for 3-4 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with deionized water and absolute ethyl alcohol for 3-4 times, and drying to obtain a rigid monomer, wherein the dosage ratio of 3-carboxybenzaldehyde, dicyclohexylcarbodiimide, 4-dimethylaminopyridine, N-dimethylformamide to 2-amino-4-hydroxy-6-methylpyrimidine is 1.5-2.5g:2.5-4.1g:1.2-2.2g:45-65mL of 2-3g, N-dimethylformamide is taken as a solvent, dicyclohexylcarbodiimide is taken as a dehydrating agent, 4-dimethylaminopyridine is taken as a catalyst, and an amino group on 2-amino-4-hydroxy-6-methylpyrimidine and a carboxyl group on 3-carboxybenzaldehyde are subjected to amidation reaction to obtain a rigid monomer;
the molecular structural formula of the rigid monomer is shown as follows;
step A2, dissolving L-cystine dimethyl ester dihydrochloride in N, N-dimethylformamide, adding EDC and NHS, activating and stirring for 0.5h, adding a monomer A, heating to 70-75 ℃, stirring and reacting for 2h, adding a 0.1M sodium ethoxide aqueous solution to adjust pH to neutrality after the reaction is finished, carrying out suction filtration, washing to remove sodium ethoxide hydrochloride, and drying to obtain an ester monomer, wherein the dosage ratio of the L-cystine dimethyl ester dihydrochloride to the N, N-dimethylformamide, EDC, NHS and the monomer A is 0.8-1.1g:25-45mL:1.8-2.8g:1.0-1.6g, 2-3g, using N, N-dimethylformamide as a solvent, EDC and NHS as condensation promoters, carrying out amidation reaction on carboxyl on the monomer A and amino on L-cystine dimethyl ester dihydrochloride, and controlling the amount of substances of the monomer A to be slightly higher than twice the amount of the L-cystine dimethyl ester dihydrochloride in the reaction process so that the amino on the L-cystine dimethyl ester dihydrochloride can be completely consumed to obtain an ester monomer containing double bonds;
the molecular structural formula of the monomer A is shown as follows;
step A3, dissolving an ester monomer in N, N-dimethylformamide, heating to 45-55 ℃, adding hydrazine hydrate, stirring for reaction for 1.5-2.5h, and after the reaction is finished, carrying out suction filtration and drying to obtain an elastic element; dissolving the rigid monomer obtained in the step A1 in isopropanol, opening condensed water, adding an elastic element under stirring, heating to 70-75 ℃, stirring for reacting for 2 hours, carrying out suction filtration, and drying to obtain a heat-resistant tackifying component, wherein the dosage ratio of the ester monomer to N, N-dimethylformamide to hydrazine hydrate to the rigid monomer to isopropanol is 1.5-2.5g:55-65mL:0.12-0.2mL:0.7-2.3g:8-12mL, controlling the adding amount of the hydrazine hydrate to the rigid monomer to be slightly higher than twice the adding amount of the ester monomer, enabling the ester group on the ester monomer to be fully consumed, carrying out ester condensation reaction on the hydrazine hydrate and the ester monomer in the reaction process to obtain the heat-resistant tackifying component containing the acylhydrazone group, and enabling the hydrazide group on the elastic element to continuously carry out Schiff condensation reaction with the aldehyde group on the rigid monomer to obtain the heat-resistant tackifying component containing the acylhydrazone group, wherein unsaturated double bond can continuously participate in the subsequent reaction process through polymerization reaction;
the structural formula of the heat-resistant tackifying component is shown below:
further, the preparation method of the monomer A comprises the following steps:
step B1, adding 3-aminobenzenesulfonic acid into deionized water, stirring uniformly at room temperature, adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring for 0.5h, controlling the reaction temperature to be 65-75 ℃, stirring and reacting for 2-4h, and drying after the reaction is finished to obtain a quaternary ammonium salt compound, wherein the dosage ratio of 3-aminobenzenesulfonic acid, deionized water and 2, 3-epoxypropyl trimethyl ammonium chloride is 3-5g:45-55mL of 2.5-4.1g, and taking deionized water as a solvent, and carrying out ring-opening reaction on amino on 3-aminobenzenesulfonic acid and 2, 3-epoxypropyl trimethyl ammonium chloride to obtain a quaternary ammonium salt compound; the structural formula of the quaternary ammonium salt compound is shown as follows:
