CN113372496B - Modified cyclodextrin and preparation method and application thereof - Google Patents
Modified cyclodextrin and preparation method and application thereof Download PDFInfo
- Publication number
- CN113372496B CN113372496B CN202110758345.3A CN202110758345A CN113372496B CN 113372496 B CN113372496 B CN 113372496B CN 202110758345 A CN202110758345 A CN 202110758345A CN 113372496 B CN113372496 B CN 113372496B
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- product
- weight ratio
- solvent
- cyclodextrin
- sodium
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class 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 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000005553 drilling Methods 0.000 claims abstract description 53
- 239000012530 fluid Substances 0.000 claims abstract description 51
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 50
- -1 hydroxypropyl cyclodextrin Chemical compound 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 33
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 27
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims description 57
- 229910021641 deionized water Inorganic materials 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 41
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 14
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical group C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 6
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 6
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 5
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 5
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 5
- 235000019252 potassium sulphite Nutrition 0.000 claims description 5
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 4
- UNCPEAUIVGCHJJ-UHFFFAOYSA-M sodium;2-sulfoethenolate Chemical compound [Na+].OS(=O)(=O)C=C[O-] UNCPEAUIVGCHJJ-UHFFFAOYSA-M 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims 3
- 150000003839 salts Chemical class 0.000 abstract description 14
- 239000000047 product Substances 0.000 description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000005098 hot rolling Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 17
- 235000009827 Prunus armeniaca Nutrition 0.000 description 14
- 244000018633 Prunus armeniaca Species 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 8
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 8
- 239000001116 FEMA 4028 Substances 0.000 description 8
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound 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)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 HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 8
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound 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 description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 8
- 229960004853 betadex Drugs 0.000 description 8
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound 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)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 GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 7
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- KJVRLFWTIGWXFK-UHFFFAOYSA-N n-prop-2-enylbenzamide Chemical compound C=CCNC(=O)C1=CC=CC=C1 KJVRLFWTIGWXFK-UHFFFAOYSA-N 0.000 description 5
- 229940092782 bentonite Drugs 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229940097362 cyclodextrins Drugs 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 229940080314 sodium bentonite Drugs 0.000 description 2
- 229910000280 sodium bentonite Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 101000823934 Caenorhabditis elegans Serine palmitoyltransferase 3 Proteins 0.000 description 1
- 101100534168 Danio rerio supt6h gene Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 101000663444 Homo sapiens Transcription elongation factor SPT4 Proteins 0.000 description 1
- 101000702364 Homo sapiens Transcription elongation factor SPT5 Proteins 0.000 description 1
- 101000698001 Homo sapiens Transcription initiation protein SPT3 homolog Proteins 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 102100027677 Protein SPT2 homolog Human genes 0.000 description 1
- 101710122478 Serine palmitoyltransferase 1 Proteins 0.000 description 1
- 102100022068 Serine palmitoyltransferase 1 Human genes 0.000 description 1
- 101710122477 Serine palmitoyltransferase 2 Proteins 0.000 description 1
- 102100038997 Transcription elongation factor SPT4 Human genes 0.000 description 1
- 102100030402 Transcription elongation factor SPT5 Human genes 0.000 description 1
- 102100027912 Transcription initiation protein SPT3 homolog Human genes 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 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 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 101150003163 spt6 gene Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/20—Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives
- C09K8/206—Derivatives of other natural products, e.g. cellulose, starch, sugars
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the field of oilfield chemistry, and discloses a preparation method of modified cyclodextrin, which comprises the following steps: (1) in the presence of a catalyst, carrying out a first reaction on hydroxypropyl cyclodextrin and 3-propylene isocyanate in a first solvent to obtain a first product; (2) and in the presence of an initiator, carrying out a second reaction on the first product, a vinyl sulfonate monomer, an alkenyl alcohol monomer and acrylamide in a second solvent to obtain the modified cyclodextrin. The modified cyclodextrin has a star-shaped molecular structure, can effectively improve the viscosity of the water-based drilling fluid, has strong rheological property adjusting capability, excellent temperature resistance and salt resistance, and is environment-friendly.
Description
Technical Field
The invention relates to the field of oilfield chemistry, and particularly relates to modified cyclodextrin and a preparation method and application thereof.
Background
The rheological property of the drilling fluid plays an important role in solving the problem of cuttings carried by the drilling fluid and ensuring the safety of drilling construction, so that the rheological property of the drilling fluid needs to be adjusted by adding a flow type regulator into the drilling fluid. However, under the conditions of high salt and high temperature, the performance of the flow pattern regulator for the water-based drilling fluid is obviously affected, the viscosity and the shearing force of the drilling fluid are insufficient, rock debris cannot be effectively suspended, and the problems of increased filtration loss, instability of a well wall and the like are caused.
At present, the commonly used flow pattern regulators for water-based drilling fluids are generally classified into natural modified polymers and synthetic polymers. The natural modified polymer flow pattern regulator comprises xanthan gum, modified cellulose, modified starch and the like, has good environmental protection performance, but has poor temperature resistance and salt resistance, and can not be applied to drilling engineering at the temperature of more than 140 ℃; the synthetic polymer flow pattern regulator can resist high temperature of more than 180 ℃ and also has better salt resistance, but the monomers used in the preparation process have toxicity or degradation products can pollute the stratum, and the environmental protection performance is poorer.
