TWI802550B - 氟界面活性劑 - Google Patents
氟界面活性劑 Download PDFInfo
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- TWI802550B TWI802550B TW106137852A TW106137852A TWI802550B TW I802550 B TWI802550 B TW I802550B TW 106137852 A TW106137852 A TW 106137852A TW 106137852 A TW106137852 A TW 106137852A TW I802550 B TWI802550 B TW I802550B
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- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229930182470 glycoside Natural products 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 125000006850 spacer group Chemical group 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000206 photolithography Methods 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- 150000005215 alkyl ethers Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000003010 ionic group Chemical group 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000006117 anti-reflective coating Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- 239000003905 agrochemical Substances 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000675 fabric finishing Substances 0.000 claims description 2
- 238000009962 finishing (textile) Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 150000002338 glycosides Chemical class 0.000 claims description 2
- 239000000976 ink Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011253 protective coating Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000005871 repellent Substances 0.000 claims 1
- 230000002940 repellent Effects 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 239000012071 phase Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
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- 239000000047 product Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- -1 alkali metal cations Chemical class 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
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- 150000001298 alcohols Chemical class 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
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- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 230000002085 persistent effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N aconitic acid Chemical class OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
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- 125000003827 glycol group Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 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 2
- 229910052697 platinum Inorganic materials 0.000 description 2
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- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
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- 150000003568 thioethers Chemical class 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- KPPVNWGJXFMGAM-UUILKARUSA-N (e)-2-methyl-1-(6-methyl-3,4-dihydro-2h-quinolin-1-yl)but-2-en-1-one Chemical compound CC1=CC=C2N(C(=O)C(/C)=C/C)CCCC2=C1 KPPVNWGJXFMGAM-UUILKARUSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=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-M 0.000 description 1
- VHJLVAABSRFDPM-UHFFFAOYSA-N 1,4-dithiothreitol Chemical compound SCC(O)C(O)CS VHJLVAABSRFDPM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XOGTZOOQQBDUSI-UHFFFAOYSA-M Mesna Chemical compound [Na+].[O-]S(=O)(=O)CCS XOGTZOOQQBDUSI-UHFFFAOYSA-M 0.000 description 1
- 150000005857 PFAS Chemical class 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
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- 238000007046 ethoxylation reaction Methods 0.000 description 1
- PGAFCJWTBHYLDN-UHFFFAOYSA-N ethyne-1,2-diamine Chemical compound NC#CN PGAFCJWTBHYLDN-UHFFFAOYSA-N 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 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
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- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
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- 231100000027 toxicology Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
- C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
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- C07—ORGANIC CHEMISTRY
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Abstract
本發明係關於含有氟化端基之新穎化合物、其作為表面活性物質之用途及包含該等化合物之組合物。
Description
本發明係關於含有氟化端基之新穎化合物、其作為表面活性物質之用途及包含該等化合物之組合物。
氟界面活性劑係工業製程化學品中之重要成分。由於其持久性及毒性，該等材料對於使用者及環境存在許多問題。含氟界面活性劑可用於極廣泛種類之應用且有助於(例如)表面之經改良潤濕。因此，其在油漆、塗料或黏結劑中用作(例如)界面促進劑或乳化劑或降黏劑。古典氟界面活性劑係自長鏈、全氟化烷基鏈(C6-C8)建構且被認為潛在地生物累積且有毒的。然而，一般而言，氟界面活性劑含有全氟烷基取代基，其在環境中藉由生物及其他氧化過程分解，獲得全氟烷羧酸及全氟烷磺酸。認為該等係持久的且在一些情形中懷疑造成健康損害(G.L.Kennedy,Jr.、J.L.Butenhoff、G.W.Olsen、J.C.O′Connor、A.M.Seacat、R.G.Perkins、L.B.Biegel、S.R.Murphy、D.G.Farrar,Critical Reviews in Toxicology 2004,34,351-384)。此外，較長鏈之全氟烷羧酸及磺酸在食物鏈中累積。較短鏈氟建構組元更多係關於其生態毒理學特性，但通常在其應用領域中展現更差性質。WO 2006/072401及WO 2010/003567闡述含有三氟甲氧基之表面活性化合物。含有氟化烷基之其他氟界面活性劑闡