step B2, adding dimethyl vinyl chlorosilane and triethylamine into toluene, uniformly stirring, dropwise adding a mixed solution a of a quaternary ammonium salt compound and N, N-dimethylformamide, controlling the dropwise adding speed to be 1-2 drops/second, introducing nitrogen, heating to reflux, stirring for reacting for 6-8h, filtering after the reaction is finished, distilling filtrate under reduced pressure to remove toluene, dissolving a rotary evaporation product in acetone, filtering to remove triethylamine hydrochloride, and rotary evaporating the filtrate to remove acetone to obtain an organic silicon monomer containing unsaturated double bonds, wherein the dosage ratio of dimethyl vinyl chlorosilane to triethylamine to toluene to mixed solution a to acetone is 1.2-2.2mL:1-2mL:55-65mL:15-25mL, and the dosage ratio of the quaternary ammonium salt compound to N, N-dimethylformamide in the mixed solution a is 3.5-5.5g:15-25mL, using triethylamine as an acid binding agent, and carrying out substitution reaction on chlorine atoms on dimethylvinylchlorosilane and hydroxyl groups in quaternary ammonium salt compounds in the mixed solution to obtain an organosilicon monomer;
the structural formula of the organosilicon monomer is shown as follows:
adding an organosilicon monomer, imidazole-4, 5-dicarboxylic acid into N, N-dimethylformamide, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, heating to 55-65 ℃, stirring and reacting for 4-6h, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake, and freeze-drying to obtain a monomer A, wherein the dosage ratio of the organosilicon monomer to the imidazole-4, 5-dicarboxylic acid to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine to the N, N-dimethylformamide is 2-4g:0.9-2.1g:1.4-3.2g:0.7-1.7g:35-55mL, taking N, N-dimethylformamide as a solvent, taking dicyclohexylcarbodiimide as a dehydrating agent, and taking 4-dimethylaminopyridine as a catalyst, carrying out amidation reaction on secondary amino with strong nucleophilic property on the organosilicon monomer and the carboxyl of the imidazole-4, 5-dicarboxylic acid to obtain the monomer A, and controlling the imidazole-4, 5-dicarboxylic acid to be slightly higher than the organosilicon monomer in the reaction process, so that the organosilicon monomer can fully react;
the structural formula of the monomer A is shown as follows:
the invention has the beneficial effects that:
compared with other gelatinizer systems, the gelatinizer prepared by the invention has the advantages of high temperature resistance, shearing resistance, stability and salt resistance, and the gelatinizer has the advantages that firstly, the gelatinizer is added with a heat-resistant tackifying component which contains rich sulfonic acid groups, carboxyl groups, quaternary ammonium salts, pyrimidol, disulfide bonds, hydrazone bonds, amide groups, siloxane groups, benzene rings and imidazole rings, the sulfonic acid groups and carboxyl groups are acidic, the acid resistance of the gelatinizer is improved, the hydration of the gelatinizer is enhanced, the quaternary ammonium salts have amphoteric and supermolecular network structures formed based on the electrostatic action between anions and cations, the viscosity of the gelatinizer is improved, the pyrimidinyl alcohol can generate conversion of pyrimidinone under acid heat condition, the pyrimidinone has multiple hydrogen bonds, can enhance the stability and high temperature resistance of the gelatinizer together with high temperature resistant stable good disulfide bond with reversible dynamic chemical bond and acylhydrazone bond with dynamic reversible reaction under acid condition, the existence of siloxane group and amido group has good chemical inertia and low surface energy, the stability is good, the acid resistance of the gelatinizer is further improved, on the other hand, the pyrimidinyl alcohol cooperates with rigid benzene ring and imidazole ring, the high temperature resistance of the gelatinizer is improved, on the other hand, the modified beta cyclodextrin is added, on the one hand, the introduction of the modified beta cyclodextrin makes the space network structure of the gelatinizer solution more complex, the molecular structure is not easy to deform under high temperature and high shear effect, the modified beta cyclodextrin is inserted in the network structure with complicated and intricate acrylic acid molecular chain, the modified beta cyclodextrin is similar to a large framework