CN105833790B - Fluorine-containing phosphate surfactant and preparation method thereof - Google Patents
Fluorine-containing phosphate surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-containing phosphate surfactant and a preparation method thereof, wherein 4-perfluoro-alkenyloxy benzene sulfonyl chloride and 2-methylamino ethanol are used as raw materials, and the raw materials react in an organic solvent for 2-12 h at 0-150 ℃ in the presence of an acid-binding agent, and then are subjected to post-treatment to obtain a product N-hydroxyethyl-N-methyl-4-perfluoro-alkenyloxy benzene sulfonamide; mixing the N-hydroxyethyl-N-methyl-4-perfluoro-alkenyloxy benzene sulfonamide with an inorganic phosphorus compound, reacting at 30-200 ℃ for 2-24 h, adding an alkali liquor for continuous reaction, and separating, dehydrating and drying the obtained reaction liquid to obtain the fluorine-containing phosphate ester surfactant. The synthetic method is simple, the obtained fluorine-containing surfactant has excellent performance and high reaction yield, and the prepared fluorine-containing phosphate surfactant has low surface tension, high activity, better waterproof and oilproof performance, wettability and emulsifying capacity and good environmental friendliness, and can be used as an emulsifier, a wetting agent and the like to be applied to actual life.
Description
Technical Field
The invention relates to the field of surfactants, in particular to a fluorine-containing phosphate surfactant and a preparation method thereof.
Background
The fluorine surfactant has special performance of three high and two high, and is attracted by people increasingly, is the highest surface activity of all the surfactants at present, is mainly applied to special occasions with higher technical requirements or fields which are difficult to be met by common surfactants and have poorer application effects, and the fluorine-containing hydrocarbon group of the fluorine surfactant is hydrophobic and oleophobic [ new chemical material, 2004,32(8):46 ]. The fluorine-containing surfactant gradually develops to the environment-friendly type, high surfactant and low cost in the 21 st century. The fluorine-containing surfactant developed in foreign countries and China mainly takes 8-carbon perfluorooctyl as raw materials to synthesize various fluorine surfactants. Various experimental researches show that perfluorooctyl sulfonyl compounds (PFOS), perfluorooctanoic acid and salts thereof (PFOA) compounds hardly undergo any observable degradation under various physical and chemical conditions, are one of the most difficult degradable organic pollutants in the world at present, and have high bioaccumulation and human multi-organ toxicity. Thus, in the end of 2006, the european union formally issued PFOS sales and use restriction instructions. According to the predictions of international environmental scientists, PFOS/PFOA-containing surfactants and finishes have in recent years been used only to a limited extent globally until complete disablement.
Now, it is urgent to develop substitutes for PFOS and PFOA. The branched fluorocarbon surfactant developed by taking hexafluoropropylene trimer as a raw material is easy to degrade under various physical and chemical conditions, has small biological accumulation, and is an ideal substitute of PFOS/PFOA, U.S. DuPont reports a process flow of telomerizing ethylene, tetrafluoroethylene and perfluoroalkyl iodide in a patent US 8049040B 2, and then preparing the ethylene-tetrafluoroethylene phosphate composition fluorocarbon anionic surfactant through a series of reaction steps, the surfactant obtained in the patent has excellent surface performance, but the telomerization process of ethylene, tetrafluoroethylene and perfluoroalkyl iodide is complex, the yield is low, the cost is high, the industrialization is difficult, a new process for preparing the perfluoroalkyl phosphate fluorocarbon anionic surfactant by taking hexafluoropropylene dimer as a raw material is reported in a patent US20110092410A1, the process has too many reaction steps and complex process, and expensive reagents such as cesium fluoride, bromopropylene and the like are adopted, the production cost is high, and patent WO 9104978(JP 3123786A) reports a preparation method of monophosphate ester fluorocarbon anionic surfactant, but the raw material does not contain omega-H fluorinated alkyl alcohol, so that the raw material is difficult to obtain, and the production cost is high.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides the fluorine-containing phosphate ester surfactant and the preparation method of the perfluoro alkenyl-containing phosphate ester fluorine surfactant, which has the advantages of convenient raw material source, simple synthesis method and high reaction yield.
