CN107442037A - A kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent and preparation method - Google Patents
A kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent and preparation method Download PDFInfo
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- CN107442037A CN107442037A CN201710748341.0A CN201710748341A CN107442037A CN 107442037 A CN107442037 A CN 107442037A CN 201710748341 A CN201710748341 A CN 201710748341A CN 107442037 A CN107442037 A CN 107442037A
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- ocf
- fluorine
- carboxylic acid
- active agent
- surface active
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 97
- 239000011737 fluorine Substances 0.000 title claims abstract description 97
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 55
- 239000003513 alkali Substances 0.000 title claims abstract description 52
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 48
- 235000016068 Berberis vulgaris Nutrition 0.000 title claims abstract description 47
- 241000335053 Beta vulgaris Species 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 halide compound Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 150000004820 halides Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 74
- 150000001408 amides Chemical group 0.000 claims description 43
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- 238000006467 substitution reaction Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 claims description 2
- ODJZWVFLHZHURI-UHFFFAOYSA-M [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] Chemical compound [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] ODJZWVFLHZHURI-UHFFFAOYSA-M 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 239000002280 amphoteric surfactant Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 3
- 229920002313 fluoropolymer Polymers 0.000 abstract 1
- 239000004811 fluoropolymer Substances 0.000 abstract 1
- 150000004702 methyl esters Chemical class 0.000 abstract 1
- 235000019000 fluorine Nutrition 0.000 description 73
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- 239000013067 intermediate product Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 20
- 238000002390 rotary evaporation Methods 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000012043 crude product Substances 0.000 description 17
- 230000005311 nuclear magnetism Effects 0.000 description 17
- 239000002994 raw material Substances 0.000 description 12
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 8
- UHCUUHRJIQKFHI-UHFFFAOYSA-N 2-(2-propoxypropoxy)propanoic acid Chemical class CCCOC(C)COC(C)C(O)=O UHCUUHRJIQKFHI-UHFFFAOYSA-N 0.000 description 7
- 229960003237 betaine Drugs 0.000 description 7
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 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 6
- 238000004064 recycling Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000005639 Lauric acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- AEDIXYWIVPYNBI-UHFFFAOYSA-N heptanamide Chemical compound CCCCCCC(N)=O AEDIXYWIVPYNBI-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229940005605 valeric acid Drugs 0.000 description 4
- XWVXXVQCDFVDMW-UHFFFAOYSA-N 2-chloropropanoic acid;sodium Chemical compound [Na].CC(Cl)C(O)=O XWVXXVQCDFVDMW-UHFFFAOYSA-N 0.000 description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- ZHHHDUSWMATTFE-UHFFFAOYSA-N 1,1-dipropylhydrazine Chemical compound CCCN(N)CCC ZHHHDUSWMATTFE-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C*1C2C1C2)C1C(C**)=C1CCC1CC(C)=*C1 Chemical compound CC(C*1C2C1C2)C1C(C**)=C1CCC1CC(C)=*C1 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 description 1
- AIAVNRXRUQWQTA-UHFFFAOYSA-N CC(NCCN(C)CCNC(C)=O)=O Chemical compound CC(NCCN(C)CCNC(C)=O)=O AIAVNRXRUQWQTA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 108091027305 Heteroduplex Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JHROQORAJUWVCD-UHFFFAOYSA-N methyl 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoate Chemical class COC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JHROQORAJUWVCD-UHFFFAOYSA-N 0.000 description 1
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent and preparation method.The present invention fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent chemical general formula be：Wherein, Rf C3‑C20Fluorine-containing chain radicals it is any,For CH2OrAny of group, R1For C2‑C5Any of divalent group of alkane chain, R2For C1‑C6Any of alkyl, phenyl or benzyl, R3For C1‑C4The divalent group of alkane chain.The preparation method of the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent of the present invention also comprises the following steps：Intermediate (I) is prepared with alkane alkenyl triamine in perfluoroacyl halide compound or perfluor methyl esters, intermediate (I) reacts to obtain intermediate (II) with halides, and intermediate (II) obtains sulfonic fluoropolymer type amphoteric surfactant with halogenated carboxylic acid reactant salt.Wherein, the chemical formula of intermediate (I) isThe chemical formula of intermediate (II) is
Description
Technical field
The present invention relates to amphoteric surfactant technical field, more particularly to a kind of fluorine-containing carboxylic acid type beet alkali ampholytic from
Sub- surfactant and preparation method.
Background technology
Fluorine-containing hydrocarbon-based surfactant with its unique " three high ", " two hate " performance, i.e., surface-active, heat-resistant stability and
Chemical stability is high.With the increasingly increase of domestic and international market, fluorine-containing surfactant excellent performance is with high content of technology, attached
It is value added big, cause the great interest of lot of domestic and foreign researcher.Its fluorine-containing alkyl have water and oil repellant [new chemical materialses, 2004,
32(8)：46], it is widely used in oil exploitation, coal is metallurgical, mechanical industry, medicine, agricultural etc. field [household chemicals,
2011,41(4)：40-43].The excellent application performance of fluorine-containing surfactant, the accreditation in market, demand day have gradually been obtained
Benefit increase, although the added value of fluorine-containing surfactant is high, technology content is also high.Nearly ten years, novel fluorine surface-active
Agent molecule structure continues to bring out, and has the novel fluorines such as double carbon fluorine chains, the hydrocarbon heteroduplex of carbon fluorine, double hydrophilic chains, more hydrophilic chains
Surfactant is reported in succession.Although the development of fluorine-containing surfactant has obtained significant progress, but still suffers from quantity
Less, the state of single varieties, as perfluor anion surface active PFOA products are difficult to degrade, its application is restricted.
Betaines amphoteric surfactant is relatively early commercialized surfactant, due to internal salt structure be present in molecule
Characteristic makes it not only have fabulous salt-resistance, and good surface-active can be also kept in the range of wider pH value, still wide so far
It is general to be applied in the industries such as daily use chemicals, printing and dyeing.But in some special application fields, as fabric finishing agent, levelling agent, extinguishing chemical,
Demulsifier and collection finish etc. still feel deficiency；And fluorine-containing aliphatic alkyl betaine type amphoteric surfac-tant is in extremely low critical glue
Beam concentration also has excellent surface-active, is much better than amphoteric surfactant containing alkyl betaine-type.
