CN116410104A - Branched fluorocarbon surfactant and preparation method thereof - Google Patents
Branched fluorocarbon surfactant and preparation method thereof Download PDFInfo
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- CN116410104A CN116410104A CN202111649668.5A CN202111649668A CN116410104A CN 116410104 A CN116410104 A CN 116410104A CN 202111649668 A CN202111649668 A CN 202111649668A CN 116410104 A CN116410104 A CN 116410104A
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- fluorocarbon surfactant
- branched fluorocarbon
- branched
- fluorine
- difluoro
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 48
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title description 11
- -1 difluoro halogenated ethyl acetate Chemical class 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- YHAAEMITOHIABS-UHFFFAOYSA-N 1,1,1,2,4,4,4-heptafluoro-3-(trifluoromethyl)but-2-ene Chemical compound FC(F)(F)C(F)=C(C(F)(F)F)C(F)(F)F YHAAEMITOHIABS-UHFFFAOYSA-N 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 239000011737 fluorine Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000004673 fluoride salts Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- IRSJDVYTJUCXRV-UHFFFAOYSA-N ethyl 2-bromo-2,2-difluoroacetate Chemical compound CCOC(=O)C(F)(F)Br IRSJDVYTJUCXRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- GVCAWQUJCHZRCB-UHFFFAOYSA-N ethyl 2-chloro-2,2-difluoroacetate Chemical compound CCOC(=O)C(F)(F)Cl GVCAWQUJCHZRCB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000005956 quaternization reaction Methods 0.000 abstract description 2
- 238000009987 spinning Methods 0.000 abstract description 2
- 238000005809 transesterification reaction Methods 0.000 abstract description 2
- 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 6
- 238000003756 stirring Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 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 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HGWXXIZVRRTDKT-UHFFFAOYSA-N ethyl 2,2-difluoro-2-iodoacetate Chemical group CCOC(=O)C(F)(F)I HGWXXIZVRRTDKT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
- A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a computer system with CF 3 CF 2 C(CF 3 ) 2 CF 2 -structural branched fluorocarbon surfactant and process for preparing the same. Perfluoro-2-methyl-2-butene is used as a precursor, and is subjected to addition reaction with difluoro halogenated ethyl acetate, and then is subjected to amine transesterification and quaternization reaction with alkyl diamine to obtain the branched catalystChain type fluorocarbon surfactant. The fluorocarbon surfactant has excellent surface activity and can be applied to the fields of chemical industry, oil fields, fire protection, spinning, papermaking and the like.
Description
Technical Field
The invention relates to the field of surfactants, in particular to a branched fluorocarbon surfactant and a preparation method thereof.
Background
The fluorine-containing surfactant is a surfactant with high surface activity, and has excellent properties such as hydrophobicity and lipophobicity due to high surface activity, high heat resistance stability and high chemical stability, so that the fluorine-containing surfactant has wide application in the fields of petroleum, fire protection, electronics, papermaking, textile, cleaning agents and the like.
Currently, widely used long fluorocarbon chain surfactants such as PFOA and PFOS-type chemicals (C8) have been demonstrated to have environmental durability and bioaccumulation, and in 2009 are included in the category of Persistent Organic Pollutants (POPs) by the schde gol convention on persistent organic pollutants, production and use are severely limited.
Therefore, developing a new degradable fluorocarbon surfactant to replace the existing PFOS/PFOA fluorocarbon surfactant comprehensively and evaluate the biodegradability and the influence on the environment at the same time has become one of urgent theoretical research problems and has attracted great attention from researchers in various countries.
Researches indicate that the shorter fluorocarbon chain (such as C4) has no obvious durable bioaccumulation, can be discharged out of the body along with metabolism of a human body in a short time, but has larger oil repellency with the shortening of the carbon chain than the level of PFOS (C8); the preparation of C6-based products by telomerization is also highly controversial, and C6 is also exceedingly difficult to decompose and has 3 to 5 times greater toxicity to certain aquatic organisms than C8.