According to one aspect of the technical scheme, the invention provides a fluorine-containing phosphate ester surfactant which is characterized in that the structural general formula of the fluorine-containing phosphate ester surfactant is as shown in formula I:
wherein n is 2 or 3, M is Na, K, Mg, Ca or NH4。
According to another aspect of the technical scheme of the invention, the fluorine-containing phosphate ester surfactant comprises the following reaction steps:
1) taking 4-perfluoro-alkenyloxy benzene sulfonyl chloride and 2-methylamino ethanol as raw materials, reacting in an organic solvent in the presence of an acid-binding agent, and performing post-treatment to obtain a product N-hydroxyethyl-N-methyl-4-perfluoro-alkenyloxy benzene sulfonamide;
2) mixing the N-hydroxyethyl-N-methyl-4-perfluoro-alkenyloxy benzene sulfonamide with an inorganic phosphorus compound for reaction, adding alkali liquor for continuous reaction, and separating, dehydrating and drying the obtained reaction liquid to obtain the fluorine-containing phosphate ester surfactant.
According to the method provided by the technical scheme, in the step 1), the reaction temperature is 0-150 ℃, and the reaction time is 2-12 hours; in some embodiments of the invention, the reaction temperature of step 1) is 0 ℃, 30 ℃, 50 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 140 ℃; the reaction time is 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12 h.
In some embodiments of the invention, the reaction temperature in the step 2) is 30-200 ℃, and the reaction time is 2-24 h; in other embodiments of the present invention, the reaction temperature in step 2) is 60 to 150 ℃, and the reaction time is 3 to 6 hours; in other embodiments of the present invention, the reaction temperature in step 2) is 30 ℃, 50 ℃, 70 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 170 ℃, 180 ℃ or 190 ℃, and the reaction time is 2h, 4h, 6h, 8h, 9h, 11h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h.
In some embodiments of the invention, 4-perfluoroalkyleneoxybenzenesulfonyl chloride (formula I), 2-methylaminoethanol (formula II), and N-hydroxyethyl-N-methyl-4-perfluoroalkyleneoxybenzenesulfonamide (formula III) have the following structural formulas: wherein n is 2 or 3;
in some embodiments of the invention, the ratio of the amounts of the 4-perfluoroalkyleneoxy benzene sulfonyl chloride, the 2-methylaminoethanol and the acid-binding agent in step 1) is 1:1 to 5; in other embodiments of the present invention, the ratio of the amounts of the 4-perfluoroalkyleneoxy benzene sulfonyl chloride, the 2-methylaminoethanol, and the acid-binding agent is 1:2 to 5; in other embodiments of the present invention, the ratio of the amounts of the 4-perfluoroalkyleneoxy benzene sulfonyl chloride, the 2-methylaminoethanol, and the acid-binding agent is 1:2.5 to 4.5.
In some embodiments of the invention, the organic solvent in step 1) is selected from acetonitrile, ethyl acetate, dichloroethane, trichloroethane, dichloromethane, chloroform, chlorobenzene, nitrobenzene, tetrahydrofuran, N-dimethylformamide or dimethyl sulfoxide.
In some embodiments of the invention, the mass ratio of the organic solvent to the 4-perfluoroalkenyloxy benzenesulfonyl chloride is 1-3: 1; in other embodiments of the present invention, the mass ratio of the organic solvent to the 4-perfluoroalkyleneoxy benzenesulfonyl chloride is 1.5 to 3: 1.
In some embodiments of the invention, the lye is selected from KOH solution, NaOH solution or ammonia.
In some embodiments of the invention, the inorganic phosphorus compound is selected from phosphorus pentoxide or phosphorus oxychloride.
In some embodiments of the invention, the acid-binding agent is selected from at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate or carbonic acid, triethylamine, diethylamine, ethylamine, aniline, phenethylamine or n-butylamine.
In some embodiments of the invention, the work-up described in step 1) comprises distillation under reduced pressure and recrystallization.