述於WO 2009/149807、WO 2010/003567、WO 2010/149262、WO 2011/082770、WO 2012/084118、WO 2015/124290及WO 2016/096129中。
而且，業內需要較佳不會在降解時分解以獲得長鏈持久化合物之替代表面活性物質。現在已發現適宜作為表面活性物質且較佳不具有一或多個上述缺點之新穎化合物。本發明首先係關於式(I)化合物(R1-CHF-CF2-Y-)m間隔基(X)n (I)
其中R1=視情況含有雜原子之氟化、直鏈或具支鏈烷基，間隔基=單鍵或二價有機基團，X=親水基團，Y=S、SO或SO2，m係
1；且n係
1，其中不包括其中Rf=視情況含有雜原子之全氟化烷基且R'=H或C1-C4-烷基之化合物(A)、(B)及(C)，
本發明之化合物較佳不含-O-O-鍵。新穎化合物較佳含有以下變量：R1=直鏈或具支鏈、視情況含有雜原子之全氟化烷基、較佳全氟化C1-C6-烷基、尤佳全氟化C1-C4-烷基、具體而言全氟化C1-C3-烷基，間隔基=視情況含有雜原子之飽和或不飽和、具支鏈或不具支鏈烴單元，其中不存在-O-O-鍵，X=陰離子、陽離子、非離子或兩性基團，Y=S、SO或SO2，較佳S，m=1、2、3、4、5或6、較佳2-4、具體而言2-3，且n=1、2、3或4，較佳1或2。
式(I)之尤佳化合物係其中所有變量具有較佳含義之彼等。
氟化基團R1較佳選自以下基團：CF3-(CF2)0-3-、CF3-(CF2)0-3-O-、CF3-(CF2)0-3-O-(CF2)1-3-、CF3-(CF2)0-3-O-(CF2)1-3-O-、CF3-(CF2)0-3-O-(CF2)1-3-O-CF2-、CF3-(CF2)0-3O-(CF2-O)1-8-及CF3-(CF2)0-3-O-(CF2-O)1-8-CF2-。
氟化基團R1尤佳係CF3-(CF2)1-2-O-基團、具體而言CF3-CF2-CF2-O基團。
較佳陰離子基團X可選自COO-、-SO3 -、-OSO3 -、-PO3 2-、-OPO3 2-、-OP(O)(O-)O-、-(OCH2CH2)s-O-(CH2)t-COO-、-(OCH2CH2)s-O-(CH2)t-SO3 -、-
(OCH2CH2)s-O-(CH2)t-OSO3 -、-(OCH2CH2)s-O-(CH2)t-PO3 2-、-(OCH2CH2)s-O-(CH2)t-OPO3 2-或式A至C，
其中s代表在1至1000範圍內之整數，t代表選自1、2、3或4之整數且w代表選自1、2或3之整數。
較佳陰離子基團在此處具體而言包括-COO-、-SO3 -、-OSO3 -、-PO3 2-、-OPO3 2-、-OP(O)(O-)O-、子式A、及-(OCH2CH2)s-O-(CH2)t-COO-、-(OCH2CH2)s-O-(CH2)t-SO3 -及-(OCH2CH2)s-O-(CH2)t-OSO3 -，其中該等基團之每一者自身可較佳。X亦可代表相應酸。
極佳陰離子基團在此處包括-SO3 -、-OSO3 -、-COO-、-PO3 2-、-OP(O)(O-)O-或OPO3 2-。具體而言，磺酸根基-SO3 -係較佳的。
陰離子基團X之較佳相對離子係單價陽離子、具體而言H+、鹼金屬陽離子或NR4 +，其中R=H或C1-C6-烷基，且所有R可相同或不同。尤佳者係H+、Na+、K+、Li+及NH4 +，尤其較佳係Na+。
含相對離子Z-的較佳陽離子基團X可選自-NR1R2R3+Z-、-PR1R2R3+Z-，
其中R代表在任何期望位置之H或C1-4-烷基，Z-代表Cl-、Br-、I-、CH3SO3 -、CF3SO3 -、CH3PhSO3 -、PhSO3 -，R1、R2及R3各自彼此獨立地代表H、C1-30-烷基、Ar或-CH2Ar，且Ar代表具有6至18個C原子之未經取代或單取代或多取代之芳香族環或稠環系統，此外其中一或兩個CH基團可經N替代。
較佳陽離子基團在此處具體而言包括-NR1R2R3+Z-及
其中該等基團之每一者自身可係較佳的。
較佳非離子基團X可選自：直鏈或具支鏈烷基，其中一或多個非毗鄰C原子已經O、S及/或N替代，-OH、-SH、-O-(醣苷)o'、-S-(醣苷)o'、-OCH2-CHOH-CH2-OH、-OCH2Ar(-NCO)p'、-OAr(-NCO)p'、胺氧化物，
u代表在1至6、較佳1至4範圍內之整數，o'代表在1至10範圍內之整數，p'代表1或2，Ar代表具有6至18個C原子之未經取代、單取代或多取代芳香族環或稠環系統，此外其中一或兩個CH基團可經C=O替代，且，
醣苷代表醚化碳水化合物、較佳單、二、三或寡醣苷。
較佳非離子基團X在此處具體而言包括直鏈或具支鏈烷基(其中一或多個非毗鄰C原子已經O、S及/或N替代)、-OH及-O-(醣苷)o'。