to support and connect a space structure of an acrylic acid molecular chain, so that the molecular chain of the acrylic acid is more complex, the molecular structure is more favorable to be unchanged, the chain generation of the acrylic acid molecular chain is improved, the viscosity of the acrylic acid molecular chain is enhanced, the molecular chain is not easy to open under the actions of shearing and high temperature, and meanwhile, the high temperature resistance and the acid resistance of the acrylic acid molecular chain are more excellent under the combined action of the chemical action of polymer molecules and the physical action of the modified beta cyclodextrin; on the other hand, the hydrophobic nature of the long-chain alkyl chain causes intramolecular and intermolecular association of the macromolecular chain, and the macromolecular chain is introduced into the gelling agent, and can act synergistically with the hydrophobic siloxane groups in the heat-resistant tackifying component to jointly improve the tackiness of the gelling agent.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preferably, the present embodiment provides a method for preparing monomer a, including the steps of:
step B1, adding 4g of 3-aminobenzenesulfonic acid and 55mL of deionized water into a three-necked flask, uniformly stirring at room temperature, adding 3.3g of 2, 3-epoxypropyl trimethyl ammonium chloride, stirring for 0.5h, controlling the reaction temperature to be 70 ℃, stirring and reacting for 3h, and drying to obtain a quaternary ammonium salt compound after the reaction is finished;
step B2, adding 1.7mL of dimethylvinylchlorosilane, 1.5mL of triethylamine and 60mL of toluene into a three-necked flask, uniformly stirring, dropwise adding 20mL of mixed solution a, controlling the dropwise adding speed to be 2 drops/second, introducing nitrogen, heating to reflux, stirring for 7h, filtering after the reaction is finished, distilling the filtrate under reduced pressure to remove the toluene, dissolving a rotary evaporation product in 30mL of acetone, filtering to remove triethylamine hydrochloride, and rotary evaporating the filtrate to remove the acetone to obtain an organic silicon monomer containing unsaturated double bonds, wherein the dosage ratio of a quaternary ammonium salt compound to N, N-dimethylformamide in the mixed solution a is 4.5g:20mL;
and B3, adding 3g of organic silicon monomer, 1.5g of imidazole-4, 5-dicarboxylic acid and 45mL of N, N-dimethylformamide into a three-neck flask, adding 2.3g of dicyclohexylcarbodiimide and 1.2g of 4-dimethylaminopyridine, heating to 60 ℃, stirring for reaction for 5 hours, cooling to room temperature after the reaction is finished, filtering, washing a filter cake, and freeze-drying to obtain the monomer A.
Example 2
Preferably, this embodiment provides a method for preparing a heat-resistant tackifying component, comprising the steps of:
step A1, adding 2.0g of 3-carboxybenzaldehyde, 3.3g of dicyclohexylcarbodiimide, 1.7g of 4-dimethylaminopyridine and 55mL of N, N-dimethylformamide into a three-neck flask, uniformly stirring, adding 2.5g of 2-amino-4-hydroxy-6-methylpyrimidine, heating to 45-55 ℃, stirring for reacting for 3-4 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with deionized water and absolute ethyl alcohol for 3-4 times, and drying to obtain a rigid monomer;
step A2, adding 0.9g L-cystine dimethyl ester dihydrochloride and 35mL of N, N-dimethylformamide into a three-neck flask, adding 2.3g of EDC and 1.3g of NHS, activating and stirring for 0.5h, adding 2.5g of the monomer A prepared in the example 1, heating to 72 ℃, stirring and reacting for 2h, adding 0.1M sodium ethoxide aqueous solution to adjust pH to be neutral after the reaction is finished, carrying out suction filtration, washing to remove sodium ethoxide hydrochloride, and drying to obtain an ester monomer;
step A3, adding 2.0g of ester monomer and 60mL of N, N-dimethylformamide into a three-neck flask, uniformly stirring, heating to 50 ℃, adding 0.11mL of hydrazine hydrate, stirring for 2.0h, filtering after the reaction is finished, and drying to obtain an elastic element; and C, dissolving 1.5g of the rigid monomer obtained in the step A1 in 10mL of isopropanol, opening condensed water, adding the elastic element under stirring, heating to 72 ℃, stirring for reaction for 2 hours, filtering, and drying to obtain the heat-resistant tackifying component.