The drying in the invention refers to a process of gasifying water or solvent in the material by energy and taking away generated steam. The drying mode employed in some embodiments of the present invention is oven drying. It should be noted that drying methods that can achieve the same effect also include, but are not limited to, oven drying, vacuum drying, freeze drying, air flow drying, microwave drying, infrared drying, high frequency drying, and the like. In some embodiments of the invention, the drying temperature is 100 ℃ or less.
The term "separation" as used herein refers to the separation of fluids from non-fluids by a medium under the action of gravity or other external forces, including but not limited to filter paper, gauze, filter elements, semi-permeable membranes, filters, etc., and theoretically, materials containing porous structures can be used as the filtering medium; filtration devices include, but are not limited to, vacuum or pressure reduction devices, pressurization devices, centrifugation devices, and the like.
The water used in the embodiments of the present invention is deionized water.
All ranges cited herein are inclusive, unless expressly stated to the contrary. For example, the "reaction temperature in step 2) is 30 to 200 ℃ and means that the reaction temperature T is in the range of 30 ℃ to 200 ℃.
The term "or" as used herein means that alternatives, if appropriate, can be combined, that is, the term "or" includes each listed individual alternative as well as combinations thereof. For example, the phrase "the inorganic phosphorus compound is selected from phosphorus pentoxide or phosphorus oxychloride" means that the inorganic phosphorus compound may be one of phosphorus pentoxide or phosphorus oxychloride, or a combination of one or more thereof.
The invention has the beneficial effects that:
the invention provides a new surfactant, namely a fluorine-containing phosphate ester surfactant, the surfactant aqueous solution has low surface tension and high activity, has better waterproof and oilproof properties, wettability and emulsifying capacity and good environmental friendliness, and can be used as an emulsifier, a wetting agent and the like to be applied to actual life; in addition, the method for synthesizing the fluorine-containing phosphate surfactant is simple, the raw materials are cheap and easy to obtain, and the obtained fluorine-containing surfactant has excellent performance and high reaction yield.
Detailed Description
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that various changes and modifications based on the inventive concept herein will occur to those skilled in the art and are intended to be included within the scope of the present invention. The starting materials used in the examples are all commercially available.
Example 1
30mL of acetonitrile, 6.22g (0.01mol) of 4-perfluorononenoyloxybenzenesulfonyl chloride, 0.75g (0.01mol) of 2-methylaminoethanol and 1.06g (0.01mol) of anhydrous sodium carbonate are added into a 100mL four-neck flask, the mixture is stirred, the temperature is raised to 0 ℃, the mixture is kept stirring for 2 hours, the reaction solution is distilled under reduced pressure until no solvent is removed, the mixture is cooled to room temperature, the obtained viscous oily substance is washed with water and recrystallized by acetonitrile to obtain white crystal N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide, the yield is 85 percent, the obtained N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide is put into a 250mL four-neck flask provided with a stirrer, a condenser and a thermometer, the temperature of the stirrer is raised to 30 ℃, 3.55g of phosphorus pentoxide is added in batches, the temperature is gradually raised, and the reaction starts, maintaining the reaction temperature at 30 ℃ for 24h, cooling the temperature to room temperature, adding the mixture into 5g of 30% sodium hydroxide solution, stirring, reacting for 5h, dehydrating to obtain a target product, wherein the yield is 87.5%, and the measured lowest surface tension of the aqueous solution of the target product with the use amount of 0.1% is 19 dynes/cm.