若X=烷基，其中一或多個非毗鄰C原子已經O、S及/或N替代，則其較佳等於R4-(B-A)m"-，其中R4=H或C1-4-烷基、具體而言H或CH3，A=較佳具有1至10個碳原子、具體而言具有1至4個碳原子之直鏈或具支鏈伸烷基，B=O或S、較佳O，且m"=較佳在1至100、尤佳1至30範圍內之整數。
非離子基團X尤佳係基團R4-(O-CH2CHR5)m"-，其中m"=較佳在1至100、尤佳1至30、具體而言亦1-25範圍內之整數，且R4及R5=H或C1-4-烷基、具體而言H或CH3。R4-(B-A)m"-尤佳係聚乙二醇或聚丙二醇單元。
非離子基團X尤佳係基團-CH(OH)-CH2-NH-sach(其中sach=各種糖)及基團-Y-(CH2-CH2-O)v-R4，其中Y=S、O或NH、較佳O，R4=H或烷基、較佳H或CH3，且v=1至100、較佳1至30、具體而言亦1至25。
較佳兩性基團X可選自官能基乙醯基二胺、N-烷基胺基酸、N-烷基胺基磺酸、甜菜鹼、磺基甜菜鹼或相應衍生物、具體而言選自以下，其中M代表H或鹼金屬離子、較佳Li+、Na+或K+：
本發明之尤佳化合物係含有較佳陰離子基團、較佳非離子基團或較佳兩性離子基團中之一者作為親水基團X之彼等。
尤佳者係含有基團-SO3 -、-OSO3 -、-COO-、-PO3 2-、-OP(O)(O-)O-或OPO3 2-、聚乙二醇或聚丙二醇、-CH(OH)-CH2-NH-sach、-Y-(CH2-CH2-O)v-R4、甜菜鹼或磺基甜菜鹼之化合物。較佳相對離子在此處係H+、Na+、K+及NH4 +、具體而言Na+。尤佳者係：-SO3 -、-COO-、-OP(O)(O-)O-或-OPO3 2-、聚乙二醇或聚丙二醇、磺基甜菜鹼、基團-CH(OH)-CH2-NH-sach及基團-Y-(CH2-CH2-O)v-R4。在此處，sach=各種糖且Y=S、O或NH、較佳O，R4=H或烷基、較佳H或CH3，且v=1至100、較佳1至30、具體而言亦1至25。其中X=-SO3 -之化合物亦可特別有利。
式(I)化合物之間隔基的烴單元可為脂肪族或芳香族單元，視情況提供有雜原子。間隔基較佳係飽和、具支鏈或不具支鏈烴單元、較佳飽和、
具支鏈或不具支鏈伸烷基，其中一或多個非毗鄰C原子可由O或N、較佳O替代，或連接至O。較佳者係例如C1-C6-伸烷基、具體而言C1-C4-伸烷基。
在本發明之變化形式中，所用較佳含有雜原子之烴單元係聚乙二醇或聚丙二醇單元。
較佳者係式(II)至(V)之化合物，其中R1及R2彼此獨立地係視情況含有雜原子之氟化、直鏈或具支鏈烷基，o=0至100、較佳1至30及5至30、具體而言3、5、6、10、12、15、18、20或24，且X1及X2彼此獨立地係親水基團、具體而言陰離子、陽離子、非離子或兩性基團、較佳針對X之較佳基團中之一者，或在式(IIa)、(IIb)、(IIc)及(V)中亦為H：
在式(II)至(V)之化合物的較佳變化形式中，X1及X2彼此獨立地係陰離子或非離子基團、具體而言較佳針對X之基團，且R1及R2彼此獨立地係CF3-(CF2)1-2-O-基團。R1與R2、及X1與X2較佳相同。
尤佳者係含有基團-SO3 -、-OSO3 -、-COO-、-PO3 2-、-OP(O)(O-)O-或-OPO3 2-、聚乙二醇或聚丙二醇、-CH(OH)-CH2-NH-sach、-Y-(CH2-CH2-O)v-R4、甜菜鹼、或磺基甜菜鹼作為X1及/或X2之化合物。較佳相對離子在此處係H+、Na+、K+及NH4 +、具體而言Na+。尤佳者係：-SO3 -、-COO-、-OP(O)(O-)O-或-OPO3 2-、聚乙二醇或聚丙二醇、磺基甜菜鹼、基團-CH(OH)-CH2-NH-sach及基團-Y-(CH2-CH2-O)v-R4。在此處，sach=各種糖且Y=S、O或NH、較佳O，R4=H或烷基、較佳H或CH3，且v=1至100、較佳1至30、具體而言亦1至25。其中X=-SO3 -之化合物亦可特別有利。式(IIa)及(III)至(V)之化合物、尤其具有較佳變量之彼等係尤佳的。
在本發明之另一變化形式中，氟化化合物較佳基於馬來酸及烏頭酸之酯。該等化合物係由式(VI)及(VII)表示，其中L1、L2及L3彼此獨立地係視情況含有雜原子之飽和或不飽和、具支鏈或不具支鏈烴單元，其中不存在-O-O-鍵，具體而言直鏈或具支鏈C1-C6-烷基、尤佳C1-C4-烷基，X
係親水基團且R1、R2及R3彼此獨立地係視情況含有雜原子之氟化、直鏈或具支鏈烷基：
在式(VI)及(VII)之化合物的較佳變化形式中，L1、L2及L3彼此獨立地係直鏈或具支鏈C1-C6-烷基、尤佳C1-C4-烷基，X係陰離子或非離子基團且R1、R2及R3彼此獨立地係CF3-(CF2)1-2-O-基團。較佳地，L1、L2及L3相同且R1、R2及R3相同。
其中一或多個變量具有較佳含義之式(I)至(VII)之化合物係特別有利的。其中所有該等變量具有較佳含義、具體而言尤佳含義之式(I)至(VII)之化合物係特別有利的。
尤佳者係式(VIII)至(XVIII)之化合物，其中變量具有針對式(I)至(VII)所指示之含義、具體而言較佳含義，且PEG代表聚乙二醇、聚丙二醇、聚乙二醇烷基醚或聚丙二醇烷基醚，且Ra、Rb及Rc=H或C1-4-烷基、具體而言H或CH3。烷基醚較佳係C1-C4-烷基醚、具體而言C1-C2-烷基醚、尤其甲醚：