Chinese patent CN112174859a discloses a method for preparing fluorocarbon surfactant containing perfluorobutyl structure, the surface tension of the surfactant reaches 17-19 mN/m, but the perfluorobutyl sulfonyl fluoride used in the method needs to be prepared by electrolytic fluorination, and the cost and energy consumption are high.
Chinese patent CN109851529A, CN104941508A discloses a branched fluorocarbon surfactant which can be applied to a water film-forming foam extinguishing agent after being compounded, and the method introduces branched chains in fluorocarbon chains and is an effective strategy for synthesizing PFOA/PFOS substitutes. However, the method has the advantages of complex design of the connecting group, high preparation difficulty and relatively non-improvement of the surface activity compared with a linear structure.
Disclosure of Invention
In order to solve the problems, the invention provides a novel branched fluorocarbon surfactant, wherein the main chain of the surfactant has a C4 structure and a branched structure, and the branched fluorocarbon surfactant forms a C6 type fluorocarbon hydrophobic chain together, has excellent surface activity and is environment-friendly, can replace PFOA/PFOS (PFOA/PFOS) to be applied to the industries of fire protection, textile and the like, and is particularly used as an aqueous film-forming foam extinguishing agent. The surfactant disclosed by the invention is simple in preparation process, low in cost and good in industrial application prospect.
The invention aims at realizing the following technical scheme:
a branched fluorocarbon surfactant, which has the following structural formula (I):
wherein,,
n is selected from any integer from 1 to 5;
R 1 and R is 2 Independently selected from C1-C6 alkyl;
a is selected from O, (CH) 2 )mCH 3 X (X is halogen), (CH) 2 ) mCOO or (CH) 2 )mSO 3 M is selected from any integer from 1 to 10.
Further, n is an integer from 2 to 4.
The invention also provides a preparation method of the branched fluorocarbon surfactant, which takes perfluoro-2-methyl-2-butene as a precursor, and the branched fluorocarbon surfactant is obtained through an addition reaction with difluoro halogenated ethyl acetate, an amine transesterification reaction with alkyl diamine and a quaternization reaction.
The preparation method of the branched fluorocarbon surfactant comprises the following steps:
s1, reacting perfluoro-2-methyl-2-butene with difluoro halogenated ethyl acetate at 60-100 ℃ in the presence of a solvent, fluoride salt and a catalyst to obtain a fluorine-containing intermediate M1 with a structural formula shown as the following formula (M1),
s2, reacting the fluorine-containing intermediate M1 prepared in the step S1 with alkyl diamine to obtain a fluorine-containing intermediate M2 shown in the structural formula (M2),
s3, reacting the fluorine-containing intermediate M2 prepared in the step S2 with a quaternizing agent to obtain the branched fluorocarbon surfactant.
In the preparation method of the branched fluorocarbon surfactant, specifically, in the step S1, in order to provide anions for attacking carbon-carbon double bonds, fluoride salt is adopted as an anion donor. Preferably, the fluoride salt is at least one selected from cesium fluoride, rubidium fluoride, potassium fluoride, sodium fluoride; more preferably, the fluoride salt is cesium fluoride or potassium fluoride. The anion donors used are generally composed of positively and negatively charged moieties, and aprotic polar solvents are generally selected to weaken the positively charged moiety between positive and negative charges. Preferably, the solvent is at least one selected from acetonitrile, dimethylformamide, dimethyl sulfoxide, and 1, 3-dimethyl-2-imidazolidinone. The selection of the catalyst promotes the reaction and a suitable catalyst may trap positively charged moieties in the anion donor, exposing the anion to increase its activity. Preferably, the catalyst is selected from at least one of tertiary amine, quaternary ammonium salt or crown ether.
The difluoro halogenated ethyl acetate is at least one selected from difluoro iodic ethyl acetate, difluoro bromoacetic acid ethyl ester, difluoro chloroacetic acid ethyl ester and trifluoro acetic acid ethyl ester; preferably, the ethyl difluorohaloacetate is ethyl difluoroiodoacetate or ethyl difluorobromoacetate.