Usually contain C3-C12Fluorohydrocarbon based surfactants all there is excellent surface-active, but perfluorochemical is wide
It is general to apply a series of environmental problems also brought, as perfluorooctanoic acid salt (PFOA) has the basic of persistent environmental organic pollution
Feature.2006, main fluorine material manufacturer of 8 worlds including Du Pont, 3M, great Jin, A Kema etc. signed PFOA
Emission reduction agreement, promise stop using PFOA stage by stage.PFOA will be all prohibitted the use of in all products in 2015 and can be derived
PFOA compound.Meanwhile existing fluorine-containing surfactant poor-performing, in some extreme environment, as in high salt
In environment, surface tension shows poor, influences using effect, reduces application.
The content of the invention
It is an object of the present invention to provide a kind of fluorine-containing carboxylic acid type sweet tea in hypersaline environment with excellent properties
Dish alkali zwitterionic surfactant.
The present invention one lives further objective is that to provide one kind and prepare fluorine-containing carboxylic acid type beet alkali ampholytic ion surface
The preparation method of property agent.
Especially, the invention provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, its chemical general formula
For：
Wherein, Rf C3-C20Fluorine-containing chain radicals it is any,For CH2OrAppointing in group
One kind, R1For C2-C5Any of divalent group of alkane chain, R2For C1-C6Alkyl, any in phenyl or benzyl
Kind, R3For C1-C4The divalent group of alkane chain.
Alternatively, the C3-C20Fluorine-containing chain radicals are the perfluoroalkyl that oxygen atom is inserted in perfluoro alkane base, straight chain
Or there is any one in the perfluoro alkane base that hydrogen substitutes end.
Alternatively, the perfluoroalkyl for oxygen atom being inserted in the straight chain is-CF2OCF(CF3)2、 -CF(CF3)
OCF2CF3、-CF2CF2OCF2CF3、-CF(CF3)OCF(CF3)2、 -CF2CF2OCFCF3OCF2CF3、-CF2CF(CF3)OCF
(CF3)2、 -CF2CF(CF3)OCF2CF2CF3、-CF2CF(CF3)OCF2CF2OCF2CF3、 -CF2CF2OCF2CF2OCF2(CF3)2、-
CF2CF(CF3)OCF2CF2OCF2(CF3)2、 -CF(CF3)OCF2CF(CF3)OCF2CF2CF3、-CF2CF2OCF2CF(CF3)
OCF2CF2CF3、 -CF2CF(CF3)OCF2CF2OCF2CF2CF3、-CF2CF2OCF(CF3)OCF2CF2OCF(CF3)2、 -
CF2CF2OCF(CF3)OCF2CF2OCF2CF2CF3、 -CF2CF(CF3)OCF2CF(CF3)OCF(CF3)2、 -CF2CF(CF3)OCF2CF
(CF3)OCF(CF3)2、 -CF2CF(CF3)OCF2CF(CF3)OCFCF2CF3、 -CF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)
OCF2CF(CF3)2Or-CF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)2Any of.
Alternatively, the perfluoro alkane base that the end has hydrogen to substitute is-CF2CF2CF2CF2CF2CF2CF2CF2H、-
CF2CF2CF2CF2CF2CF2CF2H、 -CF2CF2CF2CF2CF2CF2H、-CF2CF2CF2CF2CF2H、-CF2CF2CF2CF2H or-
CF2CF2CF2Any of H.
Alternatively, the R1For any of propylidene, butylidene or pentylidene.
The present invention also provides a kind of preparation method of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, comprising as follows
Step：
(1) preparation of the triamine intermediate (I) of perfluor acid amides substitution
Monosubstituted alkyl triamine is mixed with organic solvent, perfluoroalkyl etheride is added dropwise under ice-water bath and stirs mixed
Close, be warmed to room temperature after dripping, be stirred for 2-6h, obtain the triamine intermediate (I) of perfluor acid amides substitution, the perfluor acid amides
The chemical formula of substituted triamine intermediate (I) is：
Wherein, RfFor C3-C20Fluorine-containing chain radicals it is any,For CH2OrAppointing in group
One kind, R1For C2-C5Any of divalent group of alkane chain；
(2) preparation of the triamine intermediate (II) of perfluor acid amides substitution
The triamine intermediate (I) that the perfluor acid amides substitutes is mixed with halide in alkali organic solvent, and adds and urges
Agent, flow back 12-24h under agitation, obtains the triamine intermediate (II) of the perfluor acid amides substitution, the perfluor acid amides substitution
The chemical formula of triamine intermediate (II) be：
Wherein, R2For C1-C6Any of alkyl, phenyl or benzyl；
(3) preparation of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent
The triamine intermediate (II) that the perfluor acid amides is substituted and the halogenated carboxylic acid salt alkalescent solvent in return
Stream reaction 10-16h, it is therefore preferable to, 10-12h, the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent is obtained, it is described
The chemical formula of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent is：
Wherein, R3For C1-C4The divalent group of alkane chain.
Alternatively, in the preparation process of the triamine intermediate (I) of perfluor acid amides substitution, the monosubstituted alkyl three
The mol ratio of amine and the perfluoroalkyl etheride is 1:2~1：3, it is therefore preferable to 1:2.1~1:2.2；The perfluoroalkyl
It is one or more that etheride is selected from perfluoroalkyl acyl chlorides, perfluoroalkyl acyl fluorides or perfluoroalkyl acid esters.
Alternatively, in the preparation process of the triamine intermediate (II) of perfluor acid amides substitution, the catalyst is four
Butylammonium bromide, and the addition of catalyst is a small amount of, generally raw material 0.01% or so；The three of the perfluor acid amides substitution
The mol ratio of amine intermediate (I) and the halide is 1:1~1:2.5, it is therefore preferable to 1:1.2；
The alkali organic solvent is in sodium methoxide and anhydrous THF mixtures or sodium methoxide and absolute ether mixture
It is a kind of.
