CN104058976B - A kind of preparation method of fluorine-containing cationic surfactant - Google Patents
A kind of preparation method of fluorine-containing cationic surfactant Download PDFInfo
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 32
- 239000011737 fluorine Substances 0.000 title claims abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003093 cationic surfactant Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000013638 trimer Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000006837 decompression Effects 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 9
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical class CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims description 2
- 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 claims description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 claims description 2
- 230000000269 nucleophilic effect Effects 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- 239000003995 emulsifying agent Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 239000008396 flotation agent Substances 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract 1
- IPMWIVQWGGRTLD-UHFFFAOYSA-N n'-[2-(propylamino)ethyl]ethane-1,2-diamine Chemical class CCCNCCNCCN IPMWIVQWGGRTLD-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical group [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a kind of Preparation method and use of fluorine-containing cationic surfactant, methods described includes：With hexafluoropropylene trimer and N, N dimethylated propyl diethylenetriamines are raw material, the nucleophilic substitution in the presence of organic solvent and base catalyst；Then alkyl halide is added thereto and carries out quaternary ammonium reaction, and solvent is distilled off in filtration of crude product, filtrate decompression, and fluorine-containing cationic surfactant is made in " one kettle way ".Such fluorine-containing cationic surfactant can be used as emulsifying agent, metal conditioner, levelling agent, fire extinguishing agent addition agent, foam flotation agents or oil evaporation inhibitor etc..
Description
Technical field
The present invention relates to cationic surfactant field, and in particular to a kind of preparation of fluorine-containing cationic surfactant
Method.
Background technology
Fluorine-containing surfactant has " three high ", the characteristic of " two hate ", with high surface, high thermal stability and heightization
The characteristics of stability etc. is prominent is learned, with the popularization of its application, the domestic, demand of international market increasingly increases.Fluorochemical surface is lived
Property agent is divided into anion surfactant, cationic surfactant, amphoteric surfactant and nonionic surfactant four
Major class.Fluorine-containing cationic surfactant have good foaminess, do not influenceed by pH value, the not characteristic such as facile hydrolysis, therefore into
For a main direction of studying.Fluorine-containing cationic surfactant is broadly divided into amine salt type and the major class of quaternary two, and with season
Ammonium salt type purposes is most wide.
It can be used for fluorine-containing surfactant of the synthesis with side chain by raw material of oligomerization of hexafluoropropylene body.Patent
In CN101293860A, raw material is difficult to obtain to perfluorinated nonene epoxide benzene sulfonyl chloride, and expensive.The fluorine-containing cationic of synthesis
The yield of surfactant is general between 77.8-82.1%, active not high, the critical micelle concentration of gained cationic surface agent
Under surface tension be 21.7mN/m.In patent CN101293853A, required raw material is to the same valency of perfluorinated nonene p-methoxybenzoic acid
Lattice are expensive, it is difficult to obtain, and thionyl chloride toxicity is big, and environmental pollution is serious, while the fluorine-containing cationic surfactant
Complex process is not easy to amplification production.In patent CN101033205A, the surface of synthesized anionic fluorochemical surfactant
Activity is poor, and under 0.1% concentration, surface tension is only 21mN/m.In patent JP2007060096, it is synthesized it is fluorine-containing it is cloudy from
The surface-active of sub- surfactant is higher, but the yield of product is relatively low, and only 65.2%.
The content of the invention
It is an object of the invention to overcome it is of the prior art it is not enough there is provided a kind of yield it is high, be easy to industrialized production, it is honest and clean
The preparation method of valency and the high fluorine-containing cationic surfactant of surface-active.To reach above-mentioned purpose, the present invention proposes " one pot
Method " fluorine-containing cationic surfactant processed.
Technical scheme provides a kind of preparation method of fluorine-containing cationic surfactant：With hexafluoropropene three
Aggressiveness and N, N- dimethylated propyl diethylenetriamine are raw material, in the presence of organic solvent and base catalyst, and it is anti-that 0-50oC carries out nucleophilic displacement of fluorine
Should；After reaction terminates, alkyl halide is added thereto, and 0-100oC carries out quaternary ammonium reaction, filtration of crude product, filtrate decompression distillation
Remove solvent and obtain fluorine-containing cationic surfactant.
Above-mentioned preparation method is comprised the steps of：
1）Hexafluoropropylene trimer and base catalyst are added and stirred in organic solvent, N, N- dimethyl propylenes are added afterwards
Diamines, 0-50oC stirring reactions carry out nucleophilic substitution in 0.5-10 hours；
2）To step 1）Alkyl halide is added in gained mixed liquor, 0-100oC, which reacts 0.5-6 hours, carries out quaternary ammonium reaction,
Filtration of crude product, filtrate decompression is distilled off solvent and obtains fluorine-containing cationic surfactant.
Some preferred embodiment in, above-mentioned steps 1）Nucleophilic substitution, reaction temperature is 20-50oC, reaction
Time is 4-8 hours；Step 2）The quaternary ammonium reaction temperature is 50-100oC, and the reaction time is 2-4 hours.
In some embodiments, base catalyst is selected from sodium carbonate, potassium carbonate, sodium acid carbonate, triethylamine, trimethylamine, pyrrole
Pyridine, piperidines or N- methyl piperidines.
In some embodiments, solvent is selected from ethyl acetate, acetone, tetrahydrofuran, ether, dichloromethane, N, N- bis-
NMF or cyclohexanone.
In some embodiments, alkyl halide is selected from iodomethane, iodoethane, bromomethane, bromoethane or chloroethanes.
In some embodiments, hexafluoropropylene trimer, N, N- dimethylated propyl diethylenetriamines, base catalyst, alkyl halide rub
You are than being 1:1-3:1-2:1-4.
Other preferred embodiment in, hexafluoropropylene trimer, N, N- dimethylated propyl diethylenetriamines, base catalyst, halogen
Mol ratio for alkane is 1:1.2-1.5:1.2-1.5:1.5-2.5.
Present invention also offers the fluorine-containing cationic surfactant according to obtained by above-mentioned preparation method.
Fluorine-containing cationic surfactant prepared by the preparation method of fluorine-containing cationic surfactant of the present invention,
Emulsifying agent, metal conditioner, levelling agent, fire extinguishing agent addition agent, foam flotation agents or oil evaporation is can apply to suppress
In agent.
Terminology used in the present invention "or" represents alternative, if appropriate, can combine them, that is,
Say, term "or" includes each listed independent alternative and combinations thereof.For example, " base catalyst is selected from carbonic acid
Sodium, potassium carbonate, sodium acid carbonate, triethylamine, trimethylamine, pyridine, piperidines or N- methyl piperidines " represents that base catalyst can be carbonic acid
One kind or one among sodium, potassium carbonate, sodium acid carbonate, triethylamine, trimethylamine, pyridine, piperidines, N- methyl piperidines
Plant the combination of the above.
Unless explicitly stated otherwise in contrast, otherwise, all scopes that the present invention is quoted include end value.For example, " 0-
100oC progress quaternary ammonium reaction " represents that the temperature T of quaternary ammonium reaction scope is 0oC≤T≤100oC.
Preparation method of the present invention uses " one kettle way ", and method is simple, and reaction yield is high, and fluorine-containing cationic table is made
Face activating agent surface-active is high.
Embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferable to carry out
Formula.It should be pointed out that for those skilled in the art on the basis of this innovation and creation design, some deformations for making and
Improve, belong to protection scope of the present invention.
Embodiment 1
Sodium carbonate 5.3g, acetonitrile 30mL and hexafluoropropylene trimer 22.5g are added in 100mL there-necked flask, stirring is equal
Stirring reaction 8 hours under N, N- dimethylated propyl diethylenetriamines 5.1g, 20oC are added after even；State then up and bromoethane is added in reaction solution
5.5g, is warming up to 100oC stirring reactions 4 hours.By reaction solution suction filtration, filtrate decompression distillation removes solvent and obtains fluorine-containing cationic table
Face activating agent, yield 96.2%.
Products obtained therefrom is configured to the aqueous solution that mass fraction is 0.1%, surface tension is 18.8mN/ during 25oC after testing
m。
Embodiment 2
Sodium carbonate 8.0g, acetone 30mL and hexafluoropropylene trimer 22.5g are added in 100mL there-necked flask, stirring is equal
Stirring reaction 5 hours under N, N- dimethylated propyl diethylenetriamines 10.2g, 10oC are added after even；Addition iodine first in reaction solution is stated then up
Alkane 8.5g, is warming up to 50oC stirring reactions 2 hours.By reaction solution suction filtration, filtrate decompression distillation removes solvent and obtains fluorine-containing cationic
Surfactant, yield 95.5%.
Products obtained therefrom is configured to the aqueous solution that mass fraction is 0.1%, surface tension is 18.9mN/ during 25oC after testing
m。
Embodiment 3
Triethylamine 7.6g, ethyl acetate 30mL and hexafluoropropylene trimer 22.5g are added in 100mL there-necked flask, is stirred
Mix stirring reaction 5 hours under uniform rear addition N, N- dimethylated propyl diethylenetriamines 15.3g, 40oC；State in reaction solution and add then up
Bromoethane 9.0g, is cooled to 30oC stirring reactions 1 hour.By reaction solution suction filtration, filtrate decompression distillation removes solvent and obtains fluorine-containing sun
Ionic surface active agent, yield 97.3%.