CN111363526B discloses an application of modified apricot kernel powder as a flow pattern regulator for an environment-friendly drilling fluid, wherein the modified apricot kernel powder is a product of apricot kernel powder modified as follows: mixing the apricot kernel powder with acid liquor to obtain suspension, and stirring for acidification; then, neutralizing by using an alkali solution until the pH value is 6-7, and performing centrifugal separation to obtain an acidified product; dispersing the acidified product in water, adding the aqueous alkali to adjust the acidified product to be alkalescent, and adding an etherifying agent and an initiator to carry out etherification reaction; after the etherification reaction is finished, adjusting the pH value to be neutral by using the acid liquor, and separating and drying to obtain the modified apricot kernel powder; the apricot kernel powder is prepared by crushing at least one of golden sun apricot, greenhouse king apricot, Katy apricot, golden apricot, Hongfeng apricot, New century apricot, pearl oil apricot and special early-maturing test tube apricot, and sieving with 200 mesh sieve. The flow pattern regulator has good environmental protection performance and flow pattern improving effect, but only shows the high temperature resistance of 130 ℃, and simultaneously does not relate to salt resistance, thereby greatly limiting the practical application of the flow pattern regulator.
CN103409118B discloses a method for synthesizing a water-based drilling fluid ultra-high temperature stabilizer, which comprises the following steps: (1) acrylamide, acrylic acid and N-allyl benzamide are used as monomers, sodium bisulfite and ammonium persulfate are used as initiators, ethylene diamine tetraacetic acid is used as a molecular weight regulator, alkylphenol polyoxyethylene ether is used as an emulsifier, the total monomer concentration is 20 mass%, and the mass ratio of the three monomers is acrylamide: acrylic acid: the preparation method comprises the following steps of (1) preparing N-allyl benzamide, wherein the ratio of the N-allyl benzamide to 14:5.5-5.7:0.3-0.5, the adding amount of a molecular weight regulator is 0.5 mass% of the total amount of monomers, and the adding amount of an initiator is 0.5 mass% of the total amount of the monomers, and preparing polyacrylamide/sodium acrylate/N-allyl benzamide in a solution polymerization mode; (2) activating humic acid with sodium hydroxide, and then performing crosslinking reaction on the humic acid and polyacrylamide/sodium acrylate/N-allylbenzamide for 5 hours at 70 ℃ through the crosslinking action of zirconium tetrachloride to obtain the ultra-high temperature stabilizer. The stabilizer has excellent temperature resistance, can keep better rheological property and lower filtration loss of the water-based drilling fluid under the condition of ultrahigh temperature, but does not have salt resistance.
In conclusion, the development of the flow pattern regulator with high temperature resistance, salt resistance and environmental protection is of great significance for meeting the deep well operation of the water-based drilling fluid.
Disclosure of Invention
The invention aims to solve the problem that the prior flow pattern regulator for water-based drilling fluid is difficult to consider high temperature resistance, salt resistance and environmental protection, and provides modified cyclodextrin and a preparation method and application thereof.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing a modified cyclodextrin, the method comprising:
(1) in the presence of a catalyst, carrying out a first reaction on hydroxypropyl cyclodextrin and 3-propylene isocyanate in a first solvent to obtain a first product;
(2) and in the presence of an initiator, carrying out a second reaction on the first product, a vinyl sulfonate monomer, an alkenyl alcohol monomer and acrylamide in a second solvent to obtain the modified cyclodextrin.
In a second aspect, the present invention provides a modified cyclodextrin obtainable by the process of the first aspect as hereinbefore described.
In a third aspect, the present invention provides a water-based drilling fluid comprising a modified cyclodextrin as described in the second aspect above.
In a fourth aspect, the present invention provides the use of a modified cyclodextrin as described in the second aspect above as a flow pattern modifier in an aqueous based drilling fluid.
Through the technical scheme, the modified cyclodextrin provided by the invention has the following beneficial effects:
(1) the star-shaped molecular structure is adopted, so that the viscosity increasing performance is excellent, the viscosity of the water-based drilling fluid can be effectively improved, and the rheological property adjusting capability is strong;
(2) has excellent temperature resistance and salt resistance: 1% of the modified cyclodextrin is added into 4% of sodium bentonite fresh water-based slurry and 4% of sodium bentonite saturated saline water-based slurry at normal temperature respectively, so that the apparent viscosity of the drilling fluid is higher than 25mPa & s, and on the basis, after the drilling fluid is hot rolled for 16 hours at 200 ℃, the viscosity retention rates of the fresh water slurry and the saturated saline water slurry are higher than 65%;
(3) the preparation method is easy to biodegrade, environment-friendly and wide in raw material source for preparation;
(4) has better compatibility and strong applicability.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides, in a first aspect, a process for the preparation of a modified cyclodextrin, the process comprising:
(1) in the presence of a catalyst, carrying out a first reaction on hydroxypropyl cyclodextrin and 3-propylene isocyanate in a first solvent to obtain a first product;
(2) and in the presence of an initiator, carrying out a second reaction on the first product, a vinyl sulfonate monomer, an alkenyl alcohol monomer and acrylamide in a second solvent to obtain the modified cyclodextrin.
In some embodiments of the present invention, in step (1), the hydroxypropyl cyclodextrin may be prepared by a method conventional in the art for preparing hydroxypropyl cyclodextrins, preferably by the following method:
(a) dissolving cyclodextrin in an alkaline solution to obtain a solution A;
(b) carrying out a third reaction on the solution A, epoxy chloropropane and deionized water together, and then drying a reaction product to prepare hydroxypropyl cyclodextrin; wherein,
in step (a), the cyclodextrin may be at least one of α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin; the alkaline solution may be an aqueous solution of sodium hydroxide and/or potassium hydroxide, preferably at a concentration of 1-4 wt%; preferably, the ratio of cyclodextrin: the weight ratio of the alkaline solution can be (4-16): 40.
in step (a), the dissolving conditions may include: the temperature is room temperature, the time is 0.5-1h, and the stirring speed is 600-1000 rpm.