尤佳者係式(VIII)至(XVIII)之化合物，其中氟化基團R1及R2或R1、R2及R3彼此獨立地選自以下基團：CF3-(CF2)0-3-、CF3-(CF2)0-3-O-、CF3-(CF2)0-3-O-(CF2)1-3-、CF3-(CF2)0-3-O-(CF2)1-3-O-、CF3-(CF2)0-3-O-(CF2)1-3-O-CF2-、CF3-(CF2)0-3O-(CF2-O)1-8-及CF3-(CF2)0-3-O-(CF2-O)1-8-CF2-。
氟化基團R1及R2或R1、R2及R3尤佳彼此獨立地係CF3-(CF2)1-2-O基團、具體而言CF3-CF2-CF2-O基團。特別佳地，R1及R2相同且R1、R2及R3相同。o較佳等於1-30、具體而言3、5、6、10、12、15、18、20或24、
具體而言3、10或18。式(VIII)至(XIV)及(XV)、(XVI)、(XVII)及(XVIII)之化合物、尤其具有較佳變量之彼等係尤佳的。
具體而言，式(XIX)至(XXIV)之以下化合物(其中o=0、10或18且R=甲基或乙基)係尤佳的：
式(XIXa)及(XX)至(XXIX)之化合物、尤其具有較佳變量之彼等係尤佳的。
本發明基於全氟烯烴之氟界面活性劑具有較習用氟界面活性劑低之
穩定性且因此可更易於藉由物理/化學過程降解，且較佳不持久。本發明之氟界面活性劑可因在水溶液中極其有效的降低表面張力能而著稱。此外，該等化合物較佳具有低CMC及低起泡行為。
而且，硫橋之引入使能夠擴展分子結構之變化。眾所周知，硫化物可使用熟習此項技術者自文獻得知之方法轉化為亞碸，其允許分子極性關於親水性之額外「修整」。
本發明之化合物可藉由熟習此項技術者已知之方法製備。借助全氟烯烴及雜官能分子，可特定製備能夠組合許多正面效應之新穎氟界面活性劑。已發現，硫醇化合物由於其增加之親核性而具有比相當的醇顯著更高之反應性。此優點現在可藉由醚化單-或多官能醇加以利用，該等醇另外亦含有一或多個選擇性地在硫基團上之硫醇基團而不需引入保護基團。然後，自由OH基團可進一步在第二步驟中反應。此性質使得其與相應醇化合物相比可能極大地簡化合成性能且使得產率增加。
以下方案1至6顯示本發明化合物之說明性合成。該等製程通常已為熟習此項技術者已知且可在習用條件下實施。較佳使用以實例方式提及之以下全氟烯烴化合物：CF3-CF=CF2 CF3-CF2-CF2-OCF=CF2
CF3-CF2-CF=CF2 CF3-CF2-OCF=CF2
CF3-CF2-CF2-CF=CF2 CF3-OCF=CF2。
本發明化合物、具體而言式(II)至(VII)之化合物較佳可藉由以下合成途徑(以實例方式針對其中R1=CF3CF2CF2O-之化合物所示)製備。
方案1：
方案2a：
方案5：
本發明之其他化合物可類似於以上所示之說明性反應或藉由本身已為熟習此項技術者自文獻得知之其他方法製備。特別佳者在此處係式(VIII)至(XXIV)之化合物。該等製程通常已為熟習此項技術者已知且可在習用條件下實施。所用起始化合物係市售購得及/或其製備為熟習此項技術者熟知。
本發明化合物之優點具體而言係：- 關於效率及/或有效性，表面活性等於或優於習用烴界面活性劑，- 物質之生物及/或非生物降解性，而不形成持久的全氟化降解產物，例如PFOA(全氟辛酸)或PFOS(全氟辛烷磺酸酯)，- 可藉由簡單製程製備，- 弱起泡作用及/或低泡沫穩定，
- 在調配物中之良好加工性，及/或- 儲存穩定性。
本發明之化合物較佳可具有特定表面活性。本發明之式(I)化合物、具體而言式(II)及(VII)且較佳式(VIII)至(XXIV)之化合物可另外具有經改良之環境性質，此乃因其不會化學或生物降解而獲得長鏈PFCA或PFAS。本發明之化合物較佳可藉由相應環境影響完全轉化為可礦化/可再生化合物。
用於降解含氟化合物之製程包含以下步驟：a)生物及/或非生物降解含氟化合物之碳骨架，同時形成具有足夠高蒸氣壓之較佳無毒的含氟化合物，b)將在步驟a)中所形成具有高蒸氣壓之含氟化合物轉化為氣相，c)藉由在氣相中UV輻照使在步驟a)中所形成具有高蒸氣壓之含氟化合物降解，獲得低分子量化合物，d)將在步驟c)中所形成之低分子量化合物自氣相轉化為液相及/或固相，e)將在步驟d)中所形成之液相及/或固相之低分子量化合物礦化。
較佳地，在步驟a)中不形成含氟鹽。
具體而言，在步驟a)中不形成全氟化化合物。
式(I)至(XXIV)之化合物較佳可用作表面活性劑、較佳界面活性劑、疏水劑、界面促進劑、降黏劑、泡沫穩定劑或乳化劑。
此外，本發明係關於本發明之化合物及上述較佳實施例作為表面活性劑用於(例如)改良塗料調配物之流動行為及潤濕能力之用途。較佳使用式(I)至(VII)、具體而言式(VIII)至(XXIV)之氟界面活性劑、具體而言尤
佳所提及化合物。
除式(I)化合物、具體而言式(II)至(VII)、尤其式(VIII)至(XXIV)之較佳化合物以外，本發明之混合物亦可包含溶劑、添加劑、助劑及填充劑以及未氟化界面活性劑。可以實例方式提及聚矽氧粒子、塑化劑及表面經修飾顏料。