Alternatively, also include adding during the preparation of the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent
Enter TBAB to react as catalyst, the triamine intermediate (II) and halogenated carboxylic acid of the perfluor acid amides substitution
The mol ratio of salt is 1:2~1:3.5, it is preferable that the triamine intermediate (II) and halogenated carboxylic acid salt of the perfluor acid amides substitution
Mol ratio is 1:2.4-1:3.And preferably, halogenated carboxylic acid salt may be selected from sodium chloroacetate or chloropropionic acid sodium.
There is the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent of the present invention relatively low concentration (to be less than 10-
100mg/L), while also there is good reduction aqueous phase system surface tension 14.5mN/m (0.1%).Live on this surface
Property agent has preferable salt-resistance, and more excellent table can be kept under hypersaline environment (% of salinity 3.34 human configuration sea salt)
Face activity (15.2-18.9mNm-1)。
Further, the preparation method of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent of the invention is simple, examination
Agent is common, and preparation condition is gentle, the extreme condition such as no HTHP, can prepare at room temperature, and what is prepared contains carboxylic acid fluoride
Type beet alkali ampholytic ionic surface active agent has higher yield.
According to hereafter will become more apparent that the present invention to the detailed description of the specific embodiment of the invention, those skilled in the art
Above-mentioned and other purposes, advantages and features.
Embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1
The present embodiment provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, and it has following structure：
The above-mentioned fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent that the present embodiment provides is according to following steps system
For what is obtained：
(1) intermediate product (I) is prepared：Intermediate product (I) in the present embodiment is N, N '-(imino group -2,1- second diyl)
Enjoy a double blessing fluorine (2,5- dimethyl -3,6- dioxanonanoic acids) acid amides
0.01mol (1.03g) divinyl three is added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring
Amine and 20mL absolute ethers, reaction system are cooled down with ice-water bath.Under agitation, by 0.021mol (10.81g) perfluor (2,5- bis-
Methyl -3,6- dioxanonanoic acids) acyl chlorides is slowly dropped into reaction system by dropping funel.After dripping off, it is warmed to room temperature.It is stirred for
React 4h.TLC tracks reaction end.Reaction is finished, and reactant mixture is washed 2 times with 2% sodium hydroxide.Organic layer is separated, then
By washing, then dried with anhydrous magnesium sulfate, reclaim ether, vacuum distillation removes excessive diethylenetriamine.Obtain 9.94g
Pale yellow viscous liquid product, purity GC analyses are more than 95%, yield 93.8%.Product can also use column chromatography further pure
Change.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.86(s,2H)；3.36-3.34(t,4H)；2.73-2.71(t,4H)； 1.74
(s,1H)。
19(400MHz,CDCl3)：- 80.12~-80.16 (s, 6F)；- 80.19~-80.22 (s, 6F)；- 81.52~-
81.57(t,6F)；- 82.66~-82.74 (m, 4F)；-83.74(m,2F)；- 129.75~-129.78 (m, 4F)； -113.15
(m,2F)；- 132.75~-132.85 (m, 4F).
(2) intermediate product (II) is prepared：Intermediate product (II) in the present embodiment is N, N '-[(methyl imido) -2,1-
Second diyl] fluorine of enjoying a double blessing (2,5- dimethyl -3,6- dioxanonanoic acids) acid amides
Added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring 0.001mol (1.06g) N, N '-
(imino group -2,1- second diyl) fluorine of enjoying a double blessing (2,5- dimethyl -3,6- dioxanonanoic acids) acid amides, 0.0012mol's (0.064g)
Sodium methoxide and 10mL absolute ethers, a small amount of TBABs are added as catalyst.Under agitation, by 0.0012mol
(0.18g) iodomethane is dissolved in the anhydrous THF of 5ml, then is slowly dropped into by dropping funel in reaction system.After dripping off, it is stirred for
React 12h.GC detects the consumption of raw material, judges reaction end with this.After completion of the reaction, filter, filter vacuum rotary evaporation obtains
To light yellow paste.Then 2% sodium hydroxide solution 10ml stirrings fully dissolving is added, adds 8ml × 2 time dichloromethane
Extraction, organic layer in vacuo rotary evaporation obtain light yellow liquid crude product, can use ethyl acetate/methanol (2:1) crystallize, obtain
0.93g products, yield 86.6%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.00(s,2H)；3.41-3.39(t,4H)；2.53-2.50(t,4H)； 2.17
(s,1H)。
19(400MHz,CDCl3)：- 80.12~-80.16 (t, 6F)；- 80.19~-80.22 (m, 6F)；- 81.52~-
81.56(m,6F)；- 82.66~-82.74 (m, 4F)；-83.14(m,2F)；- 129.75~-129.78 (m, 4F)； -113.15
(m,2F)；- 132.75~-132.85 (m, 4F).
(3) fluorine-containing glycine betaine product is synthesized：In the 250mL round-bottomed flasks equipped with stirring, 0.024mol is separately added into
The sodium chloroacetate of (2.8g) and 0.01mol (10.7g) N, N '-[(methyl imido) -2,1- second diyl] fluorine of enjoying a double blessing (2,5- diformazans
Base -3,6- dioxanonanoic acids) acid amides and 60mL isopropanol/waters mixed solvent (1:1) it is former, to be stirred at reflux reaction 10h, TLC detection
The consumption of material, reaction end is judged with this.After completion of the reaction, rotary evaporation in vacuo recycling design.Residue is added into isopropanol
Middle dissolving, it is filtered to remove excessive sodium chloroacetate, then rotary evaporation in vacuo recovery isopropanol.It is thick that cooling obtains yellow maltose shape
Product.Crude product can use ethyl acetate/methanol (1:1) crystallize, obtain 9.94g light yellow solid products, yield 87.9%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,DMSO_D6)：7.82(s,2H)；4.46(s,3H)；3.68-3.63(t,4H)； 3.53-
3.50(t,4H)；3.17(s,1H).
19(400MHz,DMSO_D6)：- 80.11~-80.15 (t, 6F)；- 80.16~-80.21 (m, 6F)；- 81.52~-
81.56(m,6F)；- 82.66~-82.74 (m, 4F)；-83.18(m,2F)；- 129.75~-129.78 (m, 4F)；-113.17
(m,2F)；- 132.75~-132.85 (m, 4F).