Example 2
30mL of methylene chloride, 6.22g (0.01mol) of 4-perfluorononenoxybenzenesulfonyl chloride, 3.75g (0.05mol) of 2-methylaminoethanol and 4.04g (0.04mol) of triethylamine are added into a 100mL four-neck flask, the mixture is stirred, the temperature is raised to 80 ℃, the temperature is kept and stirred for 12 hours, the reaction solution is distilled under reduced pressure until no solvent is removed, the mixture is cooled to room temperature, the obtained viscous oily substance is washed with water and recrystallized by acetonitrile to obtain white crystal N-hydroxyethyl-N-methyl-4-perfluoroeneoxy benzenesulfonamide, the yield is 98.7 percent, the obtained N-hydroxyethyl-N-methyl-4-perfluoroeneoxy benzenesulfonamide is put into a 250mL four-neck flask provided with a stirrer, a condenser and a thermometer, the temperature of the stirrer is raised to 80 ℃, 3.55g of phosphorus pentoxide is added in batches, the temperature is gradually raised, the reaction is started, maintaining the reaction temperature at 90-110 ℃ for 6h, reducing the temperature to 45 ℃, adding the mixture into 5g of 30% potassium hydroxide solution, stirring for 3.5h, dehydrating to obtain a target product, wherein the yield is 98.5%, and the lowest surface tension of the aqueous solution with the target product dosage of 0.1% is 18.7 dynes/cm through measurement.
Example 3
30mL of N, N-dimethylformamide, 6.22g (0.01mol) of 4-perfluorononenoyloxybenzenesulfonyl chloride, 1.5g (0.02mol) of 2-methylaminoethanol and 6.9g (0.05mol) of anhydrous potassium carbonate are added into a 100mL four-neck flask, the mixture is stirred, the temperature is increased to 150 ℃, the temperature is kept and stirred for 6 hours, the reaction solution is distilled under reduced pressure until no solvent is removed, the mixture is cooled to room temperature, the viscous oily substance obtained by water washing is recrystallized by acetonitrile to obtain white crystal N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide, the yield is 93 percent, the temperature of the obtained N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide is increased to 200 ℃ in a 250mL four-neck flask provided with a stirrer, a condenser and a thermometer, the stirrer is started, 3.55g of phosphorus pentoxide is added in batches, gradually raising the temperature, starting the reaction, maintaining the reaction temperature at 180-200 ℃, reacting for 10 hours, lowering the temperature to 45 ℃, adding the solution into 5g of ammonia water solution (35%), stirring for 3 hours, dehydrating to obtain a target product, wherein the yield is 92%, and the lowest surface tension of the aqueous solution with the target product dosage of 0.1% is 18.5 dyne/cm through measurement.
Example 4
30mL of tetrahydrofuran, 6.22g (0.01mol) of 4-perfluorononenoyloxybenzenesulfonyl chloride, 1.5g (0.02mol) of 2-methylaminoethanol and 0.8(0.02mol) of sodium hydroxide are added into a 100mL four-neck flask, the mixture is stirred, the temperature is raised to 90 ℃, the temperature is kept and stirred for 8 hours, the reaction solution is distilled under reduced pressure until no solvent is removed, the mixture is cooled to room temperature, the obtained viscous oily substance is washed with water and recrystallized by acetonitrile to obtain white crystal N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide, the yield is 95.6 percent, the obtained N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide is put into a 250mL four-neck flask provided with a stirrer, a condenser and a thermometer, the temperature of the stirrer is raised to 90 ℃, 3.55g of phosphorus pentoxide is added in batches, the temperature is gradually raised, the reaction starts, maintaining the reaction temperature at 120-130 ℃, reacting for 12h, reducing the temperature to 35 ℃, adding the mixture into 5g of ammonia water solution (35%), stirring for 2h, dehydrating to obtain a target product, wherein the yield is 94%, and the measured lowest surface tension of the aqueous solution of the target product is 0.1% of the target product is 20 dyne/cm.
Example 5
30mL of chloroform, 6.22g (0.01mol) of 4-perfluorononenoyloxybenzenesulfonyl chloride, 2.25g (0.03mol) of 2-methylaminoethanol and 1.2(0.03mol) of sodium hydroxide are added into a 100mL four-neck flask, the mixture is stirred, the temperature is raised to 70 ℃, the temperature is kept and stirred for 6 hours, the reaction solution is distilled under reduced pressure until no solvent is removed, the mixture is cooled to room temperature, the obtained viscous oily substance is washed with water and recrystallized by acetonitrile to obtain white crystal N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide, the yield is 96 percent, the obtained N-hydroxyethyl-N-methyl-4-perfluoroeneoxybenzenesulfonamide is put into a 250mL four-neck flask provided with a stirrer, a condenser and a thermometer, the temperature of the stirrer is raised to 80 ℃, 3.55g of phosphorus pentoxide is added in batches, the temperature is gradually raised, and the reaction starts, maintaining the reaction temperature at 110-120 ℃, reacting for 10h, reducing the temperature to 35 ℃, adding the solution into 5g of ammonia water solution (35%), stirring for 0.5h, dehydrating to obtain a target product with the yield of 91%, and measuring the lowest surface tension of the aqueous solution with the target product dosage of 0.1% to be 19 dynes/cm.