The reaction temperature in the step S1 is 60-100 ℃ and the reaction time is 12-72 h; preferably, the reaction temperature is 70-90 ℃ and the reaction time is 24-48 h.
In the step S2, the length of the connecting group and the size of the hydrophilic group have certain influence on the surface activity, and the alkyl diamine has better surface activity when being used as the connecting group, preferably, the alkyl diamine is at least one selected from N, N-dimethyl (ethylene) ethylene (propylene) diamine and N-methyl-N-ethyl ethylene (propylene) diamine, the reaction temperature is 80-180 ℃, and the reaction time is 8-24; preferably, the reaction temperature is 100-150 ℃ and the reaction time is 10-20 h.
In the step S3, the quaternizing agent is at least one of hydrogen peroxide, halogenated alkyl carboxylic acid and halogenated alkyl sulfonate, the reaction temperature is 0-120 ℃, and the reaction time is 6-24 hours; preferably, the reaction temperature is 25-100 ℃ and the reaction time is 8-15 h.
The branched fluorocarbon surfactant of the present invention has excellent surface activity, and the surface tension of the aqueous solution containing the branched fluorocarbon surfactant at a concentration of not more than 0.5% is lower than 19mN/m. The branched fluorocarbon surfactant can be applied to the fields of chemical industry, oil fields, fire protection, spinning, papermaking and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. the branched fluorocarbon surfactant disclosed by the invention has the green and environment-friendly performance of the C4 type fluorocarbon surfactant and the excellent surface activity of the C6 type fluorocarbon surfactant, so that the development field of fluorocarbon surfactant substitutes is widened;
2. the preparation method has the advantages of simple preparation process, mild reaction condition, low cost, less three wastes and suitability for industrial production.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the invention to these specific embodiments. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
S1, 30.0g (0.12 mol) of perfluoro-2-methyl-2-butene, 26.4g (0.13 mol) of ethyl difluorobromoacetate, 8.1g (0.14 mol) of KF, 0.45g (1.7 mmol) of 18-crown ether-6, 80ml of anhydrous acetonitrile and stirring for reaction at 80 ℃ for 48h are put into a 250ml three-necked flask with a condensing reflux device. Pouring the organic phase into diethyl ether, washing with deionized water and saturated saline water in sequence, and purifying to obtain 40.0g of fluorine-containing intermediate M with the yield of 85%;
s2, adding 131.4g (0.08 mol) of the fluorine-containing intermediate M prepared in the step S1 and 8.8g (0.10 mol) of N, N-dimethyl ethylenediamine into a 250ml three-port bottle with a condensing reflux device, stirring and reacting at 135 ℃ for 12 hours, concentrating and purifying the reaction solution to obtain 27.1g of the fluorine-containing intermediate M2-A, and obtaining 78% yield;
s3, 21.7g (0.05 mol) of the fluorine-containing intermediate M2-A prepared in the step S2, 19.5g (0.125 mol) of ethyl iodide, 100ml of tetrahydrofuran, stirring and reacting for 12 hours at 60 ℃, cooling and filtering, and washing the solid with acetone to obtain 26.8g of the target product branched fluorocarbon surfactant A with the yield of 91%.
The structural formula of the branched fluorocarbon surfactant A is shown as (A):
the structural formula of the fluorine-containing intermediate M2-A is shown as (M2-A):
example 2
S1, preparing a fluorine-containing intermediate M1 in the same way as in example 1;
s2, adding 31.4g (0.08 mol) of the fluorine-containing intermediate M and 13.0g (0.10 mol) of N, N-diethyl propylene diamine into a 250ml three-port bottle with a condensing reflux device, stirring and reacting for 15h at 125 ℃, concentrating and purifying the reaction solution to obtain 32.0g of the fluorine-containing intermediate M2-B, and obtaining 84% yield;
s3, adding 23.8g (0.05 mol) of the fluorine-containing intermediate M2-B into a 250ml three-port bottle with a condensing reflux device, reacting 11.6g (0.10 mol) of sodium chloroacetate with 150ml of ethanol at 80 ℃ for 8 hours under stirring, cooling, filtering, decompressing and evaporating filtrate to dryness, and washing the solid with acetone to obtain the target product branched fluorocarbon surfactant B26.7g, wherein the yield is 96%.