Embodiment 2
The present embodiment provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, and it has following structure：
The above-mentioned fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent that the present embodiment provides is according to following steps system
For what is obtained：
(1) intermediate product (I) is prepared：Intermediate product (I) in the present embodiment is N, N '-(imino group -2,1- second diyl)
Enjoy a double blessing fluorine (2,5- dimethyl -3,6- dioxanonanoic acids) acid amides：The present embodiment step is identical with the step of example 1 (1).
(2) intermediate product (II) is prepared：Intermediate product (II) in the present embodiment is N, N '-[(benzyl imido) -2,1-
Second diyl] fluorine of enjoying a double blessing (2,5- dimethyl -3,6- dioxanonanoic acids) acid amides
Added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring 0.001mol (1.06g) N, N '-
(imino group -2,1- second diyl) fluorine of enjoying a double blessing (2,5- dimethyl -3,6- dioxanonanoic acids) acid amides, 0.0012mol's (0.064g)
Sodium methoxide and the anhydrous THF of 10mL, add a small amount of TBABs as catalyst.Under agitation, by 0.0012mol
(0.21g) cylite is dissolved in the anhydrous THF of 5ml, then is slowly dropped into by dropping funel in reaction system.After dripping off, it is stirred for
React 24h.GC detects the consumption of raw material, judges reaction end with this.After completion of the reaction, filter, filter vacuum rotary evaporation obtains
To yellow paste.Then 2% sodium hydroxide solution 10ml stirrings fully dissolving is added, adds 10ml × 2 time dichloromethane
Extraction, organic layer in vacuo rotary evaporation obtain light yellow liquid crude product, can use ethyl acetate/methanol (2:1) crystallize, obtain
0.98g products, yield 85.3%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：8.22(s,2H)；7.46(m,1H)；7.26(m,1H)； 7.21(m,1H)；3.68
(s,2H)；3.35-3.32(t,4H)；2.57-2.55(t,4H).
19(400MHz,CDCl3)：- 80.12~-80.16 (t, 6F)；- 80.16~-80.21 (m, 6F)；- 81.53~-
81.57(m,6F)；- 82.66~-82.74 (m, 4F)；-83.16(m,2F)；- 129.75~-129.79 (m, 4F)； -113.15
(m,2F)；- 132.77~-132.88 (m, 4F).
(3) fluorine-containing glycine betaine product is synthesized：In the 250mL round-bottomed flasks equipped with stirring, 0.024mol is separately added into
The sodium chloroacetate of (2.8g) and 0.01mol (11.5g) N, N '-[(benzyl imido) -2,1- second diyl] fluorine of enjoying a double blessing (2,5- diformazans
Base -3,6- dioxanonanoic acids) acid amides and 60mL ethanol/water mixed solvents (1:1) a small amount of TBABs, are added as catalysis
Agent, the consumption of reaction 12h, TLC detection raw material is stirred at reflux, reaction end is judged with this.After completion of the reaction, rotary evaporation in vacuo
Recycling design.Residue is added in isopropanol and dissolved, is filtered to remove excessive sodium chloroacetate, then rotary evaporation in vacuo recovery is different
Propyl alcohol.Cooling obtains yellow maltose shape crude product.Crude product can use ethyl acetate/methanol (1:1) crystallize, it is shallow to obtain 9.26g
Yellow solid product, yield 76.7%.
Its course of reaction is as follows：
The said goods detect its nuclear-magnetism：
1H-NMR(400MHz,DMSO_D6)：8.32(s,2H)；7.44(m,1H)；7.26(m,1H)； 7.21(m,1H)；
3.65(s,2H)；3.36-3.32(t,4H)；2.56-2.54(t,4H).
19(400MHz,DMSO_D6)：- 80.12~-80.16 (t, 6F)；- 80.16~-80.21 (m, 6F)； -81.53
~-81.57 (m, 6F)；- 82.66~-82.74 (m, 4F)；-83.16(m,2F)；- 129.75~-129.79 (m, 4F)；-
113.15(m,2F)；- 132.77~-132.88 (m, 4F).
Embodiment 3
The present embodiment provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, and it has following structure：
The above-mentioned fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent that the present embodiment provides is according to following steps system
For what is obtained：
(1) intermediate product (I) is prepared：Intermediate product (I) in the present embodiment is N, N '-(imino group -2,1- second diyl)
Enjoy a double blessing fluorine heptamide
0.01mol (1.03g) divinyl three is added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring
Amine and the anhydrous THF of 20mL, reaction system are cooled down with ice-water bath.Under agitation, by 0.022mol (8.32g) perfluoro-heptanoic acid methyl esters
It is slowly dropped into by dropping funel in reaction system.After dripping off, it is warmed to room temperature.It is stirred for reacting 4h.GC tracks reaction end.Instead
It should finish, vacuum distillation removes solvent.Obtain 7.48g yellow and be more than 95% compared with thick liquid product, purity GC analyses, yield
94.1%.Product can also be further purified using column chromatography.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.82(s,2H)；3.65-3.61(t,4H)；2.56-2.52(t,4H)； 2.14
(s,1H)。
19(400MHz,CDCl3)：- 80.89~-80.92 (t, 6F)；- 120.16~-120.19 (m, 4F)； -121.95
~-121.98 (m, 4F)；- 122.86~-122.89 (m, 4F)；- 123.20~-123.28 (m, 4F)；- 126.20~-
126.24(t,4F)。
(2) intermediate product (II) is prepared：Intermediate product (II) in the present embodiment is N, N '-[(methyl imido) -2,1-
Second diyl] fluorine heptamide of enjoying a double blessing
Added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring 0.002mol (1.59g) N, N '-
(imino group -2,1- second diyl) fluorine heptamide of enjoying a double blessing, 0.0024mol (0.13g) sodium methoxide and the anhydrous THF of 15mL, add small