Example 3
Preferably, the embodiment provides a preparation method of modified beta cyclodextrin, which comprises the following steps:
adding 4.5g of beta cyclodextrin and 35mL of N, N-dimethylformamide into a three-neck flask, uniformly stirring at the temperature of 35 ℃, adjusting the pH value to 9 by using a 1M sodium hydroxide solution, then dropwise adding a mixed solution of 1.5g of octadecenyl succinic anhydride and 15mL of isopropanol, heating to 90 ℃ after the dropwise adding is finished, continuously stirring for reacting for 5 hours, adjusting the pH value to 6 by using a hydrochloric acid solution, washing for 4 times by using acetone and deionized water, recrystallizing, and drying at 40 ℃ to obtain the modified beta cyclodextrin.
Example 4
The embodiment provides a preparation method of a high-temperature-resistant acid liquid gelling agent, which comprises the following steps:
the embodiment provides a preparation method of a high-temperature-resistant acid liquid gelling agent, which comprises the following steps:
step S1, mixing monomers, namely stirring and mixing 12 parts of acrylic acid, 3 parts of methacrylic acid, 1 part of hydroxyethyl acrylate and 5 parts of the heat-resistant tackifying component prepared in the example 2 for 20 minutes to obtain a monomer mixture;
s2, preparing a high-temperature-resistant acid liquid gelatinizing agent, namely adding 2 parts by weight of a composite emulsifier into 100 parts by weight of white oil, dissolving 6 parts by weight of the monomer mixture prepared in the step S1 and 6 parts by weight of the modified beta cyclodextrin prepared in the example 3 into 50 parts by weight of water, stirring and mixing for 15-20min, adding 0.1 part by weight of sodium persulfate under the protection of nitrogen, and regulating the pH value of the solution to 6.9 to obtain a water phase; adding 30 parts by weight of water phase into 50-70 parts by weight of oil phase, emulsifying for 10min at 12000r/min, stirring for reaction for 30min, adding 2 parts by weight of 2wt% sodium bisulphate water solution, heating to 40 ℃, stirring for reaction for 3h, adding 0.6 part by weight of hexadecyl dimethyl benzyl ammonium chloride to obtain a high-temperature resistant acid liquid gelling agent, wherein the composite emulsifying agent is span-20 and tween-20, and the mass ratio is 3:5.
Example 5
The embodiment provides a preparation method of a high-temperature-resistant acid liquid gelling agent, which comprises the following steps:
step S1, mixing 13.5 parts of acrylic acid, 3.5 parts of methacrylic acid, 1.5 parts of hydroxyethyl acrylate and 6.5 parts of heat-resistant tackifying component, and stirring and mixing for 30min to obtain a monomer mixture;
step S2, preparing a high-temperature resistant acid liquid gelatinizing agent, namely adding 2.5 parts by weight of a composite emulsifier into 105 parts by weight of white oil, dissolving 9 parts by weight of the monomer mixture prepared in the step S1 and 8 parts by weight of modified beta cyclodextrin into 50 parts by weight of water, stirring and mixing for 17.5min, adding 0.3 part by weight of an initiator under the protection of ammonia gas, and regulating the pH value of the solution to 7.0 to obtain a water phase; adding 40 parts by weight of water phase into 60 parts by weight of oil phase, emulsifying for 12.5min at 13500r/min, stirring for reaction for 40min, adding 3 parts by weight of 2.5wt% sodium bisulphite aqueous solution, heating to 60 ℃, stirring for reaction for 4h, and adding 0.7 part by weight of cetyl trimethyl sodium bromide to obtain the high-temperature resistant acid liquid gelling agent, wherein the composite emulsifier is prepared by mixing span-40 and tween-40 according to a mass ratio of 4:6.
Example 6
The embodiment provides a preparation method of a high-temperature-resistant acid liquid gelling agent, which comprises the following steps:
step S1, mixing monomers, namely stirring and mixing 15 parts of acrylic acid, 4 parts of methacrylic acid, 2 parts of hydroxyethyl acrylate and 8 parts of heat-resistant tackifying components for 40 minutes to obtain a monomer mixture;
step S2, preparing a high-temperature-resistant acid liquid gelling agent: adding 3 parts by weight of a composite emulsifier into 110 parts by weight of white oil to obtain an oil phase; dissolving 12 parts by weight of the monomer mixture prepared in the step S1 and 10 parts by weight of modified beta-cyclodextrin in 50 parts by weight of water, stirring and mixing for 20min, adding 0.5 part by weight of an initiator under the protection of fluorine gas, and regulating the pH value of the solution to 7.2 to obtain a water phase; adding 50 parts by weight of water phase into 70 parts by weight of oil phase, emulsifying for 15min at 15000r/min, stirring for reaction for 50min, adding 4 parts by weight of 3wt% sodium bisulphate water solution, heating to 60 ℃, stirring for reaction for 5h, adding 0.8 part by weight of octadecyl dimethyl benzyl ammonium chloride to obtain a high temperature resistant acid liquid gelling agent, wherein the composite emulsifying agent is prepared by mixing span-40 and tween-40 according to a mass ratio of 5:7.