Example 6
The prepared target product is tested for surface tension performance, wettability, contact angle, water resistance and oil resistance, and the specific test method and the result are as follows:
1) interfacial tension
Testing the influence of the interfacial tension of the oil-water system: the fluorinated polyoxyethylene ether nonionic surfactants prepared in examples 1 to 5 were prepared into an aqueous solution with a mass concentration of 0.1%, and then were mixed with organic solvents, toluene, cyclohexane, and ethyl acetate, respectively, and the interfacial tension was measured with a surface tension meter according to the platinum plate method, and the results were as follows:
TABLE 1 Effect on interfacial tension of oil-water systems
| Oil phase | Toluene | Cyclohexane | Ethyl acetate |
| Pure water | 35.00 | 50.46 | 6.66 |
| Example 1 | 5.56 | 5.05 | 6.19 |
| Example 2 | 5.85 | 5.54 | 6.21 |
| Example 3 | 6.25 | 5.38 | 6.34 |
| Example 4 | 6.08 | 5.52 | 6.28 |
| Example 5 | 6.21 | 5.16 | 6.38 |
The oil phase and the water phase are mixed by stirring and the like, wherein the oil phase and the water phase are immiscible, and one phase is dispersed in the other phase in the form of micro-spherical liquid drops to form a thermodynamically unstable system. In order to stabilize the resulting emulsion for a longer period of time, it is necessary to add a component that lowers its interfacial tension (i.e., an emulsifier) to make an unstable dispersion relatively stable. The emulsifying force is closely related to the interfacial tension, the lower the interfacial tension, the easier the emulsification, and from the above table, it can be known that the fluorinated phosphate ester surfactant has a lower interfacial tension and can be widely used as an emulsifier in the polymerization of fluoropolymers.
2) Measurement of wetting force:
the fluorine-containing phosphoric ester surfactants prepared in examples 1 to 5 were prepared into 0.1% aqueous solutions, and measured according to the canvas sedimentation method (GB 5557-1985 fishhook method), the results were as follows:
table 2 examples 1-5 influence of wetting power of aqueous solutions
| Test group | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| T/s | 13.4 | 13.7 | 14.3 | 13.9 | 14.7 |
From the above table, it can be seen that the synthesized fluorine-containing polyoxyethylene ether nonionic surfactant has good wetting performance, and can be widely applied to the fields of paint, ink and the like as a wetting agent.
3) Measurement of Water contact Angle:
the fluorinated phosphate surfactants prepared in examples 1 to 5 were prepared into an aqueous solution having a concentration of 0.1%, and the contact angles of the solution with synthetic leather, cotton cloth, and glass surfaces were measured respectively using a water contact angle measuring instrument, and the results were as follows:
TABLE 3 surface Water contact Angle
| Test group | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Synthetic leather | 102.1° | 99.6° | 101.2° | 97.8° | 102.8° |
| Cotton cloth | 110.2° | 108.2° | 110.0° | 102.5° | 112.0° |
| Glass | 114.0° | 110.3° | 112.0° | 109.3° | 114.6° |
From the above test results, it can be seen that the fluorinated phosphate ester surfactant has a large surface contact angle with a solid according to the well-known Young equation: the fluorinated polyoxyethylene ether nonionic surfactant is known to have good water repellency when γ S is γ SL + γ Lcos θ.