In step (b), the ratio of cyclodextrin in solution a: epoxy chloropropane: the weight ratio of the deionized water can be (2-8): (0.5-9): 100.
the conditions of the third reaction may include: the temperature is 30-40 ℃, the time is 1-1.5h, and the stirring speed is 600-.
The conditions of the drying process may include: the temperature is 40-60 ℃ and the time is 12-24 h.
In the invention, the cyclodextrin is prepared into hydroxypropyl cyclodextrin, so that the number of reaction sites on the surface of the cyclodextrin can be greatly increased.
In some embodiments of the invention, in step (1), the catalyst is an acid, preferably at least one of sulfuric acid, p-toluenesulfonic acid, and perchloric acid; the first solvent is deionized water.
In some embodiments of the present invention, in step (1), the first reaction is an esterification reaction, and a carbon-carbon double bond is introduced on the surface of hydroxypropyl cyclodextrin by the reaction. For better reaction effect, the first solvent: hydroxypropyl cyclodextrin: 3-isocyanatopropylene: the weight ratio of the catalyst can be 100: (10-40): (10-70): (1-10).
Preferably, the first solvent: hydroxypropyl cyclodextrin: 3-isocyanatopropylene: the weight ratio of the catalyst can be 100: (20-30): (25-50): (1-5).
In some embodiments of the invention, in step (1), the conditions of the first reaction comprise: the temperature is 80-140 ℃, and preferably 100-120 ℃; the time is 2 to 12 hours, preferably 6 to 8 hours; the stirring speed is 200-1500 rpm, preferably 600-1000 rpm.
In some embodiments of the present invention, in step (1), the product of the first reaction is preferably repeatedly washed with deionized water until the pH is neutral, and then dried to obtain the first product.
In the present invention, the first product has a branched structure having a plurality of carbon-carbon double bonds.
In some embodiments of the invention, in step (2), the vinyl sulfonate monomer is selected from at least one of sodium 2-acrylamido-2-methylpropane sulfonate, sodium allyl sulfonate, sodium styrene sulfonate, and sodium hydroxyvinyl sulfonate.
The alkenyl alcohol monomer is at least one selected from allyl alcohol, 2-ethyl-3-alkene butanol and methallyl alcohol.
In some embodiments of the present invention, in step (2), the second reaction is an atom transfer radical polymerization reaction, and the initiator used is composed of an oxidizing agent and a reducing agent, wherein the oxidizing agent is at least one of ammonium persulfate, potassium persulfate, and sodium persulfate; the reducing agent is at least one of sodium bisulfite, potassium sulfite, sodium thiosulfate and potassium thiosulfate; preferably, to better initiate the polymerization reaction, the oxidizing agent: the mass ratio of the reducing agent is (0.5-2): 1.
in some embodiments of the present invention, in step (2), the second solvent may be deionized water.
In some embodiments of the present invention, in the step (2), in order to obtain better reaction effect, the second solvent: a first product: vinyl sulfonate monomer: alkenyl alcohol monomer: the weight ratio of acrylamide may be 100: (1-30): (1-30): (1-20): (1-10); the first product: the weight ratio of the initiator may be (10-50): 1.
preferably, the second solvent: a first product: vinyl sulfonate monomer: alkenyl alcohol monomer: the weight ratio of acrylamide may be 100: (5-20): (2-20): (2-10): (1-7); the first product: the weight ratio of the initiator may be (10-33): 1.
in some embodiments of the present invention, in step (2), the conditions of the second reaction may include: the temperature is 55-85 ℃, preferably 60-80 ℃; the time is 2 to 8 hours, preferably 4 to 6 hours; the stirring speed is 200-1500 rpm, preferably 600-1000 rpm.
In some embodiments of the present invention, in step (2), preferably, the product of the second reaction is repeatedly washed with deionized water to remove unreacted monomers therein, and then dried to obtain the modified cyclodextrin.
In a second aspect, the present invention provides a modified cyclodextrin obtainable by the process of the first aspect as hereinbefore described. The modified cyclodextrin has a star-shaped structure, and the average molecular weight is 180-300 ten thousand g/mol.
In a third aspect, the present invention provides a water-based drilling fluid comprising a modified cyclodextrin as described in the second aspect above.
In the present invention, the modified cyclodextrin may be used in an amount of 0.5 to 5%, preferably 1 to 3%, in the water-based drilling fluid. That is, the modified cyclodextrin may be used in an amount of 0.5 to 5g, preferably 1 to 3g, relative to 100mL of the water-based drilling fluid.
In a fourth aspect, the present invention provides the use of a modified cyclodextrin as described in the second aspect above as a flow pattern modifier in an aqueous based drilling fluid.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples,
hydroxypropyl cyclodextrins (designated H1-H6) were prepared as described above, as follows:
preparation H1:
(a) adding beta-cyclodextrin into sodium hydroxide aqueous solution (the concentration is 3.2 wt%), and continuously stirring for 1h at the speed of 1000 r/min at room temperature to fully dissolve the beta-cyclodextrin to obtain solution A1; wherein, the beta-cyclodextrin: the weight ratio of the sodium hydroxide aqueous solution is 16: 40;
(b) reacting the solution A1 with epichlorohydrin and deionized water at a stirring speed of 1000 rpm and a temperature of 40 ℃ for 1.5H, and vacuum-drying a reaction product at 60 ℃ for 24H to obtain H1; wherein, the ratio of beta-cyclodextrin in the solution A1: epoxy chloropropane: the weight ratio of the deionized water is 16: 17.7: 200.
preparation H2:
(a) adding alpha-cyclodextrin into potassium hydroxide aqueous solution (the concentration is 2.3 wt%), and continuously stirring at the room temperature at the speed of 600 revolutions per minute for 0.5h to fully dissolve the alpha-cyclodextrin to obtain solution A2; wherein, the alpha-cyclodextrin: the weight ratio of the potassium hydroxide aqueous solution is 16: 40;
(b) and (3) reacting the solution A2 with epichlorohydrin and deionized water at the stirring speed of 600 rpm and the temperature of 30 ℃ for 1H, and vacuum-drying the reaction product at 40 ℃ for 12H to obtain H2. Wherein, the alpha-cyclodextrin in the solution A2: epoxy chloropropane: the weight ratio of the deionized water is 16: 8.85: 200.
preparation H3: following the procedure for preparation of H1 except that in step (a) gamma-cyclodextrin was used, the ratio of gamma-cyclodextrin: the weight ratio of the sodium hydroxide aqueous solution is 10: 40 to obtain a solution A3; in step (b) the reaction temperature was 35 ℃, the reaction time was 1h, the ratio of γ -cyclodextrin in solution a 3: epoxy chloropropane: the weight ratio of the deionized water is 10: 9.2: 200.
preparation H4: following the procedure for preparation of H1 except that, in step (a), the ratio of β -cyclodextrin: the weight ratio of the sodium hydroxide aqueous solution is 12: 40 to obtain a solution A4; in step (b), the beta-cyclodextrin in solution a 4: epoxy chloropropane: the weight ratio of the deionized water is 12: 15.2: 200.
preparation H5: following the procedure for preparation of H2 except that in step (a) gamma-cyclodextrin was used, the ratio of gamma-cyclodextrin: the weight ratio of the potassium hydroxide aqueous solution is 6: 40 to obtain a solution A5; reaction temperature in step (b) 35 ℃, γ -cyclodextrin in solution a 5: epoxy chloropropane: the weight ratio of the deionized water is 6: 2.2: 200.
preparation H6: the procedure for preparation of H1 was followed except that in step (a) α -cyclodextrin was used, α -cyclodextrin: the weight ratio of the sodium hydroxide aqueous solution is 4: 40 to obtain a solution A6; in step (b) the reaction temperature was 35 ℃, the reaction time 1h, the alpha-cyclodextrin in solution a 6: epoxy chloropropane: the weight ratio of the deionized water is 4: 1.4: 200.
in the case where no specific description is made, the materials used are those which are generally commercially available.
Example 1
(1) Adding deionized water, hydroxypropyl cyclodextrin H1 and 3-propylene isocyanate into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, dripping sulfuric acid, heating to 120 ℃, carrying out a first reaction for 8 hours at a stirring speed of 1000 revolutions per minute, repeatedly washing with deionized water after the reaction is finished to enable the pH value of the product to be about 7, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain a first product;
wherein, deionized water: hydroxypropyl cyclodextrin H1: 3-isocyanatopropylene: the weight ratio of the sulfuric acid is 100: 24: 43.2: 3;
(2) adding the first product, 2-acrylamide-2-methylpropanesulfonic acid sodium salt, allyl alcohol and acrylamide into deionized water, stirring to dissolve the raw materials, slowly pouring the mixture into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, heating to 75 ℃, adding an initiator (the weight ratio of potassium persulfate to sodium bisulfite is 1: 1), carrying out a second reaction at a stirring speed of 1000 rpm for 6h, repeatedly washing with deionized water after the reaction is finished, and carrying out vacuum drying at 60 ℃ for 12h to obtain modified cyclodextrin, wherein the modified cyclodextrin is recorded as SPT1 (molecular weight measured by a capillary viscometer is 274.8 million g/mol);
wherein, deionized water: a first product: sodium 2-acrylamido-2-methylpropanesulfonate: allyl alcohol: the weight ratio of acrylamide is 100: 16: 19.87: 6.7: 6.81; a first product: the weight ratio of the initiator is 32: 1.
example 2
(1) Adding deionized water, hydroxypropyl cyclodextrin H2 and 3-propylene isocyanate into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, dripping sulfuric acid, heating to 100 ℃, carrying out a first reaction for 6 hours at a stirring speed of 800 revolutions per minute, repeatedly washing with deionized water after the reaction is finished to enable the pH value of the product to be about 7, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain a first product;
wherein, deionized water: hydroxypropyl cyclodextrin H2: 3-isocyanatopropylene: the weight ratio of the sulfuric acid is 100: 28.3: 32.8: 2;
(2) adding the first product, sodium allylsulfonate, 2-ethyl-3-alkene butanol and acrylamide into deionized water, stirring to dissolve the raw materials, slowly pouring the mixture into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, heating to 70 ℃, adding an initiator (the weight ratio of ammonium persulfate to potassium sulfite is 2: 1, carrying out a second reaction for 5 hours at a stirring speed of 800 r/min, repeatedly washing with deionized water after the reaction is finished, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain modified cyclodextrin, wherein the modified cyclodextrin is recorded as SPT2 (molecular weight is 248.4 ten thousand g/mol in a capillary viscometer test);
wherein, deionized water: a first product: sodium allyl sulfonate: 2-ethyl-3-ene butanol: the weight ratio of acrylamide is 100: 9.25: 5.04: 9.76: 3.4; a first product: the weight ratio of the initiator is 30.8: 1.
example 3
(1) Adding deionized water, hydroxypropyl cyclodextrin H3 and 3-propylene isocyanate into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser tube, dripping p-toluenesulfonic acid, heating to 110 ℃, carrying out a first reaction for 7 hours at a stirring speed of 600 revolutions per minute, repeatedly washing with deionized water after the reaction is finished to enable the pH value of the product to be about 7, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain a first product;
wherein, deionized water: hydroxypropyl cyclodextrin H3: 3-isocyanatopropylene: the weight ratio of p-toluenesulfonic acid is 100: 25.3: 28.2: 3.75;
(2) adding the first product, sodium styrene sulfonate, methyl allyl alcohol and acrylamide into deionized water, stirring to dissolve the raw materials, slowly pouring the mixture into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, heating to 65 ℃, adding an initiator (the weight ratio of potassium persulfate to sodium thiosulfate is 3: 2), carrying out a second reaction for 4 hours at a stirring speed of 600 revolutions per minute, repeatedly washing with the deionized water after the reaction is finished, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain modified cyclodextrin, wherein the modified cyclodextrin is recorded as SPT3 (the molecular weight is 228.5 ten thousand g/mol in a capillary viscometer test);
wherein, deionized water: a first product: sodium styrene sulfonate: methallyl alcohol: the weight ratio of acrylamide is 100: 6: 3.4: 2.57: 3.6; a first product: the weight ratio of the initiator is 22: 1.
example 4
(1) Adding deionized water, hydroxypropyl cyclodextrin H4 and 3-propylene isocyanate into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, dripping p-toluenesulfonic acid, heating to 95 ℃, carrying out a first reaction for 4 hours at a stirring speed of 1400 rpm, repeatedly washing with deionized water after the reaction is finished to enable the pH value of the product to be about 7, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain a first product;
wherein, deionized water: hydroxypropyl cyclodextrin H4: 3-isocyanatopropylene: the weight ratio of p-toluenesulfonic acid is 100: 14.5: 18.5: 6.4;
(2) adding the first product, 2-acrylamide-2-methylpropanesulfonic acid sodium salt, methallyl alcohol and acrylamide into deionized water, stirring to dissolve the raw materials, slowly pouring the mixture into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, heating to 55 ℃, adding an initiator (the weight ratio of sodium persulfate to sodium bisulfite is 4: 3), carrying out a second reaction for 7 hours at a stirring speed of 1400 revolutions per minute, repeatedly washing with deionized water after the reaction is finished, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain modified cyclodextrin, which is recorded as SPT4 (the molecular weight is 187.8 ten thousand g/mol in a capillary viscometer test);
wherein, deionized water: a first product: sodium 2-acrylamido-2-methylpropanesulfonate: methallyl alcohol: the weight ratio of acrylamide is 100: 8: 8.28: 5.76: 4.2; a first product: the weight ratio of the initiator is 11.42: 1.
example 5
(1) Adding deionized water, hydroxypropyl cyclodextrin H5 and 3-propylene isocyanate into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser tube, dripping perchloric acid into the flask, heating the flask to 80 ℃, carrying out a first reaction for 2 hours at a stirring speed of 300 revolutions per minute, repeatedly washing the flask with deionized water after the reaction is finished to ensure that the pH value of the product is about 7, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain a first product;
wherein, deionized water: hydroxypropyl cyclodextrin H5: 3-isocyanatopropylene: the weight ratio of perchloric acid is 100: 33.2: 60.5: 8.7;
(2) adding the first product, sodium hydroxyvinyl sulfonate, 2-ethyl-3-alkene butanol and acrylamide into deionized water, stirring to dissolve the raw materials, slowly pouring the mixture into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, heating to 55 ℃, adding an initiator (the weight ratio of potassium persulfate to sodium thiosulfate is 2: 3), carrying out a second reaction at a stirring speed of 400 rpm for 8 hours, repeatedly washing with deionized water after the reaction is finished, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain modified cyclodextrin, wherein the modified cyclodextrin is recorded as SPT5 (molecular weight is 195.8 million g/mol in a capillary viscometer test);
wherein, deionized water: a first product: sodium hydroxyvinyl sulfonate: 2-ethyl-3-ene butanol: the weight ratio of acrylamide is 100: 6: 6.12: 10.72: 2.4; a first product: the weight ratio of the initiator is 12: 1.
example 6
(1) Adding deionized water, hydroxypropyl cyclodextrin H6 and 3-propylene isocyanate into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, dripping perchloric acid into the flask, heating the flask to 87 ℃, performing a first reaction for 11 hours at a stirring speed of 450 rpm, repeatedly washing the flask with deionized water after the reaction is finished to enable the pH value of the product to be about 7, and performing vacuum drying at 60 ℃ for 12 hours to obtain a first product;
wherein, deionized water: hydroxypropyl cyclodextrin H6: 3-isocyanatopropylene: the weight ratio of perchloric acid is 100: 19.8: 55.2: 7.8 of;
(2) adding the first product, sodium styrene sulfonate, propylene alcohol and acrylamide into deionized water, stirring to dissolve the raw materials, slowly pouring the mixture into a three-neck flask provided with a thermometer, a stirring rod and a reflux condenser, heating to 85 ℃, adding an initiator (the weight ratio of sodium persulfate to potassium thiosulfate is 1: 1), carrying out a second reaction for 3 hours at the stirring speed of 200 r/min, repeatedly washing with the deionized water after the reaction is finished, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain modified cyclodextrin, which is recorded as SPT6 (the molecular weight is 193.7 ten thousand g/mol in a capillary viscometer test);
wherein, deionized water: a first product: sodium styrene sulfonate: and (3) propylene alcohol: the weight ratio of acrylamide is 100: 6: 2: 5.1: 1.3; a first product: the weight ratio of the initiator is 15: 1.
comparative example 1
The procedure of example 1 was followed except that in step (1), β -cyclodextrin was used in place of hydroxypropyl cyclodextrin H1, and the other conditions were the same as in example 1. Product D1 (molecular weight 176.9 kg/mol according to capillary viscometer) was obtained.
Comparative example 2
The procedure of example 1 was followed except that acrylamide was not used in the step (2) and the other conditions were the same as in example 1. Product D2 (molecular weight 112.6 kg/mol in capillary viscometer) was obtained.
Comparative example 3
The procedure of example 1 was followed, except that in the step (1), acrylic acid was used in place of the 3-isocyanatopropene, and the other conditions were the same as in example 1. Product D3 (molecular weight 143.7 kg/mol as measured by capillary viscometer) was obtained.
Comparative example 4
The process of example 1 was followed except that, in step (2), deionized water: a first product: sodium 2-acrylamido-2-methylpropanesulfonate: allyl alcohol: the weight ratio of acrylamide is 100: 16: 42.2: 6.7: 6.81, the other conditions were the same as in example 1. The product D-4 (molecular weight 177.9 ten thousand g/mol as measured by capillary viscometer) was obtained.
Comparative example 5
The process of example 1 was followed except that, in step (2), deionized water: a first product: sodium 2-acrylamido-2-methylpropanesulfonate: allyl alcohol: the weight ratio of acrylamide is 100: 16: 19.87: 25.8: 6.81, the other conditions were the same as in example 1. The product D-5 (molecular weight 137.5 kg/mol in capillary viscometer) was obtained.
Comparative example 6
The process of example 1 was followed except that, in step (2), deionized water: a first product: sodium 2-acrylamido-2-methylpropanesulfonate: allyl alcohol: the weight ratio of acrylamide is 100: 16: 19.87: 6.7: 0.52, and the other conditions were the same as in example 1. The product D-6 (molecular weight 89.6 ten thousand g/mol as measured by capillary viscometer) was obtained.
Test example
The products of examples 1-6 and comparative examples 1-6 were used as flow pattern modifiers for water-based drilling fluids and tested for temperature resistance, salt resistance and compatibility and compared to the commercially available flow pattern modifier drisca-D (available from macbeth). In the following test examples, the following test examples were carried out,
the apparent viscosity (AV, mPas), the plastic viscosity (PV, mPas) were measured with a six-speed viscometer according to the method specified in GB/T29170-2012;
medium pressure fluid loss (API, mL) was measured using a medium pressure fluid loss gauge and according to the method specified in GB/T29170-2012;
the six-speed viscometer is manufactured by Qingdao Haitoda special instrument, model ZNN-D6;
the manufacturer of the medium-pressure filtration apparatus is Qingdao Haitongda special instrument company, model ZNS-2.
1. Temperature resistance
Preparing base slurry of the fresh water drilling fluid: 16g of Na-based bentonite for drilling fluid (purchased from Shandong Weifang Weihua bentonite company) and 400mL of distilled water are mixed, stirred at high speed for 30 minutes under the condition of 10000 r/min, and then kept stand for 24 hours in a closed container at room temperature to prepare 4% Na-based bentonite freshwater drilling fluid base slurry A (namely, every 100mL of water-based drilling fluid, the corresponding Na-based bentonite content is 4 g).
4g (i.e., 1% per 100mL of the base slurry A) of the products of examples 1 to 6 of the present invention and comparative examples 1 to 6 and a commercially available flow pattern modifier Driscal-D were added to 400mL of the base slurry A, and the rheological parameters (apparent viscosity, plastic viscosity) and medium pressure filtration loss of the drilling fluid before hot rolling (room temperature) and after hot rolling at 200 ℃ for 16 hours (after hot rolling to room temperature) were measured, and the viscosity retention rate was calculated according to equation 1, and the results are shown in Table 1.
Wherein:
η — viscosity retention,%;
AVAHR-apparent viscosity after hot rolling, mPa · s;
AVBHRapparent viscosity before hot rolling, mPas.
TABLE 1
Note: the hot rolling conditions in Table 1 were 200 ℃ for 16 hours.
As can be seen from Table 1, the addition of SPT1-SPT6 to drilling fluid base slurry A can significantly improve the viscosity of the drilling fluid, which indicates that the modified cyclodextrin flow pattern regulator provided by the invention has excellent tackifying performance. The rheological property and the filtration loss of the drilling fluid before and after hot rolling at 200 ℃ can be basically and effectively maintained, specifically, in the aspect of rheological property, the apparent viscosity of the drilling fluid is within the range of 30.5-35mPa before hot rolling at 200 ℃, the viscosity of the drilling fluid is slightly reduced after hot rolling at 200 ℃, the apparent viscosity can still be maintained within the range of 20.5-24.5mPa, and the viscosity retention rate is higher than 65%; in the aspect of filtration loss, the API filtration loss of the drilling fluid before and after 200 ℃ hot rolling is lower than 18mL, which shows that the modified cyclodextrin flow pattern regulator provided by the invention can resist the temperature of 200 ℃.
In contrast, although D1-D6 and the commercial flow pattern modifier Driscal-D also have tackifying performance, the rheological property of the drilling fluid is remarkably deteriorated after hot rolling at 200 ℃, the viscosity retention rate is lower than 60%, and the API (American Petroleum institute) filtration loss of the drilling fluid is also remarkably increased compared with that before hot rolling, namely the rheological property adjusting performance and the temperature resistance performance have remarkable differences from D1-D6.
2. Salt resistance
120g of sodium chloride is added into each 400mL of the base slurry A to obtain saturated brine base slurry B, then 4g of products prepared in examples 1-6 of the invention and comparative examples 1-6 and a commercially available flow pattern modifier Driscal-D are respectively added, the rheological parameters (apparent viscosity, plastic viscosity) and medium pressure filtration loss of the prepared saturated brine drilling fluid before hot rolling (room temperature) and after hot rolling at 200 ℃ for 16h (cooling to room temperature after hot rolling) are respectively tested, and the viscosity retention rate is calculated according to the formula 1, and the results are shown in Table 2.
TABLE 2
Note: the hot rolling conditions in Table 2 were 200 ℃ for 16 hours.
As can be seen from Table 2, the SPT1-SPT6 is added into the base slurry B of the saturated saline drilling fluid, the viscosity of the drilling fluid can still be remarkably improved, the apparent viscosity of the drilling fluid before hot rolling can reach about 30mPa & s, the apparent viscosity of the drilling fluid can still be kept about 20mPa & s after hot rolling at 200 ℃, and the viscosity retention rate is higher than 65%, so that the modified cyclodextrin flow pattern regulator provided by the invention has excellent salt resistance.
When the D1-D6 and the commercial flow pattern regulator Driscal-D are used in the saturated brine drilling fluid base slurry B, the apparent viscosity of the drilling fluid after hot rolling at 200 ℃ is lower than 14mPa & s, the viscosity retention rate is lower than 55%, namely, the salt resistance is obviously different from the D1-D6.
3. Compatibility of medicines
1.5g of sodium hydroxide, 8g of sulfonated phenolic resin SMP (purchased from Shandong Juxin Da chemical technology Co., Ltd.), 16g of lignite resin SPNH (purchased from Zhengzhou Yuhua auxiliary agent Co., Ltd.) and 120g of sodium chloride are sequentially added into every 400mL of the base slurry A to prepare the base slurry Z1 for the drilling fluid.
4g of each of the products obtained in examples 1 to 6 of the present invention and comparative examples 1 to 6 and a commercially available flow pattern modifier Driscal-D were added to 400mL of the base slurry Z1, and the rheological parameters (apparent viscosity, plastic viscosity) and medium pressure filtration loss of the drilling fluid obtained were measured before hot rolling (room temperature) and after hot rolling at 200 ℃ for 16 hours (after hot rolling to room temperature), respectively, and the viscosity retention was calculated according to equation 1, and the results are shown in Table 3.
TABLE 3
Note: the hot rolling conditions in Table 3 were 200 ℃ for 16 hours.
As can be seen from Table 3, the SPT1-SPT6 is added into the drilling fluid base slurry Z1 containing various additives, so that the viscosity of the drilling fluid can be still remarkably improved, the rheological property of the drilling fluid can be effectively maintained after the drilling fluid is hot rolled for 16 hours at 200 ℃, the viscosity retention rate is higher than 65%, and good compatibility is shown. SPT1-SPT6 has significant advantages over D1-D6 and Driscal-D in terms of a combination of temperature resistance, salt resistance and rheology modification.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (22)
1. A method for preparing modified cyclodextrin, the method comprising:
(1) in the presence of a catalyst, carrying out a first reaction on hydroxypropyl cyclodextrin and 3-propylene isocyanate in a first solvent to obtain a first product;
(2) in the presence of an initiator, carrying out a second reaction on the first product, a vinyl sulfonate monomer, an alkenyl alcohol monomer and acrylamide in a second solvent to obtain modified cyclodextrin; wherein,
in step (2), the second solvent: a first product: vinyl sulfonate monomer: alkenyl alcohol monomer: the weight ratio of acrylamide is 100: (1-30): (1-30): (1-20): (1-10).
2. The method of claim 1, wherein the vinyl sulfonate monomer is selected from at least one of sodium 2-acrylamido-2-methylpropane sulfonate, sodium allyl sulfonate, sodium styrene sulfonate, and sodium hydroxyvinyl sulfonate;
the alkenyl alcohol monomer is at least one selected from allyl alcohol, 2-ethyl-3-alkene butanol and methallyl alcohol.
3. The process according to claim 1 or 2, wherein, in step (1), the catalyst is selected from at least one of sulfuric acid, p-toluenesulfonic acid and perchloric acid;
and/or the first solvent is deionized water.
4. The process according to claim 1 or 2, wherein, in step (1), the first solvent: hydroxypropyl cyclodextrin: 3-isocyanatopropylene: the weight ratio of the catalyst is 100: (10-40): (10-70): (1-10);
and/or, the conditions of the first reaction comprise: the temperature is 80-140 ℃; the time is 2-12 h; the stirring rate was 200 ℃ and 1500 rpm.
5. The method of claim 4, wherein, in step (1), the first solvent: hydroxypropyl cyclodextrin: 3-isocyanatopropylene: the weight ratio of the catalyst is 100: (20-30): (25-50): (1-5);
and/or, the conditions of the first reaction comprise: the temperature is 100-120 ℃; the time is 6-8 h; the stirring speed is 600-1000 rpm.
6. The method of claim 3, wherein, in step (1), the first solvent: hydroxypropyl cyclodextrin: 3-isocyanatopropylene: the weight ratio of the catalyst is 100: (10-40): (10-70): (1-10);
and/or, the conditions of the first reaction comprise: the temperature is 80-140 ℃; the time is 2-12 h; the stirring rate was 200 ℃ and 1500 rpm.
7. The method of claim 6, wherein, in step (1), the first solvent: hydroxypropyl cyclodextrin: 3-isocyanatopropylene: the weight ratio of the catalyst is 100: (20-30): (25-50): (1-5);
and/or, the conditions of the first reaction comprise: the temperature is 100-120 ℃; the time is 6-8 h; the stirring speed is 600-1000 rpm.
8. The method according to any one of claims 1 to 2 and 5 to 7, wherein, in the step (2), the initiator consists of an oxidizing agent and a reducing agent, wherein the oxidizing agent is at least one of ammonium persulfate, potassium persulfate and sodium persulfate; the reducing agent is at least one of sodium bisulfite, potassium sulfite, sodium thiosulfate and potassium thiosulfate; the oxidant is: the mass ratio of the reducing agent is (0.5-2): 1;
and/or the second solvent is deionized water.
9. The method according to claim 3, wherein, in the step (2), the initiator consists of an oxidizing agent and a reducing agent, wherein the oxidizing agent is at least one of ammonium persulfate, potassium persulfate and sodium persulfate; the reducing agent is at least one of sodium bisulfite, potassium sulfite, sodium thiosulfate and potassium thiosulfate; the oxidant is: the mass ratio of the reducing agent is (0.5-2): 1;
and/or the second solvent is deionized water.
10. The method according to claim 4, wherein, in the step (2), the initiator consists of an oxidizing agent and a reducing agent, wherein the oxidizing agent is at least one of ammonium persulfate, potassium persulfate and sodium persulfate; the reducing agent is at least one of sodium bisulfite, potassium sulfite, sodium thiosulfate and potassium thiosulfate; the oxidant is: the mass ratio of the reducing agent is (0.5-2): 1;
and/or the second solvent is deionized water.
11. The method of any one of claims 1-2, 5-7, 9-10, wherein, in step (2), the second solvent: a first product: vinyl sulfonate monomer: alkenyl alcohol monomer: the weight ratio of acrylamide is 100: (5-20): (2-20): (2-10): (1-7);
and/or, the first product: the weight ratio of the initiator is (10-50): 1;
and/or, the conditions of the second reaction comprise: the temperature is 55-85 ℃; the time is 2-8 h; the stirring rate was 200 ℃ and 1500 rpm.
12. The method of claim 11, wherein, in step (2), the conditions of the second reaction comprise: the temperature is 60-80 ℃; the time is 4-6 h; the stirring speed is 600-1000 rpm.
13. The method of claim 3, wherein, in step (2), the second solvent: a first product: vinyl sulfonate monomer: alkenyl alcohol monomer: the weight ratio of acrylamide is 100: (5-20): (2-20): (2-10): (1-7);
and/or, the first product: the weight ratio of the initiator is (10-50): 1;
and/or, the conditions of the second reaction comprise: the temperature is 55-85 ℃; the time is 2-8 h; the stirring rate was 200 ℃ and 1500 rpm.
14. The method of claim 13, wherein, in step (2), the conditions of the second reaction comprise: the temperature is 60-80 ℃; the time is 4-6 h; the stirring speed is 600-1000 rpm.
15. The method of claim 4, wherein, in step (2), the second solvent: a first product: vinyl sulfonate monomer: alkenyl alcohol monomer: the weight ratio of acrylamide is 100: (5-20): (2-20): (2-10): (1-7);
and/or, the first product: the weight ratio of the initiator is (10-50): 1;
and/or, the conditions of the second reaction comprise: the temperature is 55-85 ℃; the time is 2-8 h; the stirring rate was 200 ℃ and 1500 rpm.
16. The method of claim 15, wherein, in step (2), the conditions of the second reaction comprise: the temperature is 60-80 ℃; the time is 4-6 h; the stirring speed is 600-1000 rpm.
17. The method of claim 8, wherein, in step (2), the second solvent: a first product: vinyl sulfonate monomer: alkenyl alcohol monomer: the weight ratio of acrylamide is 100: (5-20): (2-20): (2-10): (1-7);
and/or, the first product: the weight ratio of the initiator is (10-50): 1;
and/or, the conditions of the second reaction comprise: the temperature is 55-85 ℃; the time is 2-8 h; the stirring rate was 200 ℃ and 1500 rpm.
18. The method of claim 17, wherein, in step (2), the conditions of the second reaction comprise: the temperature is 60-80 ℃; the time is 4-6 h; the stirring speed is 600-1000 rpm.
19. A modified cyclodextrin prepared by the method of any one of claims 1-18.
20. The modified cyclodextrin of claim 19, wherein the modified cyclodextrin has a star-shaped structure and an average molecular weight of 180 to 300 million g/mol.
21. An aqueous drilling fluid comprising the modified cyclodextrin of claim 19 or 20.
22. Use of a modified cyclodextrin as claimed in claim 19 or 20 as a flow pattern modifier in an aqueous drilling fluid.
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