較佳應用領域係(例如)本發明之式(I)氟界面活性劑及較佳化合物作為添加劑於以下中之應用：表面塗層之製劑，例如油漆、塗層、保護性塗層、電子或半導體應用中之專用塗層(例如光阻劑、頂部抗反射塗層、底部抗反射塗層)或光學應用中之專用塗層(例如攝影塗層、光學元件塗層)；農用化學品、拋光劑及蠟(例如用於家具、地板及汽車、具體而言在地板拋光劑中)、滅火組合物、潤滑劑、在光微影製程、具體而言浸沒光微影製程中(例如在顯影劑溶液、沖洗溶液、浸沒油及/或在光阻劑自身中，尤其用於產生印刷電路)或用於添加至相應製劑之添加製劑。此外，根據本發明可用作界面活性劑之化合物適於洗滌及清潔應用且用作化妝品中之添加劑/界面活性劑，例如頭髮及身體護理產品(例如洗髮精、洗髮劑及潤髮乳)、泡沫浴、具有一或多種以下功能之乳液或洗劑：乳化劑、潤濕劑、起泡劑、助流劑、抗靜電劑、用於增加對皮膚油脂抗性之試劑。對於使用，通常將本發明之氟界面活性劑引入相應經設計製品中。基於整個製品，通常使用濃度係0.01重量%至1.0重量%之本發明界面活性劑。
本發明同樣係關於包含本發明氟界面活性劑之相應組合物。該等組合物較佳包含適於各別預期用途之媒劑及視情況其他活性物質及/或視情況助劑。較佳組合物係油漆及塗料製劑、滅火組合物、潤滑劑、洗滌及清
潔組合物及除冰劑或用於光微影製程、具體而言用於浸沒光微影製程且具體而言用於產生印刷電路之顯影劑溶液、沖洗溶液、浸沒油及光阻劑、農用化學品、地板拋光劑、化妝品或用於織物整理或玻璃處理之疏水組合物。較佳組合物在此處係油漆及塗料製劑及印刷墨水。此外，本發明亦係關於基於水之塗料調配物，其包含單獨或呈與添加劑之混合物之本發明氟界面活性劑。較佳使用基於以下合成成膜劑之塗料調配物：聚縮樹脂，例如醇酸樹脂、飽和/不飽和聚酯、聚醯胺/醯亞胺、聚矽氧樹脂；酚樹脂；脲樹脂及三聚氰胺樹脂、聚加成樹脂，例如聚胺基甲酸酯及環氧樹脂；聚合樹脂，例如聚烯烴、聚乙烯基化合物及聚丙烯酸酯。此外，本發明之氟界面活性劑亦適用於基於天然產物及經修飾天然產物之塗料。較佳者係基於油、多醣(例如澱粉及纖維素)、亦及基於天然樹脂(例如環狀寡萜烯、聚萜烯及/或蟲膠)之塗料。
本發明之氟界面活性劑可用於物理固化(熱塑性)塗料系統亦及交聯(彈性體及熱固性材料)水基塗料系統二者。本發明之氟界面活性劑較佳改良塗料系統之流動及潤濕性質。
本發明係關於根據本發明欲採用之氟界面活性劑、具體而言較佳化合物之此處所提及之所有用途。用於該等用途之氟界面活性劑之各別用途已為熟習此項技術者已知，此意味著根據本發明欲採用之氟界面活性劑之使用不存在任何問題。
以下實例更詳細的解釋本發明而非限制保護範圍。
NMR光譜係使用Bruker 400MHz光譜儀利用內標準品量測。
IR光譜係使用Brucker Alpha鉑-ATR光譜儀量測。
測定具有不同濃度c(克/公升)之水性界面活性劑溶液的靜態表面張力γ。
儀器：Dataphysics張力計(型號DCAT 11)
量測溶液之溫度：20°±0.2℃
所採用之量測方法：根據DIN EN 14370使用威廉姆板法(Wilhelmy plate method)量測表面張力。
板：鉑，長度=19.9mm
在板法中，界面活性劑溶液之表面或界面張力係自板之潤濕長度所
受作用力根據以下公式計算：
γ=界面或表面張力；F=作用於剩餘部分之力；L=潤濕長度(19.9mm)；θ=接觸角。板係由粗糙鉑構成且因此最佳潤濕，以使得接觸角θ接近0°。因此項cos θ大約達到值1，以使得僅所量測力及板之長度係必須考慮的。
EO 環氧乙烷單元
THF 四氫呋喃
MTBE 第三丁基甲基醚
b.p. 沸點
w% 重量%
將77.3g 1,1,1,2,2,3,3-七氟-3-三氟乙烯基氧基丙烷、52.2g 2-巰基乙醇、12.05g碳酸鉀及50ml乙腈在壓力反應器中合併。將反應混合物於100℃下攪拌20小時。將50ml水及50ml MTBE添加至反應混合物，並將各相分離。水相用2×30ml MTBE萃取。合併之有機相隨後用40ml水及40ml飽和NaCl溶液洗滌。萃取物經硫酸鈉乾燥，並蒸餾出溶劑。殘餘物然後經歷部分真空蒸餾。
此時在0.058毫巴之壓力下產物之頭溫度為49℃。產物重量：63.47g
1H-NMR：7.2ppm(dt,1 H,-CFH)；5.1ppm(t,1 H,=OH)；3.6ppm(q,2 H,-CH2-OH)；3.0ppm(t,2 H,S-CH2-CH2)
使實例1a中製備之醇與環氧乙烷在140℃及最高4巴下在壓力反應器中反應，獲得相應氟界面活性劑。端視反應時間，可達成各種鏈長度。此處所合成材料之統計EO鏈長度為3、10或18個單元。
1H-NMR：7.2ppm(dt,1 H,-CFH)；3.6ppm(q,2 H,-CH2-OH)；3.55-3.40(m,12 H,-CH2CH2-O)；3.0ppm(t,2 H,S-CH2-CH2)
1H-NMR：7.2ppm(dt,1 H,-CFH)；3.6ppm(q,2 H,-CH2-
OH)；3.55-3.40(m,42 H,-CH2CH2-O)；3.0ppm(t,2 H,S-CH2-CH2)
1H-NMR：7.2ppm(dt,1 H,-CFH)；3.6ppm(q,2 H,-CH2-OH)；3.55-3.40(m,74 H,-CH2CH2-O)；3.0ppm(t,2 H,S-CH2-CH2)
初始將11g來自實例1a之醇引入反應燒瓶中之4ml甲苯中並加熱至60℃。經10分鐘之時期緩慢添加2.00g磷醯氯。隨後將反應混合物加熱至115℃並在此溫度下攪拌5.5小時。隨後將批料冷卻至90℃並使用0.3ml水小心地水解，並將混合物在此溫度下再攪拌1小時。隨後去除溶劑，留下褐色殘餘物。
將20ml MTBE及20ml水添加至粗產物，並將各相分離。水相用2×30ml MTBE萃取。合併之有機相隨後使用氨溶液中和並分離。
產物重量：11.18g.