TBAB is measured as catalyst.Under agitation, 0.0024mol (0.23g) bromomethane is dissolved in the anhydrous THF of 5ml,
It is slowly dropped into again by dropping funel in reaction system.After dripping off, it is stirred for reacting 12h.GC detects the consumption of raw material, is sentenced with this
Disconnected reaction end.After completion of the reaction, filter, filter vacuum rotary evaporation obtains light yellow paste.Then 2% hydroxide is added
Sodium solution 10ml stirrings fully dissolving, 10ml × 2 time dichloromethane extraction is added, organic layer in vacuo rotary evaporation obtains shallow
Yellow liquid crude product, ethyl acetate/methanol (2 can be used:1) crystallize, obtain 1.42g products, yield 87.7%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.88(s,2H)；3.25-3.21(t,4H)；2.55-2.50(t,4H)； 2.24
(s,1H)。
19(400MHz,CDCl3)：- 80.88~-80.91 (t, 6F)；- 120.16~-120.18 (m, 4F)； -121.95
~-122.01 (m, 4F)；- 122.87~-122.89 (m, 4F)；- 123.20~-123.27 (m, 4F)；- 126.21~-
126.25(t,4F)。
(3) fluorine-containing glycine betaine product is synthesized：In the 250mL round-bottomed flasks equipped with stirring, 0.025mol is separately added into
The chloropropionic acid sodium of (3.27g) and 0.01mol (8.10g) N, N '-[(methyl imido) -2,1- second diyl] enjoy a double blessing fluorine heptamide and
80mL ethanol/water mixed solvents (1:1) a small amount of TBABs, are added as catalyst, are stirred at reflux reaction 12h, GC inspection
The consumption of raw material is surveyed, reaction end is judged with this.After completion of the reaction, rotary evaporation in vacuo recycling design.Residue is added different
Dissolved in propyl alcohol, be filtered to remove excessive chloropropionic acid sodium, then rotary evaporation in vacuo recovery isopropanol.Cooling obtains yellow maltose
Shape crude product.Crude product can use ethyl acetate/methanol (1:1) crystallize, obtain 7.96g light yellow products, yield 90.3%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,DMSO_D6)：7.89(s,2H)；3.65-3.62(t,4H)；3.55-3.50(t, 4H)；
3.49-3.47(t,2H)；3.24(s,1H)；2.55-2.50(t,3H).
19(400MHz,DMSO_D6)：- 80.88~-80.91 (t, 6F)；- 120.16~-120.20 (m, 4F)； -
121.95~-121.98 (m, 4F)；- 122.87~-122.89 (m, 4F)；- 123.20~-123.25 (m, 4F)； -126.21
~-126.24 (t, 4F).
Embodiment 4
The present embodiment provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, and it has following structure：
The above-mentioned fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent that the present embodiment provides is according to following steps system
For what is obtained：
(1) intermediate product (I) is prepared：Intermediate product (I) in the present embodiment is N, N '-(imino group -3,1- glyceryl)
Enjoy a double blessing fluorine (2,2,3,3,4,4,5,5,6,6 ,-ten fluorine caproic acids) acid amides
0.01mol (1.31g) 3,3'- bis- is added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring
Aminobispropylamine and the anhydrous THF of 20mL, reaction system are cooled down with ice-water bath.Under agitation, by 0.022mol (6.82g) 2,2,
3,3,4,4,5,5,6,6 ,-ten fluorine methyl caproates are slowly dropped into reaction system by dropping funel.After dripping off, it is warmed to room temperature.
It is stirred for reacting 6h.GC tracks reaction end.Reaction finishes, and vacuum distillation removes solvent.Obtain 6.42g pale yellow viscous liquids
Product, purity GC analyses are more than 94%, yield 93.4%.Product can also be further purified using column chromatography.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.92(s,2H)；5.57-5.53(m,2H)；3.51-3.48(t,4H)；2.54-
2.52(t,4H)；1.97(s,1H)；1.71-1.69(m,4H).
19(400MHz,CDCl3)：- 81.44~-81.48 (t, 4F)；- 121.75~-721.79 (m, 4F)； -122.13
~-122.16 (m, 4F)；- 122.48~-122.51 (m, 4F)；- 127.61~-127.65 (t, 4F)
(2) intermediate product (II) is prepared：Intermediate product (II) in the present embodiment is N, N '-[(methyl imido) -3,1-
Glyceryl] fluorine of enjoying a double blessing (2,2,3,3,4,4,5,5,6,6 ,-ten fluorine caproic acids) acid amides
Added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring 0.002mol (1.37g) N, N '-
(imino group -2,1- glyceryl) fluorine of enjoying a double blessing (2,2,3,3,4,4,5,5,6,6,-ten fluorine caproic acids) acid amides, 0.0024mol
The anhydrous THF of sodium methoxide and 15mL of (0.13g), adds a small amount of TBABs as catalyst.Under agitation, will
0.0024mol (0.34g) iodomethane is dissolved in the anhydrous THF of 8ml, then is slowly dropped into by dropping funel in reaction system.Drip off
Afterwards, it is stirred for reacting 12h.GC detects the consumption of raw material, judges reaction end with this.After completion of the reaction, filter, filter vacuum rotation
Turn evaporation and obtain light yellow paste.Then 2% sodium hydroxide solution 10ml stirrings fully dissolving is added, adds 10ml × 2
Secondary dichloromethane extraction, organic layer in vacuo rotary evaporation obtain light yellow liquid crude product, can use ethyl acetate/methanol (2:1)
Crystallization, obtains 1.24g products, yield 88.4%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.91(s,2H)；5.54-5.50(m,2H)；3.45-3.42(t,4H)； 2.44-
2.42(t,4H)；2.27(s,3H)；1.74-1.71(m,4H).
19(400MHz,CDCl3)：- 81.46~-81.49 (t, 4F)；- 121.72~-121.76 (m, 4F)； -122.13
~-122.15 (m, 4F)；- 122.48~-122.51 (m, 4F)；- 127.62~-127.66 (t, 4F).