The branched fluorocarbon surfactant B has the following structural formula:
the structural formula of the fluorine-containing intermediate M2-B is shown as (M2-B):
example 3
S1, preparing a fluorine-containing intermediate M1 in the same way as in example 1;
s2, preparing a fluorine-containing intermediate M2 in the same manner as in example 1;
s3, adding 21.7g (0.05 mol) of the fluorine-containing intermediate M2-A and 300ml of 30% hydrogen peroxide into a 250ml three-port bottle, stirring for 12 hours at room temperature, adding 0.08g of manganese dioxide, continuing to react for 3 hours, testing by using starch potassium iodide test paper, filtering, and evaporating the filtrate under reduced pressure to obtain 22.1g of a branched fluorocarbon surfactant of a target product, wherein the yield is 98%.
The branched fluorocarbon surfactant C has the following structural formula:
Claims (7)
1. a branched fluorocarbon surfactant characterized by: the branched fluorocarbon surfactant is shown in the following structural formula (I):
wherein,,
n is selected from any integer from 1 to 5;
R 1 and R is 2 Independently selected from C 1 ～C 6 An alkyl group;
a is selected from O, (CH) 2 )mCH 3 X (X is halogen), (CH) 2 ) mCOO or (CH) 2 )mSO 3 M is selected from any integer from 1 to 10.
2. The branched fluorocarbon surfactant of claim 1, wherein: n is selected from any integer of 2 to 4.
3. The method for preparing a branched fluorocarbon surfactant as claimed in claim 1, wherein: the method comprises the following steps:
s1, reacting perfluoro-2-methyl-2-butene with difluoro halogenated ethyl acetate at 60-100 ℃ in the presence of a solvent, fluoride salt and a catalyst to obtain a fluorine-containing intermediate M1 with a structural formula shown as the following formula (M1),
s2, reacting the fluorine-containing intermediate M1 prepared in the step S1 with alkyl diamine to obtain a fluorine-containing intermediate M2 shown in the structural formula (M2),
s3, reacting the fluorine-containing intermediate M2 prepared in the step S2 with a quaternizing agent to obtain the branched fluorocarbon surfactant.
4. A process for preparing a branched fluorocarbon surfactant as claimed in claim 3, wherein: in the step S1, the solvent is at least one selected from acetonitrile, dimethylformamide, dimethyl sulfoxide and 1, 3-dimethyl-2-imidazolone; the fluoride salt is at least one selected from cesium fluoride, rubidium fluoride, potassium fluoride and sodium fluoride; the catalyst is selected from at least one of tertiary amine, quaternary ammonium salt or crown ether; the difluoro halogenated ethyl acetate is at least one selected from difluoro iodic ethyl acetate, difluoro bromoacetic acid ethyl ester, difluoro chloracetic acid ethyl ester and trifluoro acetic acid ethyl ester.
5. A process for preparing a branched fluorocarbon surfactant as claimed in claim 3, wherein: the reaction temperature in the step S1 is 60-100 ℃ and the reaction time is 12-72 h.
6. A process for preparing a branched fluorocarbon surfactant as claimed in claim 3, wherein: in the step S2, the alkyl diamine is at least one selected from N, N-dimethyl (ethylene) ethylene (propylene) diamine and N-methyl-N-ethyl ethylene (propylene) diamine, the reaction temperature is 80-180 ℃, and the reaction time is 8-24 h.
7. A process for preparing a branched fluorocarbon surfactant as claimed in claim 3, wherein: in the step S3, the quaternizing agent is at least one of hydrogen peroxide, halogenated alkyl carboxylic acid and halogenated alkyl sulfonate, the reaction temperature is 0-120 ℃, and the reaction time is 6-24 hours.
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