1H-NMR：7.3-7.1ppm(m,2 H,-CFH)；4.0-3.2ppm(m,S-CH2-CH2)；31 P-NMR：-0.7ppm(t,2 P)；-1.8ppm(quin,1 P)，即單酯及二酯係以比率2/1存在。
使11g來自實例1c之醇與1.5g POCl3類似於實例1f進行反應。
產量11.0g
1H-NMR：7.3-7.1ppm(m,2 H,-CFH)；3.8-3.3ppm(m,4 H,S-CH2-CH2)及(m,24 H,CH2-CH2-O)；31 P-NMR：-0.7ppm(t,3 P)；-1.8ppm(quin,2 P)，即單酯及二酯係以比率2/1存在。
初始將6.5g實例1a中製備之醇引入圓底燒瓶中之24ml乙腈中，並在攪拌的同時逐滴緩慢地添加5.4ml 40%過乙酸。然後將反應混合物加熱至80℃並在此溫度下攪拌24小時。將30ml水及30ml MTBE添加至反應混合物，並將各相分離。水相用2×30ml MTBE萃取。合併之有機相隨後用40ml水及40ml飽和NaCl溶液洗滌。萃取物經硫酸鈉乾燥，並蒸餾出溶劑。產物重量：6.69g
1H-NMR：8.2及7.2ppm(m,1 H,-CFH)；4.0ppm(m,4 H,SO2-CH2-CH2-OH)
將10.49g實例1a中製備之醇、1.30g馬來酸酐及0.68g對甲苯磺酸一水合物合併於圓底燒瓶中之30ml甲苯中。將反應混合物在水分離器的回流下攪拌24小時。將30ml水及30ml MTBE添加至反應混合物，並將各相分離。水相用20ml MTBE萃取兩次。合併之有機相隨後用30ml水及30ml飽和NaCl溶液洗滌。萃取物經硫酸鈉乾燥，並蒸餾出溶劑。產物重量：10.68g
1H-NMR：7.2ppm(dt,2 H,-CFH)；6.5ppm(m,2 H,-CH=CH-)；4.3ppm(t,2 H,-CH2-CH2-O)；3.2ppm(t,2 H,-CH2-CH2-S-)
初始將10.00g含氟馬來酸酯、2.71g 39%亞硫酸氫鈉溶液及30ml 2-丙醇引入圓底燒瓶中。然後使用氫氧化鈉溶液將反應混合物之pH調整至pH 6.3。隨後將反應混合物在95℃下攪拌96小時。將30ml MTBE及30ml水添加至反應混合物，並將各相分離。水相用20ml MTBE萃取兩次。合併之有機相隨後用30ml水及30ml飽和NaCl溶液洗滌。萃取物經硫酸鈉乾燥，並蒸餾出溶劑。產量：6.64g
1H-NMR：7.2ppm(dt,2 H,-CFH)；4.2ppm(m,4 H,S-CH2-CH2)；3.7ppm(dd,1 H,-CH-SO3-)；3.2ppm(t,4 H,CH2-CH2-O)；
2.8-3.0ppm(m,2 H,-CH2-CH)；
將9.49g實例1a中製備之醇、1.50g烏頭酸及0.45g對甲苯磺酸一水合物合併於圓底燒瓶中之50ml甲苯中。將反應混合物於115℃於水分離器上攪拌72小時。將30ml水及30ml MTBE添加至反應混合物，並將各相分離。水相用20ml MTBE萃取兩次。合併之有機相隨後用30ml水及30ml飽和NaCl溶液洗滌。萃取物經硫酸鈉乾燥，並去除溶劑。產物重量：6.78g
1H-NMR：7.8-7.6ppm(m,2 H,-CFH)；6.8ppm(s,H,-C=CH-)；4.4-4.0ppm(t,2 H,-CH2-CH2-S-)；3.7ppm(s,H,CH2--C=CH-)；3.2-2.8ppm(t,2 H,-CH2-CH2-O)
初始將6.78g來自實例2c之含氟烏頭酸酯、1.22g 39%亞硫酸氫鈉溶液及24ml 2-丙醇引入圓底燒瓶中。然後使用氫氧化鈉溶液將反應混合物之pH調整至pH 6.3。隨後將反應混合物在95℃攪拌96小時。將30ml MTBE及30ml水添加至反應混合物，並將各相分離。水相用20ml MTBE萃取兩次。合併之有機相隨後用30ml水及30ml飽和NaCl溶液洗滌。萃取物經硫酸鈉乾燥，並去除溶劑。產量：6.26g
1H-NMR：7.0ppm(dt,3 H,-CFH)；4.2-3.8ppm(m,6 H,S-CH2-
CH2)；3.5-2.5ppm(m,10 H,CH2-CH2-O)及CH2-RCH-CH-SO3H
將8.63g 1.1,1.2,2.3,3-七氟-3-三氟乙烯基氧基丙烷、2.50g 1,4-二巰基丁烷-2,3-二醇、0.67g碳酸鉀及30ml乙腈在壓力反應器中組合，並在120℃攪拌20小時。將30ml水及30ml MTBE添加至反應混合物，並將各相分離。水相用20ml MTBE萃取兩次。合併之有機相隨後用30ml水及30ml飽和NaCl溶液洗滌。萃取物然後經硫酸鈉乾燥，並蒸餾出溶劑。產物重量：9.82g
1H-NMR：7.2ppm(dt,2 H,-CFH)；5.3ppm(m,2 H,-OH)；3.7ppm(dt,2 H,CH2-CH-O-)；2.9-3.2ppm(m,4 H,CH2-S)；
使所製備醇與環氧乙烷在140℃及最高4巴下在壓力反應器中反應，獲得相應氟界面活性劑。端視反應時間，可達成各種鏈長度。此處所合成材料之統計EO鏈長度為5個單元。
1H-NMR：7.2ppm(dt,2 H,-CFH)；3.85-3.4ppm(m,44 H)；2.9-3.2ppm(m,4 H,CH2-S)；
類似於實例3b實施，只是乙氧基化實施更長時間直至達到以下平均重複數為止：3c：EO=10；3d：EO=15；3e EO=20。
初始將11g來自實例3a之化合物引入反應燒瓶中之4ml甲苯中加熱至60℃。經10分鐘之時期緩慢添加1.98g磷醯氯。隨後將反應混合物加熱至115℃並在此溫度下攪拌18小時。隨後將批料冷卻至90℃並使用0.3ml水小心地水解，並將混合物在此溫度下再攪拌1小時。隨後去除溶劑，留下褐色殘餘物。
將20ml MTBE及20ml水添加至粗產物，並將各相分離。水相用2×30ml MTBE萃取。合併之有機相隨後使用氨溶液中和並分離。
產物重量：11.18g
1H-NMR：7.2ppm(dt,2 H,-CFH)；3.75ppm(m,2 H,ROCH-CHOR)；2.75ppm(m,4 H,S-CH 2-CHR)
將7.53g 1,1,1,2,2,3,3-七氟-3-三氟乙烯基氧基丙烷、3.58g 2-巰基乙磺酸鈉鹽、0.90g碳酸鉀及30ml乙腈在壓力反應器中組合並在110℃攪拌18小時。
將MTBE及水添加至反應混合物，並將各相分離。水相用2×25ml MTBE萃取，且合併之有機相用30ml水及30ml飽和NaCl溶液洗滌。
萃取物經硫酸鈉乾燥，並去除溶劑。
產物重量：6.53g
1H-NMR：7.2ppm(dt,1 H,-CFH)；3.2-2.7ppm(m,4 H,S-CH 2-CH 2-SO3Na)；表1顯示本發明化合物之靜態表面張力及CMC(臨界膠束濃度)。
Claims (8)
- 一種式(I)化合物，(R1-CHF-CF2-Y-)m間隔基(X)n (I)其中R1=CF3-(CF2)1-2-O-，間隔基=含有或未含有雜原子之飽和或不飽和、具支鏈或不具支鏈烴單元，其中不存在-O-O-鍵，X=陰離子、陽離子、非離子或兩性基團，Y=S、SO或SO2，m=1、2、3、4、5或6，且n=1、2、3或4，其中：陰離子基團X係選自COO-、-SO3 -、-OSO3 -、-PO3 2-、-OPO3 2-、-OP(O)(O-)O-、-(OCH2CH2)s-O-(CH2)t-COO-、-(OCH2CH2)s-O-(CH2)t-SO3 -、-(OCH2CH2)s-O-(CH2)t-OSO3 -、-(OCH2CH2)s-O-(CH2)t-PO3 2-、-(OCH2CH2)s-O-(CH2)t-OPO3 2-或式A至C，
- 如請求項1之化合物，其中m=2-4，且n=1或2。
- 如請求項1之化合物，其中其符合下式中之一者：
- 一種化合物，其符合下式中之一者：
- 一種化合物，其符合下式中之一者：
- 一種如請求項1至5中任一項之化合物之用途，其作為添加劑用於油漆、印刷墨水、保護性塗層、電子應用中之專用塗層、光阻劑、頂部抗反射塗層或底部抗反射塗層、用於光微影製程之顯影劑溶液及洗滌溶液、化妝品、農用化學品、地板拋光劑、攝影塗層或光學元件之塗層。
- 一種組合物，其包含如請求項1至5中任一項之化合物及媒劑。
- 如請求項7之組合物，其中該組合物係油漆及塗料製劑、滅火組合物、潤滑劑、洗滌及清潔組合物、除冰劑、用於光微影製程之顯影劑溶液及洗滌溶液及光阻劑、化妝品、農用化學品、地板拋光劑或用於織物整理或玻璃處理之疏水組合物。
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| CN102216263A (zh) * | 2008-11-13 | 2011-10-12 | 纳幕尔杜邦公司 | 氟代烷基醚磺酸盐表面活性剂 |
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