(3) fluorine-containing glycine betaine product is synthesized：
In the 250mL round-bottomed flasks equipped with stirring, be separately added into 0.015mol (1.75g) sodium chloroacetate with
0.005mol (3.50g) N, N '-[(methyl imido) -2,1- glyceryl] fluorine of enjoying a double blessing (2,2,3,3,4,4,5,5,6,6,-ten fluorine
Caproic acid) acid amides and 30mL ethanol/water mixed solvents (1:1) a small amount of TBABs, are added as catalyst, are stirred at reflux anti-
11h, TLC is answered to detect the consumption of raw material, judge reaction end with this.After completion of the reaction, rotary evaporation in vacuo recycling design.Will be surplus
Excess, which is added in isopropanol, to be dissolved, and is filtered to remove excessive sodium chloroacetate, then rotary evaporation in vacuo recovery isopropanol.Cooling obtains
Yellow maltose shape crude product.Crude product can use ethyl acetate/methanol (1:1) crystallize, obtain 3.34g light yellow solid products,
Yield 87.9%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,DMSO_D6)：7.91(s,2H)；5.52-5.49(m,2H)；4.35-4.31(t, 2H)；
3.44-3.40(t,4H)；3.29-3.26(t,3H)；3.22-3.20(t,4H)；2.05-2.02(t,4H).
19(400MHz,DMSO_D6)：- 81.46~-81.49 (t, 4F)；- 121.73~-121.75 (m, 4F)； -
122.13~-122.16 (m, 4F)；- 122.47~-122.50 (m, 4F)；- 127.62~-127.65 (t, 4F).
Embodiment 5
The present embodiment provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, and it has following structure：
The above-mentioned fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent that the present embodiment provides is according to following steps system
For what is obtained：
(1) intermediate product (I) is prepared：The intermediate product (I) of the present embodiment is N, and N '-(imino group -2,1- glyceryl) is double
Perfluor (2,2,3,3,4,4,5,5 ,-octafluoro valeric acid) acid amides
0.01mol (1.31g) 3,3'- bis- is added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring
Aminobispropylamine and the anhydrous THF of 20mL, reaction system are cooled down with ice-water bath.Under agitation, by 0.022mol (5.72g) 2,2,
3,3,4,4,5,5 ,-octafluoro methyl valerate is slowly dropped into reaction system by dropping funel.After dripping off, it is warmed to room temperature.Stir again
Mix reaction 6h.GC tracks reaction end.Reaction finishes, and vacuum distillation removes solvent.Obtain the production of 5.44g pale yellow viscous liquids
Thing, purity GC analyses are more than 94%, yield 92.6%.Product can also be further purified using column chromatography.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.89(s,2H)；5.64(m,2H)；3.47(t,4H)；2.51(t, 4H)；2.04
(s,1H)；1.74(m,4H).
19(400MHz,CDCl3)：- 81.74~-81.77 (t, 4F)；- 121.51~-121.54 (m, 4F)； -122.41
~-122.44 (m, 4F)；- 127.49~-127.53 (t, 4F).
(2) intermediate product (II) is prepared：Intermediate product (II) in the present embodiment is N, N '-[(methyl imido) -2,1-
Glyceryl] fluorine of enjoying a double blessing (2,2,3,3,4,4,5,5 ,-octafluoro valeric acid) acid amides
Added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring 0.002mol (1.17g) N, N '-
(imino group -2,1- glyceryl) fluorine of enjoying a double blessing (2,2,3,3,4,4,5,5,-octafluoro valeric acid) acid amides, 0.0024mol's (0.13g)
Sodium methoxide and the anhydrous THF of 10mL.Under agitation, 0.0024mol (0.31g) benzyl chloride is dissolved in the anhydrous THF of 5ml, added small
Amount TBAB is slowly dropped into reaction system as catalyst, then by dropping funel.After dripping off, it is stirred for reacting
12h.GC detects the consumption of raw material, judges reaction end with this.After completion of the reaction, filter, filter vacuum rotary evaporation obtains shallow
Yellow paste.Then 2% sodium hydroxide solution 10ml stirrings fully dissolving is added, adds 10ml × 2 time dichloromethane extraction
Take, organic layer in vacuo rotary evaporation obtains light yellow liquid crude product, can use ethyl acetate/methanol (2:1) crystallize, obtain
1.16g products, yield 85.6%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：7.97(s,2H)；7.37(s,2H)；7.27(s,2H)；7.21(s, 2H)；5.69
(m,2H)；3.67(t,2H)；3.45(t,4H)；2.50(t,4H)；2.04(s,1H)；1.65(m, 4H).
19(400MHz,CDCl3)：- 81.73~-81.76 (t, 4F)；- 121.51~-121.54 (m, 4F)； -122.42
~-122.46 (m, 4F)；- 127.49~-127.52 (t, 4F).
(3) fluorine-containing glycine betaine product is synthesized：In the 250mL round-bottomed flasks equipped with stirring, 0.015mol is separately added into
The sodium chloroacetate of (1.75g) and 0.005mol (3.4g) N, N '-[(methyl imido) -2,1- glyceryl] fluorine of enjoying a double blessing (2,2,3,3,
4,4,5,5 ,-octafluoro valeric acid) acid amides and 30mL isopropanol/waters mixed solvent (1:1) a small amount of TBABs conducts, are added to urge
Agent, the consumption of reaction 12h, TLC detection raw material is stirred at reflux, reaction end is judged with this.After completion of the reaction, vacuum rotating steams
Send out recycling design.Residue is added in isopropanol and dissolved, is filtered to remove excessive sodium chloroacetate, then rotary evaporation in vacuo recovery
Isopropanol.Cooling obtains yellow maltose shape crude product.Crude product can use ethyl acetate/methanol (1:1) crystallize, obtain 3.19g
Light yellow solid product, yield 86.7%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,DMSO_D6)：8.07(s,2H)；7.38(s,2H)；7.26(s,2H)； 7.24(s,2H)；
4.64(m,2H)；4.37(t,2H)；3.41(t,4H)；3.26(t,4H)；2.04(s,1H)； 1.95(m,4H).
19(400MHz,DMSO_D6)：- 81.73~-81.76 (t, 4F)；- 121.53~-121.57 (m, 4F)； -
122.42~-122.45 (m, 4F)；- 127.48~-127.51 (t, 4F).