4) Water and oil repellency test
And (3) waterproof testing: open spray water testing was performed according to AATCC-22. The spray resistance is expressed in water resistance rating. The suffix "+" attached to the data indicates that the performance is slightly better than the numerically characterized rating performance. The evaluation criteria are shown in Table 4:
oil resistance test: the test was performed according to AATCC-118, and 5 drops of test solution were gently dropped by micropipette onto the fabric, one drop at 0.05mL, and the test solution passed the test if 4 or 5 drops remained on the fabric after 30s of standing. Oil repellency is indicated by the maximum score of the test fluid by the test. The oil repellency was rated 8 grades, which were 1, 2, 3, 4, 5, 6, 7 and 8 in order from the poor grade to the excellent grade. The evaluation criteria are shown in Table 4:
TABLE 4 standards for Water and oil repellency testing
And (3) waterproof and oil-proof test: the fluorinated phosphate surfactants prepared in examples 1 to 5 were prepared as 0.1% aqueous solutions and tested according to the above test standards, with the following results:
TABLE 5 Water and oil repellency test results for fabrics
| Test group | Water repellency rating | Oil repellency rating |
| Example 1 | 5 | 5 |
| Example 2 | 4+ | 4 |
| Example 3 | 5 | 6 |
| Example 4 | 4 | 3 |
| Example 5 | 4+ | 4 |
From the above results, it is clear that the fluorinated phosphate ester surfactant has excellent water-and oil-repellency.
Claims (7)
1. The fluorine-containing phosphate ester surfactant is characterized in that the structural general formula of the fluorine-containing phosphate ester surfactant is as shown in formula (I):
wherein n is 2 or 3, M is Na, K, Mg, Ca or NH4；
The preparation method of the fluorine-containing phosphate ester surfactant comprises the following reaction steps:
1) taking 4-perfluoro-alkenyloxy benzene sulfonyl chloride and 2-methylamino ethanol as raw materials, reacting in an organic solvent in the presence of an acid-binding agent, and performing post-treatment to obtain a product N-hydroxyethyl-N-methyl-4-perfluoro-alkenyloxy benzene sulfonamide;
2) mixing the N-hydroxyethyl-N-methyl-4-perfluoro-alkenyloxy benzene sulfonamide and phosphorus pentoxide for reaction, adding the phosphorus pentoxide in batches during the reaction, adding alkali liquor for continuous reaction, and separating, dehydrating and drying the obtained reaction liquid to obtain the fluorine-containing phosphate ester surfactant;
wherein the structural formulas of the 4-perfluoroalkyleneoxy benzene sulfonyl chloride (formula I), the 2-methylaminoethanol (formula II) and the N-hydroxyethyl-N-methyl-4-perfluoroalkyleneoxy benzene sulfonamide (formula III) are as follows: wherein n is 2 or 3;
the mass ratio of the N-hydroxyethyl-N-methyl-4-perfluoroalkyleneoxy benzene sulfonamide to the phosphorus pentoxide in the step 2) is 1-3: 1.
2. The surfactant containing fluorophosphate according to claim 1, wherein the reaction temperature in step 1) is 0-150 ℃, and the reaction time is 2-12 h; in the step 2), the reaction temperature is 30-200 ℃, and the reaction time is 2-24 h.
3. The fluorine-containing phosphate surfactant according to claim 1, wherein the ratio of the amounts of the 4-perfluoroalkyleneoxybenzenesulfonyl chloride, the 2-methylaminoethanol and the acid-binding agent in step 1) is 1:1 to 5.
4. The surfactant according to claim 1, wherein the organic solvent used in step 1) is selected from acetonitrile, ethyl acetate, dichloroethane, trichloroethane, dichloromethane, chloroform, chlorobenzene, nitrobenzene, tetrahydrofuran, N-dimethylformamide, and dimethylsulfoxide.
5. The fluorine-containing phosphate ester surfactant according to claim 1 or 4, wherein the mass ratio of the organic solvent to the 4-perfluoroalkyleneoxy benzenesulfonyl chloride is 1-3: 1.
6. The surfactant of claim 1, wherein the alkali solution is selected from a KOH solution, a NaOH solution, or ammonia water.
7. The surfactant of claim 1, wherein the acid scavenger is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, triethylamine, diethylamine, ethylamine, aniline, phenethylamine, and n-butylamine.
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