Comparative example 1
This comparative example provides a 3-sulfopropyl hexadecyl dimethyl betaine.
Comparative example 2
This comparative example provides a (4-vinylphenyl) dimethylsilane.
Comparative example 3
This comparative example provides a beta cyclodextrin.
Comparative example 4
The heat resistant tackifying component of example 5 was removed, the remaining materials and preparation process were unchanged.
Comparative example 5
The heat-resistant tackifying component in example 5 was replaced with the one in comparative example 1, the remaining raw materials and the preparation process were unchanged.
Comparative example 6
The heat-resistant tackifying component in example 5 was replaced with the substance in comparative example 2, the remaining raw materials and the preparation process were unchanged.
Comparative example 7
The modified beta cyclodextrin in example 5 was removed, and the remaining raw materials and preparation process were unchanged.
Comparative example 8
The modified beta cyclodextrin in example 5 was replaced with the material in comparative example 3, and the remaining raw materials and the preparation process were unchanged.
Performance testing
(1) High temperature resistance
1wt% of the high temperature resistant acid gelling agent prepared in examples 4 to 6 and comparative examples 4 to 8 was subjected to a shear rate of 170s at room temperature, 90 ℃, 140 ℃, 160 ℃ and 200 DEG C -1 Under the condition, the apparent viscosity of the acid gelling agent is shown in Table 1.
TABLE 1
(2) Stability performance
1wt% of the high-temperature-resistant acid gelling agent prepared in examples 4 to 6 and comparative examples 4 to 8 was allowed to stand for 6 to 8 months, and the layering condition was observed, and the results are shown in Table 3;
(3) Shear resistance
1wt% of the high temperature resistant acid gelling agent obtained in examples 1 to 3 and comparative examples 4 to 8 was added at room temperature (25 ℃ C.) for 170s -1 The apparent viscosity (. Eta.1) was measured by shearing at a shearing rate for 4 hours, and the viscosity retention (%) was calculated.
At room temperature (25 ℃) for 170s by a six-speed rotational viscometer -1 Apparent viscosity is measured at shear rate and is defined as the apparent viscosity η in the initial state 0
Viscosity retention (%) = (apparent viscosity η at the time of measurement) 1 Apparent viscosity eta in the initial state 0 ) Apparent viscosity eta in initial state 0 100% and the results are shown in Table 3.
TABLE 3 Table 3
As can be seen from tables 1-3, the high-temperature resistant acid liquid gelling agent prepared in examples 4-6 of the present invention has better temperature resistance, salt resistance, stability and shear resistance, while in comparative example 4, the prepared gelling agent lacks sulfonic acid group, carboxyl group, quaternary ammonium salt, pyrimidinol, disulfide bond, acylhydrazone bond, amide group, siloxane group, benzene ring, imidazole ring and other groups, so that each performance of the obtained gelling agent is obviously reduced, and in comparative example 5, unsaturated double bond is lacking, 3-sulfopropyl hexadecyl dimethyl betaine serving as the heat resistant tackifying component cannot generate stable structure with the main body of the gelling agent, and simultaneously, lacks functional groups such as siloxane group, benzene ring, imidazole ring, quaternary ammonium salt, pyrimidinol, disulfide bond, acylhydrazone bond, amide group and the like with strong heat stability and excellent heat resistant tackifying property, so that the performance of the prepared gelling agent is reduced; the absence of an imidazole ring with strong heat stability and various functional groups with acid resistance and tackifying properties in comparative example 6 resulted in a decrease in the performance of the resulting gellant; the absence of beta cyclodextrin, which serves as a backbone, in comparative example 7 resulted in a decrease in the performance of the resulting gellant; the absence of long-chain alkyl chains and unsaturated double bonds that act as a copolymer to improve the salt resistance of the gelling agent by hydrophobic action in comparative example 8 resulted in a decrease in the properties of the resulting gelling agent.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. The preparation method of the high-temperature-resistant acid liquid gelatinizing agent is characterized by comprising the following steps of:
step S1, mixing monomers, namely stirring and mixing 12-15 parts of acrylic acid, 3-4 parts of methacrylic acid, 1-2 parts of hydroxyethyl acrylate and 5-8 parts of heat-resistant tackifying components for 20-40min to obtain a monomer mixture;