Embodiment 6
The present embodiment provides a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, and it has following structure：
The above-mentioned fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent that the present embodiment provides is according to following steps system
For what is obtained：
(1) intermediate product (I) is prepared：Intermediate product (I) in the present embodiment is N, N '-(imino group -2,1- second diyl)
Enjoy a double blessing fluorine (2,5,8- trimethyl -3,6,9- trioxas lauric acid/dodecanoic acid) acid amides
0.01mol (1.03g) divinyl three is added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring
Amine and 20mL absolute ethers, reaction system are cooled down with ice-water bath.Under agitation, by 0.021mol (14.63g) N- perfluors (2,5,
8- trimethyl -3,6,9- trioxas lauric acid/dodecanoic acid) acyl chlorides is slowly dropped into reaction system by dropping funel.After dripping off, room is risen to
Temperature.It is stirred for reacting 4h.TLC tracks reaction end.Reaction is finished, and reactant mixture is washed 2 times with 2% sodium hydroxide.Separate
Organic layer, then by washing, then dried with anhydrous magnesium sulfate, reclaim ether, vacuum distillation removes excessive diethylenetriamine.
12.96g pale yellow viscous liquid products are obtained, purity GC analyses are more than 95%, yield 93.2%.Product can also use post
Chromatography is further purified.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：8.16(s,2H)；3.34-3.32(t,4H)；2.63-2.61(t,4H)； 1.94
(s,1H)。
19(400MHz,CDCl3)：- 80.22~-80.26 (t, 6F)；-80.29(s,6F)；-82.32(m,6F)； -
83.66~-83.72 (m, 4F)；- 83.74~-83.77 (m, 2F)；- 84.58~-84.62 (m, 2F)；-113.15(s,
6F)；- 122.46~-122.49 (m, 4F)；- 129.74~-129.79 (m, 4F)；- 132.75~-132.81 (t, 4F).
(2) intermediate product (II) is prepared：Intermediate product (II) in the present embodiment is N, N '-[(methyl imido) -2,1-
Second diyl] fluorine of enjoying a double blessing (2,5,8- trimethyl -3,6,9- trioxas lauric acid/dodecanoic acid) acid amides
Added in the young and 50mL three neck round bottom flask of addition funnel equipped with stirring 0.001mol (1.39g) N, N '-
(imino group -2,1- second diyl) fluorine of enjoying a double blessing (2,5,8- trimethyl -3,6,9- trioxas lauric acid/dodecanoic acid) acid amides, 0.0012mol
The anhydrous THF of sodium methoxide and 10mL of (0.064g), adds a small amount of TBABs as catalyst.Under agitation, will
0.0012mol (0.18g) iodomethane is dissolved in the anhydrous THF of 5ml, then is slowly dropped into by dropping funel in reaction system.Drip off
Afterwards, it is stirred for reacting 14h.GC detects the consumption of raw material, judges reaction end with this.After completion of the reaction, filter, filter vacuum rotation
Turn evaporation and obtain light yellow paste.Then 2% sodium hydroxide solution 10ml stirrings fully dissolving is added, adds 8ml × 2
Secondary dichloromethane extraction, organic layer in vacuo rotary evaporation obtain light yellow liquid crude product, can use ethyl acetate/methanol (2:1)
Crystallization, obtains 1.21g products, yield 86.1%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,CDCl3)：8.02(s,2H)；3.30-3.28(t,4H)；2.52-2.48(t,4H)； 2.31
(s,1H)。
19(400MHz,CDCl3)：- 80.21~-80.25 (t, 6F)；-80.30(s,6F)；-82.35(m,6F)； -
83.67~-83.73 (m, 4F)；- 83.74~-83.78 (m, 2F)；- 84.58~-84.62 (m, 2F)；-113.16(s,
6F)；- 122.46~-122.49 (m, 4F)；- 129.74~-129.79 (m, 4F)；- 132.78~-132.82 (t, 4F).
(3) fluorine-containing glycine betaine product is synthesized：In the 250mL round-bottomed flasks equipped with stirring, 0.024mol is separately added into
The sodium chloroacetate of (2.80g) and 0.01mol (14.1g) N, N '-[(methyl imido) -2,1- second diyl] fluorine of enjoying a double blessing (2,5,8- tri-
Methyl -3,6,9- trioxas lauric acid/dodecanoic acid) acid amides and 60mL isopropanol/waters mixed solvent (1:1) a small amount of TBABs, are added
As catalyst, the consumption of reaction 12h, TLC detection raw material is stirred at reflux, reaction end is judged with this.After completion of the reaction, vacuum
Rotary evaporation recycling design.Residue is added in isopropanol and dissolved, is filtered to remove excessive sodium chloroacetate, then vacuum rotating steams
Beam back receipts isopropanol.Cooling obtains yellow maltose shape crude product.Crude product can use ethyl acetate/methanol (1:1) crystallize, obtain
12.6g light yellow solid products, yield 85.9%.
Its course of reaction is as follows：
The said goods are taken to detect its nuclear-magnetism：
1H-NMR(400MHz,DMSO_D6)：8.06(s,2H)；4.39(s,2H)；3.61-3.58(t,3H)； 3.48-
3.44(t,4H)；3.24(s,3H).
19(400MHz,DMSO_D6)：- 80.21~-80.25 (t, 6F)；-80.28(s,6F)；-82.32(m, 6F)；-
83.66~-83.71 (m, 4F)；- 83.74~-83.77 (m, 2F)；- 84.58~-84.62 (m, 2F)； -113.16(s,
6F)；- 122.46~-122.49 (m, 4F)；- 129.74~-129.79 (m, 4F)；- 132.77~-132.82 (t, 4F).
Embodiment 7
The present embodiment provides the surface tension of the measure fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent in part, uses
Platinum plate method is measured, and instrument is：The full-automatic surface tension instrument of Shanghai Fang Rui Instrument Ltd. QBZY series.Wherein concentration
It is as shown in table 1 for 0.1%, RT, determination data.
The surface tension of the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent of table 1
* it is attached：Artificial seawater prepares (salinity 3.34%, g/l water):NaCl(26.726),MgCl2(2.25),MgSO4
(3.25), CaCl2(1.153),NaHCO3(0.120),KCl(0.721),NaBr(0.058),Na2SiO3(0.0025),
Na2Si4O 9(0.0015)
There is the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent of the present invention relatively low concentration (to be less than 10-
100mg/L), while also there is good reduction aqueous phase system surface tension 14.5mN/m (0.1%).Live on this surface
Property agent has preferable salt-resistance, and more excellent table can be kept under hypersaline environment (% of salinity 3.34 human configuration sea salt)
Face activity (15.2-18.9mNm-1)。
Further, the preparation method of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent of the invention is simple, examination
Agent is common, and preparation condition is gentle, the extreme condition such as no HTHP, can prepare at room temperature, and what is prepared contains carboxylic acid fluoride
Type beet alkali ampholytic ionic surface active agent has higher yield.
