CN107973730B - Oligo polyanion sulfonate surfactant, preparation method and application thereof - Google Patents
Oligo polyanion sulfonate surfactant, preparation method and application thereof Download PDFInfo
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- CN107973730B CN107973730B CN201610939265.7A CN201610939265A CN107973730B CN 107973730 B CN107973730 B CN 107973730B CN 201610939265 A CN201610939265 A CN 201610939265A CN 107973730 B CN107973730 B CN 107973730B
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- surfactant
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- solvent
- sulfonate
- amine
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 88
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000447 polyanionic polymer Polymers 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 229960001701 chloroform Drugs 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000006277 sulfonation reaction Methods 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- 150000003871 sulfonates Chemical class 0.000 claims 1
- -1 anion sulfonate Chemical class 0.000 abstract description 23
- 238000004220 aggregation Methods 0.000 abstract description 15
- 230000002776 aggregation Effects 0.000 abstract description 14
- 125000000129 anionic group Chemical group 0.000 abstract description 14
- 238000006384 oligomerization reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 125000005647 linker group Chemical group 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000003945 anionic surfactant Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 9
- 125000001072 heteroaryl group Chemical group 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 239000000693 micelle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- IOHJQSFEAYDZGF-UHFFFAOYSA-N 2-dodecyloxirane Chemical compound CCCCCCCCCCCCC1CO1 IOHJQSFEAYDZGF-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- 125000004514 1,2,4-thiadiazolyl group Chemical group 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BQOWUDKEXDCGQS-UHFFFAOYSA-N [CH]1CCCC1 Chemical group [CH]1CCCC1 BQOWUDKEXDCGQS-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002009 alkene group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- BNBQRQQYDMDJAH-UHFFFAOYSA-N benzodioxan Chemical compound C1=CC=C2OCCOC2=C1 BNBQRQQYDMDJAH-UHFFFAOYSA-N 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
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- 238000012637 gene transfection Methods 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000000111 isothermal titration calorimetry Methods 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- BUGOPWGPQGYYGR-UHFFFAOYSA-N thiane 1,1-dioxide Chemical compound O=S1(=O)CCCCC1 BUGOPWGPQGYYGR-UHFFFAOYSA-N 0.000 description 1
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- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
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Abstract
本发明提供一种寡聚阴离子磺酸盐表面活性剂、其制备方法和用途。所述寡聚阴离子磺酸盐具有选自下式I～式V所示的结构：
The present invention provides an oligomeric anionic sulfonate surfactant, its preparation method and application. The oligomeric anion sulfonate has a structure selected from the following formulas I to V:
Description
Technical Field
The invention belongs to the field of surfactant science and application, and particularly relates to an oligo-polyanion sulfonate surfactant, a preparation method and application thereof.
Background
The traditional surfactant is an amphiphilic molecule consisting of a hydrophilic head group and a hydrophobic tail chain, and is widely applied to the fields of daily chemicals, foods, oil fields and the like. On the basis, two or more than two amphiphilic elements are connected on the head group or the position close to the head group by a connecting group in a chemical bond mode, and the dimeric (commonly called Gemini surfactant), trimeric, tetrameric and oligomeric surfactant with higher oligomerization degree is obtained. The Gemini surfactant has the characteristics superior to those of the traditional single-chain surfactant, such as lower Critical Micelle Concentration (CMC), higher surface activity, lower Krafft point, excellent rheological property, novel and various aggregate structures, better wetting effect and the like, and has stronger capacity in the aspects of washing, sterilization, emulsification, dispersion, corrosion prevention and the like, thereby showing great application potential in the fields of personal care products, tertiary oil recovery, gene transfection, drug occlusion and release, food industry, phase transfer catalysis, sterilization and antibiosis, synthesis of ordered mesoporous materials and the like. The oligomeric surfactant contains more amphiphilic elements in the molecular structure, so that the performance of the oligomeric surfactant is further improved on the basis of the traditional single-chain and Gemini surfactants, namely the oligomeric surfactant is lower in critical micelle concentration, stronger in self-aggregation capability, richer in aggregation behavior and the like. Meanwhile, the controllable factor of a linking group structure is introduced on the basis of the Gemini surfactant. Oligomeric surfactants can be classified into three types, linear, star-shaped, or cyclic, depending on the structure and characteristics of the linking group. Such as linear trimeric and tetrameric cationic quaternary ammonium salt surfactants (12-3-12-3-12 and 12-3-12-4-12-3-12) can form branched linear micelles and closed ring structures; and the star-shaped oligomeric cationic quaternary ammonium salt surfactant molecules can generate the change of molecular conformation along with the increase of concentration, and induce the conversion of the reticular pre-micelle to the spherical aggregate and micelle. Therefore, the degree of oligomerization and the linking group simultaneously influence the unique self-assembly rule of the oligomeric surfactant, which not only provides possibility for constructing more kinds of aggregate structures, but also creates a new way for realizing the conversion of molecular conformation and aggregate structure by changing concentration in a single surfactant system.