step S2, preparing a high-temperature-resistant acid liquid gelling agent: adding 2-3 parts by weight of a composite emulsifier into 100-110 parts by weight of white oil to obtain an oil phase; dissolving 6-12 parts by weight of the monomer mixture prepared in the step S1 and 6-10 parts by weight of modified beta cyclodextrin in 50 parts by weight of water, stirring and mixing for 15-20min, adding 0.1-0.5 part by weight of an initiator under the protection of inert gas, and regulating the pH value of the solution to 6.9-7.2 to obtain a water phase; adding 30-50 parts by weight of water phase into 50-70 parts by weight of oil phase, emulsifying for 10-15min at 12000-15000r/min, stirring for reacting for 30-50min, adding 2-4 parts by weight of auxiliary initiator, heating to 40-60 ℃, stirring for reacting for 3-5h, and adding 0.6-0.8 part by weight of phase inversion catalyst to obtain high-temperature resistant acid liquid gelling agent;
the preparation method of the heat-resistant tackifying component comprises the following steps:
step A1, adding 3-carboxybenzaldehyde, dicyclohexylcarbodiimide and 4-dimethylaminopyridine into N, N-dimethylformamide, stirring uniformly, adding 2-amino-4-hydroxy-6-methylpyrimidine, heating to 45-55 ℃, stirring for reacting for 3-4 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with deionized water and absolute ethyl alcohol for 3-4 times, and drying to obtain a rigid monomer;
step A2, dissolving L-cystine dimethyl ester dihydrochloride in N, N-dimethylformamide, adding EDC and NHS, activating and stirring for 0.5h, adding a monomer A, heating to 70-75 ℃, stirring and reacting for 2h, adding a 0.1M sodium ethoxide aqueous solution to adjust pH to be neutral after the reaction is finished, carrying out suction filtration, washing to remove sodium ethoxide hydrochloride, and drying to obtain an ester monomer;
step A3, dissolving an ester monomer in N, N-dimethylformamide, heating to 45-55 ℃, adding hydrazine hydrate, stirring for reaction for 1.5-2.5h, and after the reaction is finished, carrying out suction filtration and drying to obtain an elastic element; dissolving the rigid monomer obtained in the step A1 in isopropanol, opening condensed water, adding an elastic element under stirring, heating to 70-75 ℃, stirring for reaction for 2 hours, filtering, and drying to obtain a heat-resistant tackifying component;
the preparation method of the monomer A comprises the following steps:
step B1, adding 3-aminobenzenesulfonic acid into deionized water, uniformly stirring at room temperature, adding 2, 3-epoxypropyl trimethyl ammonium chloride, stirring for 0.5h, controlling the reaction temperature to be 65-75 ℃, stirring and reacting for 2-4h, and drying after the reaction is finished to obtain a quaternary ammonium salt compound;
step B2, adding dimethyl vinyl chlorosilane and triethylamine into toluene, uniformly stirring, dropwise adding a mixed solution a of a quaternary ammonium salt compound and N, N-dimethylformamide, controlling the dropwise adding speed to be 1-2 drops/second, introducing nitrogen, heating to reflux, stirring for reaction for 6-8 hours, filtering after the reaction is finished, distilling filtrate under reduced pressure to remove toluene, dissolving a rotary evaporation product in acetone, filtering to remove triethylamine hydrochloride, and rotary evaporating the filtrate to remove acetone to obtain an organosilicon monomer containing unsaturated double bonds;
step B3, adding an organosilicon monomer and imidazole-4, 5-dicarboxylic acid into N, N-dimethylformamide, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, heating to 55-65 ℃, stirring for reaction for 4-6 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake, and freeze-drying to obtain a monomer A;
in the mixed solution a, the dosage ratio of the quaternary ammonium salt compound to the N, N-dimethylformamide is 3.5-5.5g:15-25mL;
the preparation method of the modified beta cyclodextrin comprises the following steps:
adding beta cyclodextrin into N, N-dimethylformamide, stirring uniformly at 35 ℃, regulating the pH value to 9 by using a 1M sodium hydroxide solution, then dropwise adding a mixed solution of octadecenyl succinic anhydride and isopropanol, heating to 85-95 ℃ after the dropwise adding is finished, continuing stirring and reacting for 4-6 hours, regulating the pH value to 6 by using a hydrochloric acid solution, washing for 3-5 times by using acetone and deionized water, recrystallizing, and drying at 40 ℃ to obtain the modified beta cyclodextrin.
2. The method for preparing a high-temperature resistant acid gelling agent according to claim 1, wherein the dosage ratio of 3-carboxybenzaldehyde, dicyclohexylcarbodiimide, 4-dimethylaminopyridine, N-dimethylformamide and 2-amino-4-hydroxy-6-methylpyrimidine in step A1 is 1.5-2.5g:2.5-4.1g:1.2-2.2g:45-65mL, 2-3g.
3. The method for preparing a high temperature resistant acid gelling agent according to claim 1, wherein in step A2, the ratio of the amounts of L-cystine dimethyl ester dihydrochloride, N-dimethylformamide, EDC, NHS and monomer a is 0.8-1.1g:25-45mL:1.8-2.8g:1.0-1.6 g/2-3 g.
4. The method for preparing the high-temperature-resistant acid gelling agent according to claim 1, wherein in the step A3, the dosage ratio of the ester monomer, N-dimethylformamide, hydrazine hydrate, rigid monomer and isopropanol is 1.5-2.5 g/55-65 mL/0.12-0.2 mL/0.7-2.3 g/8-12 mL.
5. The method for preparing a high-temperature resistant acid gelling agent according to claim 1, wherein in the step B1, the dosage ratio of 3-aminobenzenesulfonic acid, deionized water and 2, 3-epoxypropyl trimethyl ammonium chloride is 3-5g:45-55mL, 2.5-4.1g.
6. The method for preparing the high-temperature-resistant acid liquid gelling agent according to claim 1, wherein in the step B2, the dosage ratio of the dimethylvinylchlorosilane to the triethylamine to the toluene to the mixed solution a to the acetone is 1.2-2.2mL:1-2mL:55-65mL:15-25mL:25-35mL.
7. The method for preparing a high temperature resistant acid gelling agent according to claim 1, wherein in step B3, the organosilicon monomer, imidazole-4, 5-dicarboxylic acid, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and N, N-dimethylformamide are used in a ratio of 2-4g:0.9-2.1g:1.4-3.2g:0.7-1.7g:35-55mL.
8. The method for preparing a high-temperature-resistant acid gelling agent according to claim 1, wherein in step S2, the composite emulsifier is mixed with the lipophilic emulsifier and the hydrophilic emulsifier according to a mass ratio of 3-5:5-7.
9. The method for preparing a high-temperature resistant acid solution gelling agent according to claim 1, wherein in step S2, the co-initiator is a 2-3wt% aqueous solution of sodium bisulphite, and the phase transfer catalyst is one or more of cetyldimethylbenzyl ammonium chloride, cetyltrimethyl sodium bromide, cetyltrimethyl ammonium bromide, octadecyldimethylbenzyl ammonium chloride, octadecyltrimethyl ammonium bromide and octadecyl trimethyl ammonium chloride, which are mixed according to any ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310715119.6A CN116731250B (en) | 2023-06-16 | 2023-06-16 | Preparation method of high-temperature-resistant acid liquid gelatinizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310715119.6A CN116731250B (en) | 2023-06-16 | 2023-06-16 | Preparation method of high-temperature-resistant acid liquid gelatinizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116731250A CN116731250A (en) | 2023-09-12 |
| CN116731250B true CN116731250B (en) | 2024-03-05 |
Family
ID=87916461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310715119.6A Active CN116731250B (en) | 2023-06-16 | 2023-06-16 | Preparation method of high-temperature-resistant acid liquid gelatinizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116731250B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388075A (en) * | 2014-10-27 | 2015-03-04 | 中国石油集团渤海钻探工程有限公司 | Gelatinizing agent for acidification of high temperature carbonatite and preparing method of gelatinizing agent |
| CN106047333A (en) * | 2016-05-26 | 2016-10-26 | 中国石油集团渤海钻探工程有限公司 | High-temperature-resistant gelling agent in acid liquid and method for preparing high-temperature-resistant gelling agent |
| WO2019192629A1 (en) * | 2018-04-07 | 2019-10-10 | 四川大学 | Anionic thermoviscosifying water-soluble polymer, and preparation method therefor and application thereof |