So far, although those skilled in the art will appreciate that detailed herein have shown and described multiple showing for the present invention
Example property embodiment, still, still can be direct according to present disclosure without departing from the spirit and scope of the present invention
It is determined that or derive many other variations or modifications for meeting the principle of the invention.Therefore, the scope of the present invention is understood that and recognized
It is set to and covers other all these variations or modifications.
Claims (10)
1. a kind of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, its chemical general formula are：
Wherein, Rf C3-C20Fluorine-containing chain radicals it is any,For CH2OrAny of group,
R1For C2-C5Any of divalent group of alkane chain, R2For C1-C6Any of alkyl, phenyl or benzyl, R3For
C1-C4The divalent group of alkane chain.
2. fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 1, it is characterised in that
The C3-C20Fluorine-containing chain radicals are to insert the perfluoroalkyl of oxygen atom or end in perfluoro alkane base, straight chain to have hydrogen
Any one in substituted perfluoro alkane base.
3. fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 2, it is characterised in that
The perfluoroalkyl that oxygen atom is inserted in the straight chain is-CF2OCF(CF3)2、-CF(CF3)OCF2CF3、-
CF2CF2OCF2CF3、-CF(CF3)OCF(CF3)2、-CF2CF2OCFCF3OCF2CF3、-CF2CF(CF3)OCF(CF3)2、-CF2CF
(CF3)OCF2CF2CF3、-CF2CF(CF3)OCF2CF2OCF2CF3、-CF2CF2OCF2CF2OCF2(CF3)2、-CF2CF(CF3)
OCF2CF2OCF2(CF3)2、-CF(CF3)OCF2CF(CF3)OCF2CF2CF3、-CF2CF2OCF2CF(CF3)OCF2CF2CF3、-CF2CF
(CF3)OCF2CF2OCF2CF2CF3、-CF2CF2OCF(CF3)OCF2CF2OCF(CF3)2、-CF2CF2OCF(CF3)
OCF2CF2OCF2CF2CF3、-CF2CF(CF3)OCF2CF(CF3)OCF(CF3)2、-CF2CF(CF3)OCF2CF(CF3)OCF(CF3)2、-
CF2CF(CF3)OCF2CF(CF3)OCFCF2CF3、-CF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)2Or-
CF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2CF(CF3)2Any of.
4. fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 2, it is characterised in that
The perfluoro alkane base that the end has hydrogen to substitute is-CF2CF2CF2CF2CF2CF2CF2CF2H、-
CF2CF2CF2CF2CF2CF2CF2H、-CF2CF2CF2CF2CF2CF2H、-CF2CF2CF2CF2CF2H、-CF2CF2CF2CF2H or-
CF2CF2CF2Any of H.
5. fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 1, it is characterised in that
The R1For any of propylidene, butylidene or pentylidene.
A kind of 6. preparation side of the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent any one of claim 1-5
Method, comprise the following steps：
(1) preparation of the triamine intermediate (I) of perfluor acid amides substitution
Monosubstituted alkyl triamine is mixed with organic solvent, perfluoroalkyl etheride is added dropwise under ice-water bath and is stirred,
It is warmed to room temperature after dripping, is stirred for 4-6h, obtains the triamine intermediate (I) of perfluor acid amides substitution, the perfluor acid amides substitution
The chemical formula of triamine intermediate (I) be：
Wherein, RfFor C3-C20Fluorine-containing chain radicals it is any,For CH2OrAny of group,
R1For C2-C5Any of divalent group of alkane chain；
(2) preparation of the triamine intermediate (II) of perfluor acid amides substitution
Triamine intermediate (I) that the perfluor acid amides substitutes is mixed in alkali organic solvent with halide, and adds catalysis
Agent, flow back 12-24h under agitation, obtains the triamine intermediate (II) of the perfluor acid amides substitution, the perfluor acid amides substitution
The chemical formula of triamine intermediate (II) is：
Wherein, R2For C1-C6Any of alkyl, phenyl or benzyl；
(3) preparation of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent
The triamine intermediate (II) that the perfluor acid amides is substituted and halogenated carboxylic acid salt alkalescent solvent in back flow reaction 10-
16h, obtain the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, the fluorine-containing carboxylic acid type beet alkali ampholytic ion table
The chemical formula of face activating agent is：
Wherein, R3For C1-C4The divalent group of alkane chain.
7. the preparation method of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 6, its feature
It is：
In the preparation process of the triamine intermediate (I) of perfluor acid amides substitution, the monosubstituted alkyl triamine with it is described complete
The mol ratio of fluorohydrocarbon base etheride is 1:2~1：3.
8. the preparation method of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 7, its feature
It is：
It is a kind of or more that the perfluoroalkyl etheride is selected from perfluoroalkyl acyl chlorides, perfluoroalkyl acyl fluorides or perfluoroalkyl acid esters
Kind.
9. the preparation method of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 6, its feature
It is：
In the preparation process of the triamine intermediate (II) of perfluor acid amides substitution, the catalyst is TBAB,
The alkali organic solvent is selected from sodium methoxide and anhydrous THF mixtures or sodium methoxide and one kind in absolute ether mixture.
10. the preparation method of fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent according to claim 6, its feature
It is：
In the preparation process of the fluorine-containing carboxylic acid type beet alkali ampholytic ionic surface active agent, in addition to add tetrabutyl phosphonium bromide
Ammonium reacts as catalyst.
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| CN110354755A (en) * | 2019-07-15 | 2019-10-22 | 四川轻化工大学 | Novel fluorine-containing betaine surfactant and preparation method and application thereof |
| CN116103024A (en) * | 2021-11-10 | 2023-05-12 | 中石化石油工程技术服务有限公司 | Oil-based foaming agent and preparation method thereof |
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