Products obtained therefrom is configured to the aqueous solution that mass fraction is 0.1%, surface tension is 18.8mN/ during 25oC after testing
m。
Embodiment 4
Pyridine 8.7g, tetrahydrofuran 30mL and hexafluoropropylene trimer 22.5g, stirring are added in 100mL there-necked flask
Stirring reaction 4 hours under N, N- dimethylated propyl diethylenetriamines 6.3g, 0oC are added after uniform；Addition iodine first in reaction solution is stated then up
Alkane 14.2g, is warming up to 60oC stirring reactions 6 hours.By reaction solution suction filtration, filtrate decompression distillation removes solvent and obtains fluorine-containing cationic
Surfactant, yield 95.8%.
Products obtained therefrom is configured to the aqueous solution that mass fraction is 0.1%, surface tension is 18.8mN/ during 25oC after testing
m。
Embodiment 5
Potassium carbonate 15.3g, ether 30mL and hexafluoropropylene trimer 22.5g are added in 100mL there-necked flask, stirring is equal
Stirring reaction 0.5 hour under N, N- dimethylated propyl diethylenetriamines 7.8g, 50oC is added after even；Addition iodine first in reaction solution is stated then up
Alkane 21.3g, is warming up to 60oC stirring reactions 0.5 hour.By reaction solution suction filtration, filtrate decompression distillation remove solvent obtain fluorine-containing sun from
Sub- surfactant, yield 96.7%.
Products obtained therefrom is configured to the aqueous solution that mass fraction is 0.1%, surface tension is 19.0mN/ during 25oC after testing
m。
From 1-5 of the embodiment of the present invention, technical scheme process route is simple, and reaction condition is gentle, yield
Up to 95-97%；The surface-active of synthesized fluorine-containing cationic surfactant is high simultaneously, and mass fraction is 0.1% during 25oC
The surface tension of the aqueous solution is 18.8-19.0mN/m.
Claims (4)
1. a kind of preparation method of fluorine-containing cationic surfactant, it is characterized in that：With hexafluoropropylene trimer and N, N- diformazans
Base propane diamine is raw material, in the presence of organic solvent and base catalyst, 0-50 DEG C of progress nucleophilic substitution；After reaction terminates,
Alkyl halide is added thereto, and 30-100 DEG C of progress quaternary ammonium reaction, filtration of crude product, filtrate decompression is distilled off solvent and obtains fluorine-containing
Cationic surfactant；
The hexafluoropropylene trimer, N, N- dimethylated propyl diethylenetriamines, base catalyst, the mol ratio of alkyl halide are 1:1.2-1.5:
1.2-1.5:1.5-2.5；
The reaction time of the nucleophilic displacement of fluorine is 0.5-10 hours；The reaction time of quaternary ammonium reaction is 0.5-6 hours；
The organic solvent is selected from ethyl acetate, acetone, tetrahydrofuran, ether, dichloromethane, N,N-dimethylformamide or ring
One or more in hexanone.
2. preparation method according to claim 1, it is characterized in that, described base catalyst is selected from sodium carbonate, potassium carbonate, carbon
Sour hydrogen sodium, triethylamine, trimethylamine, pyridine, piperidines or N- methyl piperidines or its combination.
3. preparation method according to claim 1, it is characterized in that, described alkyl halide is selected from iodomethane, iodoethane, bromine first
Alkane, bromoethane or chloroethanes.
4. preparation method according to claim 1, it is characterized in that, the reaction temperature of the nucleophilic substitution is 20-50
DEG C, the reaction time is 4-8 hours；The reaction temperature of quaternary ammonium reaction is 50-100 DEG C, and the reaction time is 2-4 hours.
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|---|---|---|---|---|
| JPS5942347A (en) * | 1983-03-11 | 1984-03-08 | Neos Co Ltd | Preparation of fluorine-containing quanternary ammonium salt |
| CN102153525A (en) * | 2011-03-07 | 2011-08-17 | 四川大学 | Preparation method and application of novel benzothiazole salt ionic liquid |
| CN102500087A (en) * | 2011-10-24 | 2012-06-20 | 徐衡 | Method for preparing perfluorohexane surfactant serving as main agent of aqueous film-forming extinguishing agent directly |
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| CN101293853A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Cation fluorine surfactant and preparation method thereof |
| CN101293860A (en) * | 2008-06-05 | 2008-10-29 | 浙江工业大学 | Quaternary ammonium salt fluorine surfactant preparing method |
| CN102908937B (en) * | 2012-09-12 | 2015-07-29 | 衢州学院 | Based on the cationic Shuangzi fluorine surfactant and preparation method thereof of perfluorinated nonene and perfluor hexene |
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