Anionic surfactants are the most widely used surfactants with the longest history, and can be classified into four categories, i.e., sulfonate, sulfate, carboxylate and phosphate, according to the difference of hydrophilic head groups. Two or more single-head single-chain anionic surfactant molecules are connected by a linking group on or close to a head group in a chemical bond mode to obtain the Gemini or oligomeric anionic surfactant. Compared with the traditional single-chain anionic surfactant, the anionic Gemini surfactant has stronger surface activity, better wetting property, calcium soap dispersing capacity and foam stability, and the critical micelle concentration of the anionic Gemini surfactant is reduced by orders of magnitude compared with the traditional single-chain anionic surfactant. However, the types of the oligomeric anionic surfactants reported in the literature are few. Few research results have preliminarily shown that the improvement of the degree of oligomerization can further reduce CMC, improve surface activity and aggregation capability on the basis of Gemini surfactant, and form richer aggregate structures, wherein the oligomeric anionic surfactant with rigid linking groups can form pre-micelles at an extremely low concentration. However, due to the limited kinds and limited degree of oligomerization of the oligo-anionic surfactants, systematic research and understanding on the influence of structural factors such as linking groups and degree of oligomerization are still lacking, and the fundamental reasons are that the existing synthetic routes are complex, separation and purification are difficult, and the yield is low. The anionic sulfonate surfactant is one of anionic surfactants which are widely applied, and has the characteristics of strong surface activity, low Krafft point, strong salt resistance, high temperature resistance and the like. At present, a relatively mature method for synthesizing an oligo-anionic sulfonate surfactant is proposed by Masuyama, a. subject group of japan, and a synthetic route thereof includes that polyhydric alcohol and epichlorohydrin generate an intermediate tri-epoxy compound through electrophilic substitution, the tri-epoxy compound and long-chain fatty alcohol potassium undergo a ring opening reaction to obtain an intermediate oligo-polyol containing trialkyl chain trihydroxy, and finally the oligo-polyol undergoes a sulfonation reaction with 1, 3-propanesultone to obtain a product of the tri-anionic sulfonate surfactant:
the subject group Zhou, M. of the southwest oil university in China synthesizes the trimeric sulfonate anionic surfactant by a similar method, and the synthetic route is as follows:
although the synthesis method is feasible, the synthesis method still has a plurality of defects: (1) the solvent DMSO used in the first step of the reaction makes the post-treatment difficult, and if a phase transfer catalyst is used, the yield is reduced; (2) in the second step, the use of active metal simple substance potassium causes great reaction danger and needs no water protection; (3) the reaction uses polyhydric alcohol as a raw material, and the diversity of molecular structures is limited. The defects of the method for preparing the oligoanion sulfonate surfactant urgently need to be further improved, and a preparation method with mild reaction conditions, simple post-treatment and more diverse product structures is found, so that the method not only has important theoretical research significance, but also is beneficial to expanding the application value of the oligoanion surfactant. Therefore, the search for new oligomeric anionic surfactants and the simple and efficient preparation method are the key points for promoting the property research and industrial application of the oligomeric anionic surfactants. On the basis, the invention provides an oligo-polyanion sulfonate surfactant, a preparation method and application thereof.
Disclosure of Invention
To achieve the above objects, the present invention provides a method for preparing an oligoanionic sulfonate surfactant having a structure selected from the group consisting of the following formulas I to V:
wherein R is1One selected from the following structures:
R2is unsubstituted or optionally substituted by one or more R5Substituted straight or branched C8-22An alkyl group;
R5selected from unsubstituted or optionally substituted by one or more R6Substituted C8-22Alkyl radical, C8-22Cycloalkyl radical, C8-22Alkyloxy, C8-22Cycloalkyl oxy, C8-22Alkenyl radical, C8-22An alkenyloxy group;
R6is selected from C8-22Alkyl radical, C8-22Alkoxy radical, C8-22An alkenyl group;
as an example, R2May be selected from one of the following structures:
R3selected from straight or branched C2-20Alkylene, wherein one or more carbon atoms of the alkylene may optionally be replaced by O, S, N, and/or may optionally be replaced by O, S, C3-20Cycloalkyl radical, C6-20Aryl radical, C5-20Heteroaryl group, C3-20One or more of the heterocyclic groups.
As an example, R3May be selected from one of the following structures:
R4is selected from C2-20Alkylene radical, C3-20Cycloalkylene radical, C6-20Arylene radical, C5-20Heteroarylene group, C5-20Heterocycloalkylene.
As an example, R4May be selected from one of the following structures:
m is a cation, e.g. Na+Or K+；
x is a natural number of 1-10, such as 1 or 2.
The invention also provides a preparation method of the oligo polyanion sulfonate surfactant, which comprises the following steps:
1) reacting amine with 1, 2-alkylene oxide to obtain intermediate oligo-polyol;
2) and (3) carrying out sulfonation reaction on the intermediate oligomeric alcohol and 1, 3-propane sultone.
According to the preparation method of the present invention, the amine, the 1, 2-alkylene oxide and the 1, 3-propane sultone can be commercially available chemical reagents or prepared according to methods known in the art.
According to the invention, the reaction of step 1) is a ring-opening reaction.
According to the preparation process of the present invention, the amine may be a primary or secondary amine, such as a diamine or polyamine. Preferably, the amine is selected from one or more of the following structures:
according to the preparation method of the invention, the 1, 2-alkylene oxide has the structural formula
As an example, the 1, 2-alkylene oxide may be
Wherein R is2Having the definitions described above; for example, one or more selected from the following structures:
according to the production method of the present invention, the molar ratio of the 1, 2-alkylene oxide to the N-H bond in the molecule of the starting amine is preferably (1-10): 1, for example (1-2): 1.
According to the production method of the present invention, the starting amine and the 1, 2-alkylene oxide may be reacted in an organic solvent. Preferably, the solvent may be selected from one or more of methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, n-hexane, toluene, benzene or diethyl ether.
According to the preparation method, in the reaction process of the amine and the 1, 2-alkylene oxide, the temperature can be 0-150 ℃, and the reaction time can be 4-72 hours.
According to the preparation method, the molar ratio of the sulfonation reaction raw material 1, 3-propanesultone to the intramolecular hydroxyl of the intermediate oligomer alcohol can be (1-20): 1, such as (1.2-2): 1.
According to the preparation method of the invention, the reaction of the intermediate oligoalcohol and 1, 3-propane sultone is carried out in a solvent; preferably, the solvent may be selected from one or more of tetrahydrofuran, chloroform, dichloromethane or toluene.
According to the preparation method of the present invention, the reaction of the intermediate oligohydrin with 1, 3-propanesultone can be carried out under reflux conditions, and preferably the reaction is always carried out under reflux conditions. Preferably, the reaction time may be 12 to 480 hours, for example 24 to 120 hours.
According to the scheme, after the sulfonation reaction of the intermediate oligo-alcohol and the 1, 3-propane sultone is finished, methanol or ethanol is added to finish the reaction. Preferably, the solvent is removed and the residue is recrystallized to yield the product.
The removal solvent may be removed by evaporation, for example by rotary evaporation.
The solvent for recrystallization is preferably an alcoholic solvent, a ketone solvent or a mixture thereof, for example selected from methanol, ethanol, acetone or a mixture thereof.
The invention also provides the use of the oligoanionic sulphonate surfactant.
Preferably, the oligoanion sulfonate can be used as a surfactant in the environment containing polyvalent metal ions such as calcium and magnesium ions, such as the fields of petroleum exploitation, daily chemicals, textile printing and dyeing and the like.
Term interpretation and description
Unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. Such combinations and definitions of groups and structures of compounds after combination are intended to fall within the scope of the present application.
Where a range of numerical values is recited in the specification and claims herein, and where the range of numerical values is defined as an "integer," it is understood that the two endpoints of the range are recited and each integer within the range is recited. For example, "an integer of 0 to 10" should be understood to describe each integer of 0, 1,2, 3, 4, 5, 6, 7, 8, 9, and 10. When a range of values is defined as "a number," it is understood that the two endpoints of the range, each integer within the range, and each decimal within the range are recited. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1,2, 3, 4, 5, 6, 7, 8, 9, and 10, but also to recite at least the sum of each integer and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
"alkyl" as used herein alone or as a suffix or prefix, is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. For example, "C8-22Alkyl "denotes straight and branched chain alkyl groups having 8 to 22 carbon atoms. C8-22The alkyl radical may be chosen in particular from C8-22Straight chain alkyl or C8-22Branched alkyl groups, examples of which include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.
"alkenyl" as used herein alone or as a suffix or prefix, is intended to include both branched and straight chain aliphatic hydrocarbon groups containing alkenyl or alkene groups having the indicated number of carbon atoms. For example, "C8-22Alkenyl "means alkenyl having 8 to 22 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, 3-methylbut-1-enyl, 1-pentenyl, 3-pentenyl, and 4-hexenyl.
The term "cycloalkyl" as used herein is intended to include saturated cyclic groups having the specified number of carbon atoms. These terms may include fused or bridged polycyclic ring systems. Cycloalkyl groups have 3 to 20 carbon atoms in their ring structure. In one embodiment, the cycloalkyl group has 3 to 20 carbon atoms in its ring structure. For example, "C3-6Cycloalkyl "denotes for example cyclopropyl, cyclobutyl, cycloPentyl or cyclohexyl radicals.
The term "aryl" as used herein refers to an aromatic ring structure made up of 6 to 20 carbon atoms. For example: the aromatic ring structure containing 6, 7 and 8 carbon atoms may be a monocyclic aromatic group such as phenyl; the ring structure containing 8, 9, 10, 11, 12, 13 or 14 carbon atoms may be polycyclic, for example naphthyl. The aromatic ring may be substituted at one or more ring positions with those substituents described above.
The term "aryl" also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (the rings are "fused rings"), wherein at least one of the rings is aromatic and the other cyclic rings can be, for example, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and/or heterocyclyl. Examples of polycyclic rings include, but are not limited to, 2, 3-dihydro-1, 4-benzodioxine and 2, 3-dihydro-1-benzofuran.
As used herein, "heteroaryl" refers to a heteroaromatic heterocycle having at least one ring heteroatom (e.g., sulfur, oxygen, or nitrogen). Heteroaryl groups include monocyclic ring systems and polycyclic ring systems (e.g., having 2,3, or 4 fused rings). Examples of heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, quinolinyl, isoquinolinyl, thienyl, imidazolyl, thiazolyl, indolyl, pyrrolyl, oxazolyl, benzofuryl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, triazolyl, tetrazolyl, indazolyl, 1,2, 4-thiadiazolyl, isothiazolyl, benzothienyl, purinyl, carbazolyl, benzimidazolyl, benzoxazolyl, azabenzoxazolyl, imidazothiazolyl, benzo [1,4] dioxanyl, benzo [1,3] dioxolyl, and the like. In some embodiments, heteroaryl groups have from 3 to 20 carbon atoms and in other embodiments from 3 to 20 carbon atoms. In some embodiments, heteroaryl groups contain 3 to 14, 4 to 14, 3 to 7, or 5 to 6 ring-forming atoms. In some embodiments, heteroaryl has 1 to 4, 1 to 3, or 1 to 2 heteroatoms. In some embodiments, the heteroaryl group has 1 heteroatom.
The term "heterocyclyl" as used herein, refers to a saturated, unsaturated or partially saturated monocyclic, bicyclic or tricyclic ring containing from 3 to 20 atoms, wherein 1,2, 3, 4 or 5 ring atoms are selected from N, S or O, which may be attached through carbon or nitrogen, unless otherwise specified. It is understood that when the total number of S and O atoms in the heterocyclic group exceeds 1, these heteroatoms are not adjacent to each other. If the heterocyclyl is bicyclic or tricyclic, at least one ring may optionally be a heteroaromatic ring or an aromatic ring, provided that at least one ring is non-heteroaromatic. If the heterocyclic group is monocyclic, it is not necessarily aromatic. Examples of heterocyclyl groups include, but are not limited to, piperidinyl, N-acetylpiperidinyl, N-methylpiperidinyl, N-formylpiperazinyl, N-methylsulfonylpiperazinyl, homopiperazinyl, piperazinyl, azetidinyl, oxetanyl, morpholinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, indolinyl, tetrahydropyranyl, dihydro-2H-pyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiopyran-1-oxide, tetrahydrothiopyran-1, 1-dioxide, 1H-pyridin-2-one, and 2, 5-dioxoimidazolidinyl.
One or more of the carbon atoms described herein may be optionally substituted with O, S, meaning that the carbon atom forms a carbonyl or thiol group with O or S, respectively.
According to the present invention, the solvent used may be an anhydrous solvent unless otherwise specified.
Advantageous effects
The invention takes amine, 1, 2-alkylene oxide and 1, 3-propane sultone as raw materials, and prepares a class of oligo-anionic sulfonate surfactants with different oligomerization degrees, different alkyl chain lengths and different linking group structures through two steps of ring-opening reaction and sulfonation reaction. The preparation process provided by the invention is simple, the reaction condition is mild, the reaction period is short, the post-treatment is simple, and the industrial production is easy to realize. The obtained product has good surface activity and aggregation behavior, and has wider application field.
Drawings
FIG. 1 is a nuclear magnetic resonance of a polyanionic sulfonate surfactant prepared in example 1 of the present invention1H NMR spectrum.
FIG. 2 is an ESI mass spectrum of a polyanionic sulfonate surfactant prepared in example 1 of the present invention.
FIG. 3 is a nuclear magnetic resonance of a tetra-polyanionic sulfonate surfactant prepared in example 2 of the present invention1H NMR spectrum.
FIG. 4 is a high resolution ESI mass spectrum of the tetra poly (anionic sulfonate) surfactant prepared in example 2 of the present invention.
FIG. 5 is a nuclear magnetic resonance of a hexapolyanionic sulfonate surfactant prepared in example 3 of the present invention1H NMR spectrum.
FIG. 6 is a high resolution ESI mass spectrum of a hexa-polyanionic sulfonate surfactant prepared in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments, and the embodiments described herein are only for explaining the present invention and are not intended to limit the present invention.
In the following examples, all reagents used were commercial chemicals unless otherwise specified.
The structures and abbreviations of the oligo anionic sulfonate surfactants described in examples 1-6 are shown in Table 1:
table 1 dimeric, tetrameric, and hexameric anionic sulfonate surfactant molecular structures.
Example 1:
polyanionic disulfonate DMDEA- (C)12SO3Na)2The preparation of (1):
(1) the synthesis steps of intermediate product dihydric alcohol: 0.9g (10.0mmol) of N, N' -dimethylethylenediamine was added to a solution of 6.4g (30.0mmol) of 1, 2-epoxytetradecane in 50ml of absolute ethanol and reacted at 90 ℃ for 24 hours. After the reaction is finished, removing the absolute ethyl alcohol solvent by using a rotary evaporator, dissolving the crude product in trichloromethane, then eluting and refining the crude product by using trichloromethane/methanol through a silica gel chromatographic column, and drying the refined product in vacuum to obtain the intermediate diol.
MALDI-TOF characterises the intermediate diol: 513.5(M + H).
(2) Polyanionic sulfonate surfactant DMDEA- (C)12SO3Na)2The synthesis steps are as follows: 0.3g (60%, 7.5mmol) of sodium hydride, 1.0g (8.2mmol) of 1, 3-propanesultone and 0.5g (1.0mmol) of intermediate diol are dissolved in THF, refluxed for 48 hours and then quenched by addition of methanol. And (4) removing the solvent by rotary evaporation, and recrystallizing the crude product in methanol/acetone to obtain a pure product.
The polyanionic sulfonate surfactant prepared in this example1H NMR results:1H NMR(CD3OD，400MHz)：δ＝0.900(t，6H，-CH3)，1.295-1.586(m，44H，CH3-(CH2)11-CH-)，2.036(m，4H，-O-CH2-CH2-CH2SO3Na)，2.642(s，6H，-N-CH3)，2.825-3.060(m，10H，-N-CH2-CH2-N-，-N-CH2-CH-)，3.600-3.697(m，8H，-O-CH2-CH2-CH2SO3Na)。MS-ESI(m/z)：Calcd 800.50；Found755.6([M-Na+]-)，377.5([M-2Na+]2-/2)。1the results of H NMR and MS-ESI show that the product is consistent with the target product.
Example 2:
tetrapolyanionic sulfonate surfactant EDA- (C)12SO3Na)4The preparation of (1):
(1) the synthesis of intermediate product tetrol: 0.6g (10.0mmol) of ethylenediamine was added to a solution of 12.7g (60.0mmol) of 1, 2-epoxytetradecane in 50ml of absolute ethanol and reacted at 90 ℃ for 24 hours. After the reaction is finished, removing the absolute ethyl alcohol solvent by using a rotary evaporator, dissolving the crude product in trichloromethane, then eluting and refining the crude product by using trichloromethane/methanol through a silica gel chromatographic column and drying the crude product in vacuum to obtain white powdery intermediate tetrahydric alcohol, wherein the yield is 99%.
MALDI-TOF characterises the intermediate tetrapolyol: 910.1(M + H).
(2) Tetrapolyanionic sulfonate surfactant EDA- (C)12SO3Na)4The synthesis steps are as follows: 0.6g (60%, 15.0mmol) of sodium hydride, 2.0g (16.4mmol) of 1, 3-propanesultone and 0.9g (1.0mmol) of intermediate tetrapolyol were dissolved in THF, refluxed for 48 hours, and then quenched by addition of methanol. The solvent was removed by rotary evaporation and the crude product was recrystallized from methanol/acetone to give 0.8g of pure product in 54% yield.
Preparation of the Tetrapolyanionic sulfonate surfactant prepared in this example1H NMR results:1H NMR(CD3OD，400MHz)：δ＝0.904(t，12H，CH3-)，1.301-1.677(m，88H，CH3-(CH2)11-CH-)，2.028(m，8H，-O-CH2-CH2-CH2SO3Na)，2.300-2.750(m，8H，-N-CH2-CH-)，2.885(m，8H，-N-CH2-CH2-N-，-N-CH2-CH-)，3.533-3.677(m，16H，-O-CH2-CH2-CH2SO3Na)。MS-ESI(m/z)：Calcd1484.87；Found464.63933([M-4Na++H+]3-/3)。1the results of H NMR and MS-ESI show that the product is consistent with the target product.
Example 3:
hexapolyanionic sulfonate surfactant TAEA- (C)12SO3Na)6The preparation of (1):
(1) the synthesis of intermediate product hexahydric alcohol comprises the following steps: tris (2-aminoethyl) amine (1.5 g, 10.0mmol) was added to a solution of 1, 2-epoxytetradecane (19.1 g, 90.0mmol) in absolute ethanol (50ml) and reacted at 90 ℃ for 24 h. After the reaction is finished, removing the absolute ethyl alcohol solvent by using a rotary evaporator, dissolving the crude product in trichloromethane, then eluting and refining the crude product by using trichloromethane/methanol through a silica gel chromatographic column, and drying the crude product in vacuum to obtain the intermediate hexaol.
MALDI-TOF characterises the intermediate hexameric alcohol: 1420.6(M + H).
(2) Hexapolyanionic sulfonate surfactant TAEA- (C)12SO3Na)6The synthesis steps are as follows: 1.0g (60%, 25mmol) of sodium hydride, 2.9g (23.7mmol) of 1, 3-propanesultone and 1.4g (1.0mmol) of intermediate hexahydric alcohol were dissolved in THF, refluxed for 48 hours and then quenched by addition of methanol. And (4) removing the solvent by rotary evaporation, and recrystallizing the crude product in methanol/acetone to obtain a pure product.
Preparation of the hexapolyanionic sulfonate surfactant prepared in this example1H NMR results:1H NMR(CD3OD，400MHz)：δ＝0.903(t，18H，CH3-)，1.299(m，132H，CH3-(CH2)11-CH-)，2.023-2.222(m，12H，-O-CH2-CH2-CH2SO3Na)，2.350-2.800(m，12H，-N-CH2-CH-)，2.896(m，18H，-N-CH2-CH2-N-，-N-CH2-CH-)，3.445-3.678(m，24H，-O-CH2-CH2-CH2SO3Na)。MS-ESI(m/z)：Calcd 2283.35；Found716.48166([M-6Na++3H+]3-/3)。1the results of H NMR and MS-ESI show that the product is consistent with the target product.
Because oligomeric surfactants have a strong aggregating power and typically have multiple aggregate transitions with increasing concentration, oligomeric surfactants may have two or more Critical Aggregation Concentrations (CAC) that can be measured by a variety of experimental means. The critical aggregation concentrations of anionic sulfonate surfactants of different oligomerities obtained by three experimental means of surface tension, conductance and isothermal titration microcalorimetry are presented in examples 4 to 6, respectively, and the results are summarized in table 2.
Example 4:
the surface tension was measured by the drop volume method. To completely ionize the sulfonate head group of the surfactant, all concentrations were dissolvedThe pH of the solution was controlled at 8.50. To achieve surface adsorption equilibrium, each measurement was performed in two steps: first, a quantity of droplets having a volume of about 90% of the total droplet volume is extruded from a burette; the drop suspended from the orifice is then allowed to hang for a sufficient time until it naturally drips. Each surface tension value (γ) is repeated five or more times and each surface tension curve is repeated three times. The test temperature was controlled at 25.00. + -. 0.05 ℃. Respectively measuring DMEDA- (C) with different concentrations by a drop volume method12SO3Na)2、EDA-(C12SO3Na)4And TAEA- (C)12SO3Na)6The turning point of the obtained surface tension-concentration logarithm (gamma-logc) curve is defined as the critical aggregation concentration of the surfactant.
Example 5:
the conductance test was used to determine the critical aggregation concentration of anionic sulphonate surfactants of different oligomerisation degrees. Conductivity values of the surfactant at different concentrations were measured by a conductivity meter model JENWAY model 4320. The high concentration surfactant solution was added continuously to 7.00ml of water at pH8.50 and the conductivity meter reading was read after the system had fully equilibrated. In the experimental process, circulating water is introduced into the double-layer glassware to keep the temperature at 25.0 +/-0.1 ℃. Separately measuring DMDAA- (C)12SO3Na)2、EDA-(C12SO3Na)4And TAEA- (C)12SO3Na)6The turning point of the conductance-concentration (kappa-c) curve obtained by conductance values at different concentrations is the critical aggregation concentration of the surfactant.
Example 6:
TAM III isothermal titration microcalorimeters were used to determine the critical aggregation concentrations of the different oligomeric anionic sulfonate surfactants prepared in the examples. The calorimeter cell was initially filled with 600. mu.l of pH8.50 water. The high concentration surfactant solution was added dropwise to the sample cell via a 500. mu.l Hamilton syringe controlled by a Thermometric 612Lund pump. The stirring rate was maintained at 60rpm throughout the titration period and sufficient time was maintained between successive drops to ensure that the signal returned to baseline. Observation of enthalpy (Δ H)obs) The critical aggregation concentration value is determined by an extreme value obtained by carrying out primary differentiation on a titration curve. All experiments were repeated at least twice with errors below ± 4%. The experimental temperature was controlled to be constant at 25.00 + -0.01 deg.C.
Table 2.25 ℃ critical aggregation concentration of anionic sulfonate surfactants of different oligomerities in aqueous solutions at pH 8.50.
Table 2 shows the Critical Aggregation Concentration (CAC) values for the oligoanionic sulfonate surfactant obtained from calorimetric, surface tension and conductance experiments. Studies have shown that the polyanionic sulfonate surfactant (DMDEA- (C))12SO3Na)2) There is only one aggregate transition. To increase the degree of oligomerization to tetramerization (EDA- (C)12SO3Na)4) And hexamer (TAEA- (C)12SO3Na)6) When the tetrameric and hexameric anionic sulphonate surfactants had two aggregate transition processes within the concentration range studied, the two critical aggregate concentrations were defined as CAC respectively1And CAC2(see Table 2). On the other hand, the three oligo anion Sulfonate surfactants prepared in this patent all have a one to two order of magnitude decrease in CAC as compared to the single-head single-chain Sulfonate surfactant Sodium Dodecyl sulfate reported in the literature (Hou Z., Li Z., Wang H. interaction Between PolyE and Sodium Dodecyl sulfate by Surface Tension, Conductivity, Viscosity, Electron Spin response and Nuclear Magnetic response, Cold Polymer.Sci.1999, 277: 1011-1018.). Also, the CAC of the hexa-polyanionic sulfonate surfactant was reduced by an order of magnitude compared to the dimeric and tetra-polyanionic sulfonate surfactants. Thus, the increase in the degree of oligomerization enhances the aggregating ability of the anionic sulfonate surfactant and the aggregate transition process is more abundant.
The surfactant is inevitably influenced by polyvalent metal ions such as calcium and magnesium ions in the using process, and even in hard water containing higher calcium and magnesium ion concentration, the surfactant is ineffective due to precipitation, so that the improvement of the tolerance of the surfactant to the polyvalent metal ions is very important in practical application. The polyvalent metal ions include ions of divalent or higher valent metals, such as: divalent metal ions include, but are not limited to, calcium, magnesium, copper, zinc, manganese, nickel, cobalt, mercury ions, and the like; high valence metal ions include, but are not limited to, iron, aluminum, chromium ions, and the like. Experiments prove that the polyanionic sulfonate surfactant has more sulfonate head groups and tertiary amine as chelating groups in molecules, and the polyvalent metal ion binding capacity of the polyanionic sulfonate surfactant is greatly improved compared with that of the traditional surfactant, so that the surfactant has stronger tolerance to polyvalent metal ions such as calcium and magnesium ions.
On the other hand, in the fields of emulsification and viscosity reduction of thick oil, daily chemicals, and the like, it is desired to obtain an emulsifier having high efficiency and low consumption. In general, conventional single-chain surfactants and Gemini surfactants are used as a single emulsifier, and are difficult to form an emulsion with other oil phases under the condition of low concentration. However, experiments prove that the oligomeric surfactant has a plurality of hydrophobic tail chains and shows strong aggregation capability at low concentration, so that the emulsifying capability and the stability of the formed oil-water interfacial film are enhanced, and the emulsifying property is further improved. The advantages lead the oligomeric sulfonate surfactant to have great potential in the fields of petroleum exploitation, daily chemicals, textile printing and dyeing and the like.
Through verification, the upper limit value and the lower limit value and the interval value of each raw material can realize the invention, and the lower limit value and the interval value of the related process parameters (such as temperature, time and the like) can realize the invention, and are not repeated herein.
Claims (15)
1. An oligoanionic sulfonate having a structure selected from the group consisting of those represented by formulas I through V below:
wherein，R1One selected from the following structures:
R2is unsubstituted or optionally substituted by one or more R5Substituted straight or branched C8-22An alkyl group;
R5is selected from C8-22Alkyl radical, C8-22An alkyloxy group;
R3selected from straight or branched C2-20An alkylene group;
R4is selected from
M is Na+Or K+；
x is selected from 1 or 2.
2. The oligopolyanionic sulfonate of claim 1, wherein:
R2one selected from the following structures:
R3one selected from the following structures:
3. the process for the preparation of oligoanionic sulfonates according to claim 1, comprising:
1) reacting amine with 1, 2-alkylene oxide to obtain intermediate oligo-polyol;
2) carrying out sulfonation reaction on the intermediate oligomeric alcohol and 1, 3-propane sultone;
wherein the amine is selected from one or more of the following structures:
said 1, 2-alkylene oxide is
Wherein R is2Having the definition as claimed in claim 1 or 2.
4. The production method according to claim 3, wherein:
the molar ratio of the 1, 2-alkylene oxide to the N-H bond in the amine molecule is (1-10) to 1;
the amine is reacted with a 1, 2-alkylene oxide in an organic solvent.
5. The method according to claim 4, wherein the organic solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, n-hexane, toluene, benzene or diethyl ether.
6. The method according to claim 5, wherein the reaction of the amine with the 1, 2-alkylene oxide is carried out at a temperature of 0 to 150 ℃ for a reaction time of 4 to 72 hours.
7. The production method according to any one of claims 3 to 6, wherein:
the molar ratio of 1, 3-propane sultone serving as a raw material of the sulfonation reaction to hydroxyl in the oligomer molecule of the intermediate is (1-20) to 1;
the reaction of the intermediate oligoalcohol and 1, 3-propane sultone is carried out in an organic solvent, and the solvent is selected from one or more of tetrahydrofuran, trichloromethane, dichloromethane or toluene;
the reaction of the intermediate oligo-alcohol and 1, 3-propane sultone is carried out under the reflux condition; the reaction time is 12-480 h.
8. The production method according to claim 7, wherein:
after the sulfonation reaction of the intermediate oligo-alcohol and the 1, 3-propane sultone is finished, adding methanol or ethanol to finish the reaction; the solvent is removed and the residue is recrystallized to yield the product.
9. The production method according to claim 8, wherein:
the removal solvent is removed by rotary evaporation;
the solvent for recrystallization is selected from an alcohol solvent, a ketone solvent or a mixture thereof.
10. The method of claim 9, wherein the solvent for recrystallization is selected from methanol, acetone or a mixture thereof.
11. Use of an oligoanionic sulphonate according to claim 1 or 2 as a surfactant.
12. Use according to claim 11, wherein the oligopolyanionic sulphonate is used as a surfactant in an environment containing polyvalent metal ions.
13. The use of claim 11, wherein the oligoanionic sulfonate is used as a surfactant in the fields of thickened oil emulsification viscosity reduction and daily chemicals.
14. Use according to claim 12, wherein the oligopolyanionic sulphonate is used as a surfactant in an environment containing calcium and magnesium ions.
15. Use according to claim 12, wherein the oligoanionic sulphonate is used as a surfactant in the fields of oil recovery, detergents, textile printing.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480590A (en) * | 2008-11-27 | 2009-07-15 | 齐齐哈尔大学 | Sulphonate Gemini surfactant and preparation method thereof |
| CN102690641A (en) * | 2012-06-12 | 2012-09-26 | 陕西科技大学 | Sulfonate surfactant and preparation method thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN102690641A (en) * | 2012-06-12 | 2012-09-26 | 陕西科技大学 | Sulfonate surfactant and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Aggregation behaviors of a series of anionic sulfonate gemini surfactants and their corresponding monomeric surfactant";Wang Yingxiong等;《Journal of Colloid and Interface Science》;20071221;第319卷;第534-541页 * |
| "Interactions of Divalent and Trivalent Metal Counterions with Anionic Sulfonate Gemini Surfactant and Induced Aggregate Transitions in Aqueous Solution";Liu Zhang等;《J. Phy. Chem. B》;20160420;第120卷;第4102-4113页 * |
| "寡聚表面活性剂的合成及其聚集行为的研究";韩玉淳等;《中国科学:化学》;20150420;第45卷(第4期);第327-339页 * |
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