| CN110551250A (en) * | 2018-05-31 | 2019-12-10 | 中国石油天然气股份有限公司 | emulsion type acid liquid thickener and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210108122A1 (en) * | 2020-02-17 | 2021-04-15 | Southwest Petroleum University | Cross-linked plugging agent stimulated by high density brine and preparing method thereof |
-
2023
- 2023-06-16 CN CN202310715119.6A patent/CN116731250B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388075A (en) * | 2014-10-27 | 2015-03-04 | 中国石油集团渤海钻探工程有限公司 | Gelatinizing agent for acidification of high temperature carbonatite and preparing method of gelatinizing agent |
| CN106047333A (en) * | 2016-05-26 | 2016-10-26 | 中国石油集团渤海钻探工程有限公司 | High-temperature-resistant gelling agent in acid liquid and method for preparing high-temperature-resistant gelling agent |
| WO2019192629A1 (en) * | 2018-04-07 | 2019-10-10 | 四川大学 | Anionic thermoviscosifying water-soluble polymer, and preparation method therefor and application thereof |
| CN110551250A (en) * | 2018-05-31 | 2019-12-10 | 中国石油天然气股份有限公司 | emulsion type acid liquid thickener and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116731250A (en) | 2023-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102875742B (en) | Manufacturing method of high branching degree acrylamide graft copolymer taking amylopectin as framework | |
| CN100363394C (en) | Water soluble amphoteric ion copolymer and preparation process thereof | |
| CN103044622A (en) | Preparation method of water-in-water type cationic polyacrylamide emulsion | |
| CN111393538B (en) | Zwitterionic hydrophobic modified guar gum and preparation method thereof | |
| CN112708060B (en) | Novel anti-corrosion polycarboxylate superplasticizer and preparation method thereof | |
| CN101289541B (en) | Organic-hybridization micro-hydrogels sensitive to pH value and temperature and method for preparing same | |
| CN116731250B (en) | Preparation method of high-temperature-resistant acid liquid gelatinizing agent | |
| CN106543377B (en) | A kind of copolymer fluid loss agent and preparation method thereof | |
| CN102020754B (en) | Preparation method of cationic dendrimer-star polymer papermaking additive | |
| CN115232261B (en) | Hybrid gelatinizer for oilfield acidification based on POSS (polyhedral oligomeric silsesquioxanes) based cross-linking agent and preparation method thereof | |
| CN112341575A (en) | Water-based acrylic emulsion with lasting antibacterial function | |
| CN114230714B (en) | Hydrophobic association double-network oil displacement polymer and preparation method thereof | |
| CN111393545B (en) | Temperature-resistant and salt-resistant dendritic supramolecular polymer oil-displacing agent as well as preparation method and application thereof | |
| CN111592616A (en) | Preparation method of nanoscale hyperbranched hydrophobically associating polyacrylamide | |
| EP1924618A1 (en) | Bile acid sequestrant and process for preparation thereof | |
| CN106608975A (en) | Grafted starch thickening agent copolymerization association compound and preparation method thereof | |
| CN109280129B (en) | Injectable hydrogel polymer based on salt response under physiological conditions and preparation method thereof | |
| CN106608976A (en) | Starch-containing thickening agent copolymerization association compound and preparation method thereof | |
| CN110642961A (en) | Preparation method of hydrophobically modified xanthan gum | |
| CN1982395A (en) | Cation branched-chain starch wood binder and its production | |
| CN114075310B (en) | Two-phase viscosity regulator and preparation method thereof | |
| JP3264927B2 (en) | Method for stabilizing a copolymer comprising maleic acid or maleic anhydride and vinyl alkyl ether | |
| CN114478922B (en) | Preparation process of high-solubility high-molecular-weight cationic polyacrylamide | |
| CN103848936B (en) | Seed polymer and stabilizing agent thereof and apply the method that the two prepares water in water CPAM copolymer dispersion | |
| CN1285625C (en) | Preparation for water soluble polyacrylamide, its derivative super-fine powder material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |