CN115340476B - Fluorine-containing ternary ammonium salt compound and preparation method and application thereof - Google Patents
Fluorine-containing ternary ammonium salt compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN115340476B CN115340476B CN202210929332.2A CN202210929332A CN115340476B CN 115340476 B CN115340476 B CN 115340476B CN 202210929332 A CN202210929332 A CN 202210929332A CN 115340476 B CN115340476 B CN 115340476B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- ammonium salt
- salt compound
- quaternary ammonium
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 69
- 239000011737 fluorine Substances 0.000 title claims abstract description 69
- -1 ammonium salt compound Chemical class 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000012022 methylating agents Substances 0.000 claims abstract description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002140 halogenating effect Effects 0.000 claims abstract description 7
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 238000005187 foaming Methods 0.000 abstract description 6
- 239000000693 micelle Substances 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 20
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 17
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000006260 foam Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical group [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 231100000041 toxicology testing Toxicity 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- HSDJWNJDPDJOEV-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O HSDJWNJDPDJOEV-UHFFFAOYSA-N 0.000 description 1
- 206010063003 Endocrine toxicity Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 208000037280 Trisomy Diseases 0.000 description 1
- 241001147416 Ursus maritimus Species 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007673 developmental toxicity Effects 0.000 description 1
- 231100000415 developmental toxicity Toxicity 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 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
- 229920001971 elastomer Polymers 0.000 description 1
- 231100000146 endocrine toxicity Toxicity 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 231100000334 hepatotoxic Toxicity 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 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
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/30—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups
-
- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/18—Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of fluorine-containing surfactants, and discloses a fluorine-containing ternary ammonium salt compound, a preparation method and application thereof. The method comprises the following steps: reacting p-hydroxybenzyl alcohol with perfluoroalkyl sulfonyl fluoride in the presence of a first acid binding agent and a first solvent to obtain an intermediate compound M1; reacting the intermediate compound M1 with a halogenating agent in the presence of a second acid binding agent and a second solvent to obtain an intermediate compound M2; reacting diethylenetriamine with a methylating agent to obtain pentamethyldiethylenetriamine; and (3) in the presence of a third solvent, carrying out quaternization reaction on the intermediate compound M2 and pentamethyldiethylenetriamine to obtain the fluorine-containing trisquaternary ammonium salt compound. The fluorine-containing quaternary ammonium salt compound has excellent surface activity and lower critical micelle concentration, has the recyclability of pH response, and can also control the foaming/defoaming property of the fluorine-containing quaternary ammonium salt compound aqueous solution by adjusting the pH.
Description
Technical Field
The invention relates to the technical field of fluorine-containing surfactants, in particular to a fluorine-containing ternary ammonium salt compound, a preparation method and application thereof.
Background
The fluorosurfactant is one of the most surface-active surfactants in all the surfactants so far, and the introduction of fluorine atoms imparts some unique properties to the fluorosurfactant (chem. Rev.2009,109, 1714-1792), such as the greater van der waals radius of fluorine atoms relative to hydrogen atoms, creating a certain "shielding" effect on carbon-carbon bonds, resulting in fluorosurfactants with high chemical stability; the strong electronegativity of fluorine atoms enables the fluorocarbon bonds to have extremely strong bond energy, so that the fluorine-containing surfactant is endowed with high thermodynamic stability; the low polarizability of fluorine atoms makes intermolecular attraction weak, and endows fluorocarbon chains with hydrophobic and oleophobic properties and high surface activity of fluorine-containing surfactants. Based on the characteristic of 'three high and two hydrophobic', the application potential and development of the fluorine-containing surfactant draw a great deal of attention, and the fluorine-containing surfactant is widely applied to the fields of cosmetics, energy storage materials, metal corrosion prevention, fire fighting foam, solar cells, biological medicines, petrochemical industry and the like at present.
Perfluorooctanoic acid (PFOA) and perfluorooctyl sulfonate (PFOS) and derivatives thereof are typical of fluorosurfactants. The introduction of long perfluoroalkyl chains imparts excellent surface activity to such surfactants, but toxicity studies indicate that long-term use of PFOA/PFOS-like long perfluorocarbon chain surfactants can lead to reproductive toxicity, hepatotoxicity, endocrine toxicity, developmental toxicity and neurotoxicity in humans and organisms, and also has environmental problems such as bioagglomeration, degradation difficulties, etc. due to excessive stabilization of fluorocarbon bonds, which are difficult to degrade by enzymes or metabolism under natural conditions (j.mol. Liq.2019,285, 607-615), such as PFOA half-life of 3.26 years in human blood, which has been detected in various parts of the world including rivers, oceans, glacial regions (trace detected by polar bear livers), and human cell tissues etc. (environ. Sci. Technol.2004,38, 373-380). Thus, the international schlegel convention (POPs) ranks PFOA/PFOS as persistent organic pollutants and limits their production and use in a number of fields. The U.S. Environmental Protection Agency (EPA) has also announced a gradual reduction in PFOA/PFOS application in most industries by 2010, and a complete ban in all industries by 2015. The promulgation of the ban has great influence on the PFOA/PFOS and the production industry of fluorine-containing polymers, but due to the ultra-high surface activity (the minimum surface tension can reach 15-20 mN/m) of fluorine-containing surfactants, the ban is still used in certain industries, such as the fields of compounding of aqueous film-forming foam extinguishing agents (environ. Chem. Lett.2020,18, 1277-1300), the production of fluorine rubber (Brydson's plastics. Mater.2017, 389-425) and the like. Therefore, research on PFOA/PFOS substitutes is carried out, and has important significance for sustainable development of ecology.
PFOA/FPOS alternatives are broadly divided into three classes, depending on the structure of the fluorocarbon chain: (1) Short perfluorocarbon chain surfactant (C) n F 2n+1 N is less than or equal to 6); (2) the fluorocarbon chain contains weak bond surfactant; (3) branched fluorocarbon chain type surfactant.
Among the three alternatives to PFOA, the most studied with short perfluorocarbon chain type surfactants was reported. The half-life of short perfluorocarbon chain surfactants in human blood is much shorter than the half-life of PFOA in human blood by up to 3.26 years, e.g. the half-life of perfluorobutyl sulphonic acid in male and female blood is only 24 days and 46 days, respectively (environ. Int.2013,60, 242-248), with potential non-bioaccumulation. However, as the fluorocarbon chain length is shortened, the surface activity of the short perfluorocarbon chain type surfactant is reduced because shortening the fluorocarbon chain length weakens the hydrophobicity of the surfactant. For example, zhou et al synthesizes a series of short perfluorocarbon chain nonionic surfactants by using perfluoroethyl, butyl and hexyl as hydrophobic chains, polyethylene glycol as hydrophilic groups and isophorone diisocyanate units as bridging groups through a simple two-step coupling reaction, and systematically researches the relationship between the hydrophobic chain length and the surface activity, and proposes that the surface activity gradually decreases with the shortening of the fluorocarbon chain length (J.dispersion Sci.technology.2020, 42, 152-159).
The introduction of weak bonds, such as methylene and ether linkages, in perfluoroalkyl chains can promote the degradation of fluorocarbon chains and reduce bioaccumulation (Colloids surf., a 2016,507,236-242). The weak bond-containing surfactant in the fluorocarbon chain is prepared by amidation and quaternization reaction of 2, 5-bis (trifluoromethyl) -3, 6-dioxaundecanoyl fluoride serving as a raw material and N, N-dimethylpropane by Shen et al, and the surface tension of the weak bond-containing surfactant under the critical micelle concentration is 16.41mN/m, so that the weak bond-containing surfactant shows excellent surface activity (J.Ind.Eng.chem.2017, 56, 82-89). Although such fluorosurfactants are somewhat degradable and highly active, they are much lower than short perfluorocarbon chain surfactants in terms of atom economy and have few reports.
Third stepThe class of alternatives is branched fluorocarbon chain surfactants. The branched fluorocarbon chain surfactants reported in the literature contain multiple CFs in the fluorocarbon backbone 3 -sum (CF) 3 ) 2 CF-and the like, mainly comprising hexafluoropropylene oligomers, such as hexafluoropropylene trimers and dimers, having fluorocarbon backbones of no more than 6 carbon atoms in length. For example, wei et al, which are used for specially synthesizing branched fluorocarbon chain type surfactants and short perfluorinated carbon chain type surfactants with similar structures by utilizing hexafluoropropylene trimer and perfluorohexyl sulfonyl fluoride, the surface tension data of the branched fluorocarbon chain type surfactants are compared with those of the short perfluorinated carbon chain type surfactants, so that the branched fluorocarbon chain type surfactants are lower in surface activity than those of the short perfluorinated carbon chain type surfactants (J.mol.Liq.2019, 280, 327-333).
In summary, fluorosurfactants have an irreplaceable role in some fields, but they also present a non-negligible hazard to human health and the environment. The essence of the three PFOA/PFOS substitutes is shortening the fluorocarbon chain, and the problems of low atom economy, incapability of industrial production and the like still exist. In addition, toxicological studies have shown that short perfluorocarbon chain surfactants such as perfluorobutyl sulfonic acid (PFBS) are more toxic to the liver of mammals than long perfluorocarbon chain surfactants (environ. Health per select.2019, 127, 037008).
Disclosure of Invention
The invention aims to overcome the defects of the prior fluorine-containing surfactant and provide a fluorine-containing ternary ammonium salt compound, a preparation method and application thereof.
In order to complete the invention, the inventor of the invention envisages that on the basis of research of three types of substitutes of PFOA/PFOS, a fourth type of substitute is developed through structural design, so that a target object designed and synthesized not only can have very high surface activity, but also can form a precipitate to be separated out from a solution and recovered under the stimulation of external factors, and the problem that a fluorine-containing surfactant cannot be replaced and is environment-friendly is solved.
To this end, the inventors of the present invention have found through a great deal of experiments and studies that a pH-responsive fluorine-containing cationic surfactant which is recovered as a precipitate at ph=1, exhibits surface activity between ph=2 and 12 and can generate a great deal of foam, and the foam disappears at pH ∈13. The properties exhibited by the fluorochemical cationic surfactants are fully in accordance with the above-described considerations. However, no research report about the recyclable fluorosurfactant exists in the prior art, and the synthesis of the pH-responsive recyclable fluorine-containing ternary quaternary ammonium surfactant provides a brand-new direction and thought for the research of PFOA/PFOS substitutes, which is very beneficial to the harmonious development of the fluorine-containing surfactant industry and ecological environment protection.
In particular, the invention provides a fluorine-containing tri-quaternary ammonium salt compound, the structural formula of the fluorine-containing tri-quaternary ammonium salt compound is shown as a formula (1),
wherein R is f Is perfluoroalkyl, X - Is a monovalent anion.
Preferably, R f Perfluoroalkyl of C3-C10, more preferably-C 4 F 9 、-C 6 F 13 、-C 6 F 11 、-C 8 F 17 or-C 9 F 17 。
Preferably, X is Cl, br or I.
Preferably, the structural formula of the fluorine-containing tri-quaternary ammonium salt compound is shown as a formula (2),
the invention also provides a preparation method of the fluorine-containing trisodium quaternary ammonium salt compound, which comprises the following steps:
(1) Reacting p-hydroxybenzyl alcohol with perfluoroalkyl sulfonyl fluoride in the presence of a first acid-binding agent and a first solvent to obtain an intermediate compound M1 shown in a formula (1-1);
(2) Reacting the intermediate compound M1 with a halogenating agent in the presence of a second acid binding agent and a second solvent to obtain an intermediate compound M2 shown in the formula (1-2);
(3) Reacting diethylenetriamine with a methylating agent to obtain pentamethyldiethylenetriamine;
(4) In the presence of a third solvent, carrying out quaternization reaction on the intermediate compound M2 and the pentamethyldiethylenetriamine to obtain a fluorine-containing trisodium quaternary ammonium salt compound shown in a formula (1);
wherein R is f Is perfluoroalkyl, preferably C3-C10 perfluoroalkyl, more preferably-C 4 F 9 、-C 6 F 13 、-C 6 F 11 、-C 8 F 17 or-C 9 F 17 The method comprises the steps of carrying out a first treatment on the surface of the X is Cl, br or I.
Preferably, in step (1), the first acid binding agent is potassium carbonate and the first solvent is acetonitrile.
Preferably, in the step (2), the second acid-binding agent is at least one of triethylamine, potassium carbonate and pyridine, the second solvent is acetonitrile and/or dichloromethane, and the halogenating agent is at least one of thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, NCS, NBS, hydrogen chloride, hydrogen bromide and hydrogen iodide.
Preferably, in step (3), the methylating agent is a combination of formaldehyde and anhydrous formic acid, methyl iodide, dimethyl sulfate or dimethyl carbonate.
Preferably, in step (4), the third solvent is at least one of acetonitrile, ethanol and acetone.
The invention also provides application of the fluorine-containing ternary ammonium salt compound as a surfactant or a foaming-defoaming agent.
The fluorine-containing ternary ammonium salt compound has excellent surface activity and lower Critical Micelle Concentration (CMC), CMC value and gamma CMC The values were 1.35X 10 respectively -4 mol/L and 18.30mN/m. Among them, the commercial PFOA (Curr. Opin. Colid Interface)CMC values of 8.50X10 for Sci.2012,17, 188-195) and PFOS (J.Fluorine chem.1990,48,77-84), respectively -3 mol/L and 3.10X10 -2 mol/L,γ CMC 20.00 and 24.70mN/m, respectively. In contrast, the CMC value and gamma of the fluorine-containing tri-quaternary ammonium salt compound according to the present invention CMC The values were much lower, indicating that they could reach or exceed the surface activity of PFOA/PFOS at lower concentrations. With commercial perfluorobutyric acid PFBA (gamma) of the same carbon number CMC The value is 25.50 mN/m), compared with the fluorine-containing ternary quaternary ammonium salt compound, the fluorine-containing ternary ammonium salt compound has more low surface tension and obvious advantages.
Furthermore, the fluorine-containing ternary ammonium salt compound disclosed by the invention has good foamability under the condition of pH=2-12; the solution can be rapidly defoamed and converted into turbid liquid in a strong acid or alkaline environment with pH value of 2 or 12, flocculent precipitate can be separated out after the turbid liquid is stood, and the precipitate is filtered and dissolved by water again to recover the surface activity. Therefore, the pH response recyclable property of the fluorine-containing tri-quaternary ammonium salt compound disclosed by the invention is not available for other types of surfactants, and the fluorine-containing tri-quaternary ammonium salt compound has very high environmental protection benefit and economic benefit. The pH-controllable foaming/defoaming properties derived from the recyclable nature also have certain advantages.
In addition, the fluorine-containing ternary ammonium salt compound has the advantages of short synthetic route, high yield, low-cost and easily-obtained raw materials and the like, and has potential industrial application value.
Drawings
FIG. 1 is an intermediate compound M1 prepared in example 1 1 H NMR chart;
FIG. 2 is an intermediate compound M1 prepared in example 1 13 C NMR chart;
FIG. 3 is an intermediate compound M1 prepared in example 1 19 F NMR chart;
FIG. 4 is an intermediate compound M1 prepared in example 1 1 H NMR heavy water exchange diagram;
FIG. 5 is an MS plot of intermediate compound M1 prepared in example 1;
FIG. 6 is an intermediate compound M2 prepared in example 1 1 H NMR chart;
FIG. 7 is an intermediate compound M2 prepared in example 1 13 C NMR chart;
FIG. 8 is an intermediate compound M2 prepared in example 1 19 F NMR chart;
FIG. 9 is an MS plot of intermediate compound M2 prepared in example 1;
FIG. 10 is a drawing of pentamethyldiethylenetriamine prepared in example 1 1 H NMR chart;
FIG. 11 is a drawing of pentamethyldiethylenetriamine prepared in example 1 13 C NMR chart;
FIG. 12 is an MS plot of pentamethyldiethylenetriamine prepared in example 1;
FIG. 13 is a target product of the fluorine-containing quaternary ammonium salt compound prepared in example 1 1 H NMR chart;
FIG. 14 is a target product of the fluorine-containing quaternary ammonium salt compound prepared in example 1 13 C NMR chart;
FIG. 15 is a drawing of the target product of the fluorine-containing quaternary ammonium salt compound prepared in example 1 19 F NMR chart;
FIG. 16 is an HRMS plot of the desired product of the fluorochemical quaternary ammonium salt compound prepared in example 1;
FIG. 17 is a FT-IR chart of the target product of the fluorine-containing quaternary ammonium salt compound prepared in example 1;
FIG. 18 shows the results of measuring the interfacial parameters of the fluorine-containing quaternary ammonium salt compound prepared in example 1, wherein a is a graph showing the change of surface tension with concentration, and b is a graph showing the change of surface excess concentration with derivative of curve;
FIG. 19 shows the pH responsive recoverable properties of the fluorine-containing quaternary ammonium salt compound prepared in example 1 at a concentration of 10 CMC;
FIG. 20 is a graph comparing the IR spectrum of the acid-separated solid with the fluorine-containing quaternary ammonium salt compound prepared in example 1;
fig. 21 shows the results of the foaming/defoaming performance test for pH adjustment.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The structural formula of the fluorine-containing ternary quaternary ammonium salt compound is shown as a formula (1),
in formula (1), R f Is perfluoroalkyl, preferably C3-C10 perfluoroalkyl, more preferably-C 4 F 9 、-C 6 F 13 、-C 6 F 11 、-C 8 F 17 or-C 9 F 17 。
In formula (1), X - Is a monovalent anion, preferably Cl - 、Br - Or I - . In an alternative embodiment, X - The halide ions can also be conveniently exchanged for other anions.
In the most preferred embodiment, the fluorine-containing quaternary ammonium salt compound of the present invention is N trichloride 1 -2- (dimethyl (4- (((perfluorobutylsulphonyloxy) benzyl) ammonio) ethyl) -N 1 ,N 2 ,N 2 -trimethyl-N 1 ,N 2 Bis (4- (((perfluorobutylsulfonyloxy) benzyl) ethane-1, 2-diammonium having a structural formula shown in formula (2),
the preparation method of the fluorine-containing trisomy quaternary ammonium salt compound comprises the following steps:
(1) Reacting p-hydroxybenzyl alcohol with perfluoroalkyl sulfonyl fluoride in the presence of a first acid-binding agent and a first solvent to obtain an intermediate compound M1 shown in a formula (1-1);
(2) Reacting the intermediate compound M1 with a halogenating agent in the presence of a second acid binding agent and a second solvent to obtain an intermediate compound M2 shown in the formula (1-2);
(3) Reacting diethylenetriamine with a methylating agent to obtain pentamethyldiethylenetriamine;
(4) In the presence of a third solvent, carrying out quaternization reaction on the intermediate compound M2 and the pentamethyldiethylenetriamine to obtain a fluorine-containing trisodium quaternary ammonium salt compound shown in a formula (1);
wherein R is f Is perfluoroalkyl, preferably C3-C10 perfluoroalkyl, more preferably-C 4 F 9 、-C 6 F 13 、-C 6 F 11 、-C 8 F 17 or-C 9 F 17 The method comprises the steps of carrying out a first treatment on the surface of the X is Cl, br or I.
In the method of the present invention, the reaction of step (1) and step (2) is a nucleophilic substitution reaction, the reaction of step (3) is an N-methylation reaction, and the reaction of step (4) is a quaternization reaction.
In the most preferred embodiment, in formula (1), formula (1-1) and formula (1-2), R f is-C 4 F 9 X is Cl. In this embodiment, the perfluoroalkyl sulfonyl fluoride is perfluorobutyl sulfonyl fluoride, and the reaction processes of step (1) and step (2) are shown in the following reaction formulas.
The reaction process of step (3) is shown in the following reaction scheme.
The reaction process of step (4) is shown in the following reaction scheme.
In step (1), the molar ratio of the amount of p-hydroxybenzyl alcohol to the amount of perfluoroalkyl sulfonyl fluoride may be 1:1-2, preferably 1:1.1-1.3, most preferably 1:1.2.
in step (1), the amount of the first acid-binding agent may be 1.5 to 3 times, preferably 1.8 to 2.5 times, and most preferably 2 times the amount of the p-hydroxybenzyl alcohol.
The reaction described in step (1) is preferably carried out under reflux conditions.
In the method of the present invention, the first acid-binding agent used in step (1) is most preferably potassium carbonate.
In the process according to the invention, the first solvent used in step (1) is most preferably acetonitrile.
In step (2), the molar ratio of the intermediate compound M1 to the amount of the halogenating agent may be 1:1.5-3, preferably 1:1.8-2.5, most preferably 1:2.
in step (2), the second acid-binding agent may be used in an amount of 1.5 to 3 times, preferably 1.8 to 2.5 times, most preferably 2 times the amount of the intermediate compound M1.
The reaction in the step (2) can be carried out for 0.5 to 3 hours at room temperature, and then the temperature is raised to reflux for 0.5 to 3 hours.
In the method of the present invention, the halogenating agent used in step (2) may be at least one of thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, NCS, NBS, hydrogen chloride, hydrogen bromide and hydrogen iodide, most preferably thionyl chloride.
In the method of the present invention, the second acid-binding agent used in step (2) may be at least one of triethylamine, potassium carbonate and pyridine, and most preferably triethylamine.
In the process according to the invention, the second solvent used in step (2) may be acetonitrile and/or dichloromethane, most preferably acetonitrile.
In the process according to the invention, the methylating agent used in step (3) may be a combination of formaldehyde (aqueous formaldehyde or paraformaldehyde) and anhydrous formic acid, methyl iodide, dimethyl sulphate or dimethyl carbonate, most preferably a combination of formaldehyde and anhydrous formic acid. The aqueous formaldehyde solution is preferably an aqueous formaldehyde solution having a concentration of 37% by weight.
In step (3), when the methylating agent is a combination of formaldehyde and anhydrous formic acid, the molar ratio of the amount of diethylenetriamine to formaldehyde may be 1:5-10, preferably 1:6-8, most preferably 1:7, preparing a base material; the molar ratio of the amount of diethylenetriamine to formic acid may be 1:6-12, preferably 1:7-9, most preferably 1:8.
the reaction conditions of step (3) may include: the temperature is 105-115 ℃ and the time is 5-24h.
In step (4), the molar ratio of the intermediate compound M2 to the amount of pentamethyldiethylenetriamine may be 3 to 3.5:1.
the reaction described in step (3) is preferably carried out under reflux.
In the method of the present invention, the third solvent used in step (4) may be at least one of acetonitrile, ethanol and acetone, and most preferably acetonitrile.
The fluorine-containing ternary ammonium salt compound has excellent surface activity and lower Critical Micelle Concentration (CMC), CMC value and gamma CMC The values were 1.35X 10 respectively -4 mol/L and 18.30mN/m, and thus are suitable for use as surfactants.
The fluorine-containing ternary ammonium salt compound disclosed by the invention has good foamability under the condition of pH=2-12, and can be rapidly defoamed and converted into turbid liquid in a strong acid or alkaline environment with pH <2 or pH >12, so that the fluorine-containing ternary ammonium salt compound is suitable for being used as a foaming-defoaming agent.
The fluorine-containing quaternary ammonium salt compound of the present invention, its preparation method and application are further described below by way of examples. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below are commercially available unless otherwise specified.
Example 1
(1) Preparation of intermediate compound M1
Into a dry 250mL flask was added 12.40g (0.10 mol) of p-hydroxybenzyl alcohol, dissolved with 150mL of acetonitrile, and while stirring, 27.60g (0.20 mol) of an acid-binding agent potassium carbonate was added, refluxed for half an hour, then 36.24g (0.12 mol) of perfluorobutylsulfonyl fluoride was slowly added dropwise, and TLC monitored for the end point of the reaction. The residue was removed by suction filtration, the filtrate was dried by spin-drying, 100mL of ethyl acetate was added, the mixture was washed 3 times with saturated brine (100 mL), and the organic layer was dried over anhydrous sodium sulfate. Desolventizing, separation by column chromatography (petroleum ether: ethyl acetate=10:1) gives 39.21g of the pale yellow liquid intermediate perfluorobutylsulfonyloxybenzyl alcohol (M1) in 96.58% yield. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum, the fluorine spectrum and the mass spectrum are shown in figures 1 to 5.
1 H NMR(600MHz,CDCl 3 ):δ7.43(d,J=12.0Hz,2H),7.26(d,J=12.0Hz,2H),4.70(s,2H),2.14(s,1H);
13 C NMR(151MHz,CDCl 3 ):δ149.05,141.28,128.48,121.44,64.14;
19 F NMR(376MHz,CDCl 3 ):δ-80.75(3F),-109.01(2F),-120.95(2F),-125.92(2F);
MS(EI):405.9([M–H] + ) (calculated value: 405.2).
(2) Preparation of intermediate compound M2
24.36g (0.06 mol) of intermediate compound M1 was added to a dry 250mL round bottom flask, dissolved with 100mL of acetonitrile, 12.12g (0.12 mol) of triethylamine as an acid-binding agent was added thereto, the reaction flask was placed in an ice bath, 14.28g (0.12 mol) of thionyl chloride was dropwise added with stirring, the reaction was continued at room temperature for 1 hour after the addition was completed, then the temperature was raised to 85℃for reflux reaction for 1 hour, and TLC was monitored for the reaction. The residue was removed by suction filtration, the filtrate was dried by spin-drying, 100mL of ethyl acetate was added, the mixture was washed 3 times with saturated brine (100 mL), and the organic layer was dried over anhydrous sodium sulfate. Desolventizing, separation by column chromatography (pure petroleum ether) gave a colorless transparent liquid as intermediate perfluoroalkyl sulfonyloxybenzyl chloride (M2) 14.70g in 95.47% yield.
The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum, the fluorine spectrum and the mass spectrum are shown in fig. 6 to 9.
1 H NMR(400MHz,DMSO):7.65(d,J=8.0Hz,2H),7.52(d,J=8.0Hz,2H),4.84(s,1H);
13 C NMR(101MHz,DMSO):δ149.47(s),139.24(s),131.65(s),122.19(s),45.07(s);
19 F NMR(376MHz,DMSO):δ-80.38(3F),-109.36(2F),-121.01(2F),-125.72(2F);
MS(EI):423.8([M] + ) (calculated value: 424.7).
(3) Preparation of pentamethyldiethylenetriamine
Into a dry 250mL three-necked flask, 8.24g (0.08 mol) of diethylenetriamine was charged, the flask was placed in a cold water bath, 29.41g (0.64 mol) of anhydrous formic acid was added dropwise, 45.37g of 37wt% aqueous formaldehyde solution (0.56 mol of formaldehyde) was further added, and the flask was slowly heated until no large amount of carbon dioxide gas was emitted, and the temperature of the reaction solution was raised to about 110℃and the reaction was refluxed for 12 hours. Then 20mL of concentrated hydrochloric acid was added. Desolventizing, washing with absolute methanol for 3 times to obtain a crude product of pentamethyldiethylenetriamine hydrochloride. The crude product was added to a 250mL single-necked flask, followed by 17.38g (0.11 mol) of sodium hydroxide, 100mL of methanol, and heated under reflux for 1h. Desolventizing, adding sodium metal, rectifying, collecting the fraction at 206-208 deg.C (101.325 kPa) to obtain 11.87g of colorless transparent slightly viscous pentamethyldiethylenetriamine with yield of 85.76%. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the mass spectrum are shown in fig. 10 to 12.
1 H NMR(600MHz,CDCl 3 ):δ2.49(t,J=6.0Hz,4H),2.41(t,J=6.0Hz,4H),2.25(s,3H),2.24(s,12H).
13 C NMR(151MHz,CDCl 3 ):δ57.17(s),55.96(s),45.67(s),42.53(s).
MS(EI):128.1([M–NH(CH 3 ) 2 ] + ) (calculated value: 128.2).
(4) Preparation of the present product of the fluorine-containing quaternary ammonium salt compound
Into a dry 250mL round bottom flask was added 2.31g (0.013 mol) of pentamethyldiethylenetriamine; 16.98g (0.040 mol) of the intermediate compound M2 are added; 100mL of acetonitrile was added and stirred at 85℃under reflux for 36h, desolventized, and the resulting solid was purified using V Ethanol :V Acetic acid ethyl ester The mixed solvent of=1:3 was recrystallized three times to obtain 17.30g of the target compound represented by the formula (2) as a white solid, and the yield was 89.68%. The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum, the fluorine spectrum, the high resolution mass spectrum and the infrared spectrogram are shown in figures 13-17.
1 H NMR(400MHz,MeOD):δ7.92(d,J=8.0Hz,6H),7.63(d,J=8.0Hz,6H),5.05(s,6H),4.08(t,J=12.0Hz,8H),3.53-3.49(S,15H);
13 C NMR(101MHz,MeOD):δ151.63(s),135.61(s),126.80(s),122.33(s),113.30(s),55.01(s),53.74(s),46.60(s).
19 F NMR(376MHz,D 2 O):δ-82.91(s),-110.52(s),-122.12(s),-127.41(s);
HR-MS(ESI):m/z[M-2C 14 H 14 F 9 NO 3 S-3Cl] +· ,C 14 H 13 F 9 NO 3 Actual measurement value of S is 446.0467; calculated 446.0452.
FT-IR (. Nu.cm for KBr pellet) -1 :3016,2975,1603,1502,1479,1424,1356,1242,1206,1146,1037,1015,896.
Test example 1
Determination of air/Water interface parameters of aqueous solutions of target Compounds (triQA-1) of formula (2)
The air/water interface parameters of the surfactant include Critical Micelle Concentration (CMC), surface tension at critical micelle concentration (γ) CMC ) Maximum surface excess concentration (Γ) max ) Minimum single molecular area (A) min ) pC 20 Values. The operation is as follows: a predetermined amount of the above target compound (triQA-1) was prepared by preparing solutions of the following concentration gradients (unit: mmol/L) with distilled water: 0.001,0.002,0.004,0.006,0.008,0.01,0.03,0.05,0.07,0.09,0.20,0.40,0.60,0.80,1.0,1.2,1.4,1.6,1.8,2.0 by measuring surface tension at 25deg.C with QBZY-2 type fully automatic surface tensiometer (platinum plate method), drawing trend graph of surface tension with concentration, i.e. Gibbs isothermal adsorption curve of surface tension and concentration relationship (a in FIG. 18), obtaining CMC and gamma from inflection point of the curve CMC . Performing first-order exponential decay fitting to the curve to obtain derivative of the curve, and obtaining Γ from the highest point of the curve by using formula (1) to obtain a trend curve (b in FIG. 18) of the surface excess concentration with the derivative max Values. Continuing to calculate A through formulas (2) and (3) respectively min And pC 20 Values. The air/water interface parameter values are statistically shown in table 1.
/>
pC 20 =-log C 20 (3)
Wherein C is the concentration of the fluorosurfactant, (dγ/dC) T For the slope of the tangent at the CMC, R is the ideal gas constant (8.314J mol -1 K -1 ) T is the thermodynamic temperature and N is the Avofila constant 6.02X10 23 ,C 20 The concentration of surfactant required to reduce the water surface tension value by 20 mN/m.
Table 1: air/water interface parameter value of aqueous solution of target compound
Test example 2: recoverable property test of pH response
36.21mg of the target product is accurately weighed, and 20mL of each of aqueous solutions with pH values of 1, 3, 5, 7, 9, 11 and 13 are respectively added to prepare surfactant solutions with concentration of 10 times CMC (1 mmol/L) under different pH conditions. And (5) ultrasonic dissolution for 30min, and observing the dissolution condition of the sample. As shown in fig. 19, a large amount of white insoluble solids was clearly observed at ph=1; there was also a small amount of white insoluble solids at ph=13; and under the condition that the pH value is more than or equal to 3 and less than or equal to 11, the solution is clear and transparent. From the above phenomenon, it is presumed that the aqueous solution of the target product has pH responsiveness. To verify the presumption, concentrated hydrochloric acid was added to the aqueous solution of the objective product under neutral conditions (ph=7), and the pH was adjusted to 1 with stirring, whereby a large amount of white precipitate was found to be precipitated. To verify that the precipitated white precipitate was the same as the target product, the precipitated white precipitate was collected and dried, and its structure was characterized by infrared spectroscopy and compared with the infrared spectroscopy of the target product (triQA-1), as shown in fig. 20. The infrared characteristic absorption peak of the acid-separated solid is completely consistent with the infrared characteristic absorption peak of the target product (triQA-1), which shows that the acid-separated solid is identical with the structure of the target product (triQA-1) and is the same substance.
Both the experimental phenomena and the data result show that the synthesized fluorine-containing tri-quaternary ammonium salt compound has the pH response recoverability, and the fluorine-containing tri-quaternary ammonium salt compound can be separated out from the aqueous solution by adjusting the pH of the solution to 1, so that the recovery is realized. To determine recovery, the dried acid-out solids were weighed to give 36.17mg, which was calculated to be 99.89% recovery, indicating that the fluorine-containing tri-quaternary ammonium salt compound was substantially completely recovered from the aqueous solution at ph=1.
Test example 3: foaming/defoaming performance test for pH control
From the recyclability of the pH response, it is speculated that the aqueous solution of the target product also has pH-controllable foaming/defoaming properties. To verify the presumption, 10mL of the surfactant solution at different pH as described above was placed in a test tube, stoppered with a wooden plug, and then simultaneously shaken up and down 15 times to observe foamability. As shown in fig. 21, no foam was generated at ph=1; only a small amount of foam was produced at ph=13; and a large amount of foam is generated under the condition that the pH value is more than or equal to 3 and less than or equal to 11. In addition, concentrated hydrochloric acid was added to the foam solution under neutral conditions to adjust the pH to 1, and it was also found that the foam disappeared rapidly and a white solid was precipitated. The experimental phenomenon shows that the foaming/defoaming property of the target compound aqueous solution can be controlled by adjusting the pH value, so that the fluorine-containing ternary quaternary ammonium salt compound has potential application value in the field of froth flotation.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (6)
1. A fluorine-containing tri-quaternary ammonium salt compound is characterized in that the structural formula of the fluorine-containing tri-quaternary ammonium salt compound is shown as a formula (2),
the preparation method of the fluorine-containing trisodium quaternary ammonium salt compound comprises the following steps:
(1) Reacting p-hydroxybenzyl alcohol with perfluoroalkyl sulfonyl fluoride in the presence of a first acid-binding agent and a first solvent to obtain an intermediate compound M1 shown in a formula (1-1);
(2) Reacting the intermediate compound M1 with a halogenating agent in the presence of a second acid binding agent and a second solvent to obtain an intermediate compound M2 shown in the formula (1-2);
(3) Reacting diethylenetriamine with a methylating agent to obtain pentamethyldiethylenetriamine;
(4) In the presence of a third solvent, carrying out quaternization reaction on the intermediate compound M2 and the pentamethyldiethylenetriamine to obtain a fluorine-containing trisodium quaternary ammonium salt compound shown in a formula (2);
wherein R is f is-C 4 F 9 The method comprises the steps of carrying out a first treatment on the surface of the X is Cl.
2. The fluorine-containing quaternary ammonium salt compound according to claim 1, wherein in step (1), the first acid binding agent is potassium carbonate and the first solvent is acetonitrile.
3. The fluorine-containing quaternary ammonium salt compound according to claim 1, wherein in the step (2), the second acid-binding agent is at least one of triethylamine, potassium carbonate and pyridine, the second solvent is acetonitrile and/or dichloromethane, and the halogenated agent is at least one of thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, NCS and hydrogen chloride.
4. The fluorine-containing quaternary ammonium salt compound according to claim 1, wherein in step (3), the methylating agent is a combination of formaldehyde and anhydrous formic acid, methyl iodide, dimethyl sulfate or dimethyl carbonate.
5. The fluorine-containing quaternary ammonium salt compound according to any one of claims 1 to 4, wherein in step (4), the third solvent is at least one of acetonitrile, ethanol and acetone.
6. Use of the fluorine-containing quaternary ammonium salt compound according to any one of claims 1 to 5 as a surfactant or a foam-defoaming agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210929332.2A CN115340476B (en) | 2022-08-03 | 2022-08-03 | Fluorine-containing ternary ammonium salt compound and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210929332.2A CN115340476B (en) | 2022-08-03 | 2022-08-03 | Fluorine-containing ternary ammonium salt compound and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115340476A CN115340476A (en) | 2022-11-15 |
CN115340476B true CN115340476B (en) | 2024-01-05 |
Family
ID=83949613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210929332.2A Active CN115340476B (en) | 2022-08-03 | 2022-08-03 | Fluorine-containing ternary ammonium salt compound and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115340476B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102942493A (en) * | 2012-11-09 | 2013-02-27 | 西南石油大学 | Terquaternary cation surface active agent and preparation method |
CN103446943A (en) * | 2013-09-18 | 2013-12-18 | 华中师范大学 | Gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant as well as preparation and application thereof |
CN103464049A (en) * | 2013-09-18 | 2013-12-25 | 华中师范大学 | Perfluorohexyl sulfonyloxy benzyl cation surfactant as well as preparation method and application thereof |
CN107232191A (en) * | 2017-06-22 | 2017-10-10 | 华中师范大学 | A kind of perfluoro butyl modified polyethyleneimine macromolecular fluorine-containing surfactant and its preparation and the application in pesticide slow-release |
-
2022
- 2022-08-03 CN CN202210929332.2A patent/CN115340476B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102942493A (en) * | 2012-11-09 | 2013-02-27 | 西南石油大学 | Terquaternary cation surface active agent and preparation method |
CN103446943A (en) * | 2013-09-18 | 2013-12-18 | 华中师范大学 | Gemini perfluoroalkylsulfonyloxybenzyl cationic surfactant as well as preparation and application thereof |
CN103464049A (en) * | 2013-09-18 | 2013-12-25 | 华中师范大学 | Perfluorohexyl sulfonyloxy benzyl cation surfactant as well as preparation method and application thereof |
CN107232191A (en) * | 2017-06-22 | 2017-10-10 | 华中师范大学 | A kind of perfluoro butyl modified polyethyleneimine macromolecular fluorine-containing surfactant and its preparation and the application in pesticide slow-release |
Non-Patent Citations (2)
Title |
---|
Aqueous Properties of Multichain Quaternary Cationic Surfactants;Kunio Esumi et al.;《Langmuir》;第12卷;4039-4041 * |
含短全氟烷基链有机化合物的合成及性质;王乾有;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑(月刊)》(第05期);B014-68 * |
Also Published As
Publication number | Publication date |
---|---|
CN115340476A (en) | 2022-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4383929A (en) | Fluorinated sulphobetaines and compositions containing the same | |
JP6395246B2 (en) | Fluorine surfactant and method for producing the same | |
CN101703905B (en) | Biquaternary ammonium salt and bisulfonate surfactant and synthesis method thereof | |
CN108675936B (en) | PH-responsive N-lauryl- (alpha-alkyl) -beta-aminopropionic acid amphoteric surfactant and preparation method and application thereof | |
US3759981A (en) | Esters of perfluoroalkyl terminated alkylene thioalkanoic acids | |
CN101607183A (en) | Carboxylic acid betaine type gemini surfactant and preparation method | |
US4278552A (en) | Fluorine-containing betaine compounds, and production and use thereof | |
WO2007083843A1 (en) | Aromatic compound gelatinizing agent having perfluoroalkyl group | |
CN115340476B (en) | Fluorine-containing ternary ammonium salt compound and preparation method and application thereof | |
CN116144377A (en) | Novel fluorocarbon betaine surfactant and preparation method thereof | |
US11708336B2 (en) | Anodic oxidation of 5-aminouracil | |
US5648528A (en) | Saturated fluoroalkylamines and their derivatives, and mixtures thereof | |
CN102351753A (en) | Fluorine-containing Gemini-like anionic surface active agent, its preparation method and its application | |
US4214102A (en) | Amino-ether amphoteric surface-active compounds | |
WO2010002622A1 (en) | Fluorinated alcohols | |
JPS5832200B2 (en) | Fluorine-containing surfactant and its manufacturing method | |
JPH032855B2 (en) | ||
JPS6042234B2 (en) | Method for producing fluorine-containing compounds | |
JP6523897B2 (en) | Fluorine-containing carboxylic acid compound | |
JPS5832199B2 (en) | Fluorine-containing surfactant and its manufacturing method | |
CN102351755A (en) | Fluorine-containing imine cationic surfactant preparation method and application thereof | |
JPS6217586B2 (en) | ||
CN109679610B (en) | Solid foam drainage agent with pH value response, preparation method and application | |
JPH039099B2 (en) | ||
CN117776959A (en) | Perfluoro branched short chain double chain type cation fluorocarbon surfactant and its compound system |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |