CN115057779B - Y-type fluorine-containing amphiphilic polymer and preparation and application thereof - Google Patents

Y-type fluorine-containing amphiphilic polymer and preparation and application thereof Download PDF

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CN115057779B
CN115057779B CN202210565313.6A CN202210565313A CN115057779B CN 115057779 B CN115057779 B CN 115057779B CN 202210565313 A CN202210565313 A CN 202210565313A CN 115057779 B CN115057779 B CN 115057779B
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amphiphilic polymer
type fluorine
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iodide
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CN115057779A (en
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张丽芬
王玉薛
程振平
成健楠
王金英
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Suzhou University
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
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    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols

Abstract

The invention belongs to the technical field of polymer preparation, and particularly relates to a Y-type fluorine-containing amphiphilic polymer and preparation and application thereof. The Y-type fluorine-containing amphiphilic polymer is prepared by adding perfluoroalkyl iodide and functional alpha, omega-non-conjugated diene under the induction of visible light, and transferring atoms and free radicals. The Y-type fluorine-containing amphiphilic polymer provided by the invention has good surface activity and wettability, and has a wide application prospect; the preparation method is simple and efficient, and the fluorine-containing surfactant with excellent performance is designed by introducing a fluorinated chain segment into a molecular structure and regulating the hydrophile-hydrophile ratio.

Description

Y-type fluorine-containing amphiphilic polymer and preparation and application thereof
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a Y-type fluorine-containing amphiphilic polymer and preparation and application thereof.
Background
Currently, surfactants are widely used in daily life, such as cosmetics, textiles, medicine, construction, and other fields, mainly because they are dissolved in liquids to significantly reduce the surface tension or interfacial tension of the solutions, which plays a vital role in improving the performance of the materials. Today, researchers have found that fluorinated materials tend to exhibit unique hydrophobic oleophobicity, chemical stability, thermal stability, etc., due to the small atomic radius, low polarizability, and high bond energy of fluorine atoms, fluorinated surfactants have emerged. It was found that the minimum surface tension value of fluorosurfactant at the critical micelle concentration is significantly lower than for hydrocarbon surfactant. Along with the development of industrial technology, the large-scale production and application of fluorine-containing surfactants such as perfluorooctanoic acid (PFOA), perfluorooctyl sulfonic acid (PFOS) and the like are realized, while enjoying the welfare, people gradually find that the long fluorocarbon chain compound is easy to biologically accumulate and difficult to degrade in nature due to the stable property (J.fluoro chem.2009,130, 1192-1199), which not only causes great threat to human beings, but also endangers the natural environment for the human beings to live. Therefore, it is important to design a fluorosurfactant with excellent surface activity and no bioaccumulation, mainly by developing a short fluorocarbon chain surfactant or inserting a heteroatom such as N, O in a long fluorocarbon chain to make it easy to degrade.
In recent years, various types of surfactants, such as gemini surfactants, bola surfactants (Colloids surf. B Biointerfaces 2005,46,78), multi-chain surfactants (Langmuir 2015,31,10664) and the like, are designed and developed according to actual demands, and the unique structures of the molecules improve the surface activity of the molecules, so that the molecular surfactants have important application values in the fields of oilfield exploitation, emulsion polymerization, membrane protein treatment and the like. In 2019, zhou and colleagues used polyethylene glycol (PEG) and isophorone diisocyanate (IPDI) as raw materials, and a series of nonionic urethane fluorinated surfactants (J.mol. Liq.2019,296, 111851) were rapidly synthesized by a one-pot method. The two short fluoroalkyl chains are connected to one PEG molecule through two IPDI spacers, so that the surface tension of water can be reduced to 17.8-28.7mN/m, and the mode of introducing polyurethane into the molecular structure so as to connect the two fluoroalkyl short chains opens up a new green feasible way for preparing novel fluorine-containing surfactant. Ameduri et al prepared PVDF (polyvinylidene fluoride) emulsion (chem. Commun.2018,54,11399) using the degradable fluorinated surfactant 3-hydroxy-2- (trifluoromethyl) propionic acid (MAF-OH) as an emulsifier. The average particle size of the prepared PVDF latex particles decreases with increasing concentration of MAF-OH, and when MAF-OH is 2.0wt.%, the obtained PVDF latex particles are perfectly spherical, and the particle size is about 100nm.
Recently, the addition reaction between perfluoroalkyl iodides and α, ω -nonconjugated dienes has attracted interest to researchers because fluorinated segments can be simply and efficiently introduced into the molecular structure by this method. The addition reaction based on the interaction of halogen bond (XB) provides a green and efficient strategy for preparing fluorine-containing compounds. Among them, various types of amines, phosphines, halide salts and the like can be used as catalysts to activate the carbon-iodine bond of perfluoroalkyl iodides under the induction of visible light, promoting the addition reaction with alpha, omega-nonconjugated dienes. The above work opens the possibility of proposing an optimized synthesis method to obtain novel fluorosurfactants.
Disclosure of Invention
The invention aims to provide a Y-type fluorine-containing amphiphilic polymer, and preparation and application thereof, and the obtained polymer has good surface activity and wettability, and provides a new way for designing and synthesizing a novel fluorine-containing surfactant under visible light irradiation.
According to the technical scheme of the invention, the Y-type fluorine-containing amphiphilic polymer has the following structural formula:
wherein R is H or I, n=7-12, m=3, 5 or 7.
The second aspect of the invention provides a preparation method of the Y-type fluorine-containing amphiphilic polymer, which comprises the following steps,
s1: performing ring opening reaction on 1, 12-tridecadien-7-alcohol and succinic anhydride to generate alpha, omega-unconjugated diene containing carboxyl;
s2: esterifying the alpha, omega-unconjugated diene containing the carboxyl with polyethylene glycol monomethyl ether to obtain a compound A (alpha, omega-unconjugated diene containing hydrophilic groups);
s3: dissolving the compound A, perfluoroalkyl iodide and amine accelerator in an organic solvent, and carrying out an illumination reaction to obtain a Y-type fluorine-containing amphiphilic polymer with R as I;
s4: dissolving the Y-type fluorine-containing amphiphilic polymer with R as I, azodiisobutyronitrile and tributyltin hydride in toluene, and heating for reaction to obtain the Y-type fluorine-containing amphiphilic polymer with R as H.
Further, in the step S1, 12-tridecadien-7-ol may be prepared by reacting 6-bromo-1-hexene with iodine and magnesium at 70 to 90 ℃.
Further, the temperature of the ring-opening reaction in the step S1 and the esterification reaction in the step S2 are 15-25 ℃.
Further, in the step S2, the molar ratio of the α, ω -nonconjugated diene containing a carboxyl group to the polyethylene glycol monomethyl ether is 1:1-1.5, preferably 1:1.2.
further, the amine promoter is selected from one or more of N, N' -tetramethyl ethylenediamine (TMEDA), triethylamine, ethylenediamine, ethylamine, diethylamine and pyridine, preferably TMEDA.
Further, the perfluoroalkyl iodide is perfluorohexyl iodide, perfluorooctyl iodide or perfluorobutyl iodide; preferably perfluorohexyl iodide.
Further, in the step S2, the molar ratio of the compound a, the perfluoroalkyl iodide and the amine promoter is 1.0:2.0-8.0:0.2-1.0.
Further, the organic solvent is selected from one or more of chloroform, dimethyl sulfoxide, dimethyl ethylenediamine, acetone, 1, 4-dioxane and dimethyl carbonate, preferably chloroform.
Specifically, in the step S3, the compound A, the perfluoroalkyl iodide and the amine accelerator are dissolved in an organic solvent and stirred to be homogeneous, and the stirring speed is 800-1500rpm, preferably 1000rpm.
Further, in the step S3, the wavelength of the photoreaction is 373-403nm, preferably 403nm; the reaction temperature is 20-30 ℃, preferably 25 ℃; the reaction time is 5-15h.
Further, in the step S3, the photoreaction is performed under an oxygen-removing sealed condition.
Further, in the step S4, the molar ratio of the Y-type fluorine-containing amphiphilic polymer with R being I, azobisisobutyronitrile and tributyltin hydride is 1:4-8:10-20, preferably 1:5:15.
specifically, in the step S4, the Y-type fluorine-containing amphiphilic polymer with R being I, azobisisobutyronitrile and tributyltin hydride are dissolved in toluene and stirred to be homogeneous, and the stirring speed is 800-1500rpm, preferably 1000rpm.
Further, in the step S4, the heating reaction is an oil bath reaction after the oxygen removal sealing, and the reaction temperature is 70-90 ℃, preferably 85 ℃.
Specifically, when the perfluoroalkyl iodide is perfluorohexyl iodide or perfluorobutyl iodide, the synthetic route is as follows:
the third aspect of the invention provides application of the Y-type fluorine-containing amphiphilic polymer in a surfactant.
Compared with the prior art, the technical scheme of the invention has the following advantages:
according to the invention, firstly, the alpha, omega-unconjugated diene is subjected to structural design, so that hydrophilic groups are introduced, and perfluoroalkyl iodide can carry out atom transfer radical addition reaction with the alpha, omega-unconjugated diene containing hydrophilic groups under the induction of visible light and the catalysis of amines, so that a Y-type fluorine-containing amphiphilic polymer is obtained, and the series of substances show good surface activity and stability and possibly have potential application prospects in the fields of spinning and papermaking.
In addition, the invention is based on the strong designability of the alpha, omega-nonconjugated diene, is convenient for introducing hydrophilic groups (ionic and nonionic) into the molecular structure, and carries out efficient addition reaction between perfluoroalkyl iodide and the functional alpha, omega-nonconjugated diene under the induction of visible light. This provides a viable strategy for green and simple synthesis of a novel structure fluorosurfactant under visible light irradiation.
Drawings
FIG. 1 is an alpha, omega-nonconjugated diene monomer A-OH 1 H NMR chart.
FIG. 2 is an alpha, omega-nonconjugated diene monomer A-COOH 1 H NMR chart.
FIG. 3 is a Y-type fluorine-containing amphiphilic polymer F 6 EG 13 F 6 -I (a) 1 H NMR spectrum, (b) 19 F NMR spectrum, (c) matrix assisted laser desorption time of flight mass spectrometry.
FIG. 4 is a Y-type fluorine-containing amphiphilic polymer F 6 EG 13 F 6 (a) 1 H NMR spectrum, (b) 19 F NMR spectrum, (c) matrix assisted laser desorption time of flight mass spectrometry.
FIG. 5 is F m EG n F m -static surface tension map of I (n=8, 13; m=4, 6).
FIG. 6 is F m EG n F m (n=8, 13; m=4, 6).
FIG. 7 shows (a) sodium chloride concentration and (b) pH vs. F 6 EG 13 F 6 And F 6 EG 13 F 6 -influence of I surface activity.
Fig. 8 is 0.1wt.% F m EG n F m -I,F m EG n F m And contact angle of aqueous PFOA solution on parafilm.
Fig. 9 is 0.01wt.% F m EG n F m -I,F m EG n F m And contact angle of aqueous PFOA solution on parafilm.
Fig. 10 is 0.1wt.% F m EG n F m -I,F m EG n F m And the contact angle of the aqueous PFOA solution on the polytetrafluoroethylene substrate.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The chemical reagents selected in the examples: 1, 4-diiodoperfluorobutane (98%, boschiza); 1, 6-diiodoperfluorohexane (98%, ladder love); 6-bromo-1-hexene (97%, J & K); succinic anhydride (97%, aladine); polyethylene glycol monomethyl ether 350 (AR, an Naiji chemistry); polyethylene glycol monomethyl ether 550 (AR, an Naiji chemistry); magnesium chips (99%, national medicine); dicyclohexylcarbodiimide (98%, an Naiji chemistry); 4-dimethylaminopyridine (99%, microphone); n, N' -tetramethyl ethylenediamine (TMEDA) (99%, an Naiji chemistry); ethyl formate (99%, aladine).
Example 1: specific synthesis method of each substance
Synthesis of alpha, omega-non-conjugated diene monomer A-OH: to a 250mL three-necked round bottom flask equipped with a magnetic stirrer were added 1.53g of magnesium turnings and one shot of iodine, 8.5mL of 6-bromo-1-hexene was measured and dissolved in 50mL of tetrahydrofuran (1), 10mL of the above solution (1) was removed and placed in the three-necked round bottom flask, heated to 80℃under argon atmosphere, condensed and refluxed, and left to stand until the solution turned from yellow to cloudy off-white, and then the remaining solution (1) was started to be added dropwise at a rate of 2 s/drop, and the reaction was continued at 80℃for 30 minutes after completion of the dropwise addition. After returning to room temperature, a solution of 2.2mL of ethyl formate in 50mL of tetrahydrofuran was added dropwise to the three-necked round bottom flask at a rate of 2 s/drop, and after reacting at room temperature for 12 hours, 20mL of water was added for quenching, at which time a white colloid was formed, and stirring was continued for 20 minutes. After the reaction was completed, the obtained product was dissolved with ethyl acetate, and washed with water several times. The organic layer was collected and dried over anhydrous sodium sulfate, the anhydrous sodium sulfate was removed by suction filtration, ethyl acetate was removed by rotary evaporation, and the crude product was purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give a pale yellow oily product.
FIG. 1 is an alpha, omega-nonconjugated diene monomer A-OH prepared by the above method 1 H NMR chart.
Synthesis of alpha, omega-non-conjugated diene monomer A-COOH: 1.5g of the synthesized A-OH (1.0 eq), 3.19mL of triethylamine (3.0 eq), 0.37g of 4-dimethylaminopyridine (0.4 eq) and 30mL of methylene chloride were weighed into a 100mL three-necked round bottom flask equipped with a magnetic stirrer, 1.53g of succinic anhydride (2.0 eq) was weighed and dissolved in 10mL of methylene chloride, and the mixture was added dropwise to the round bottom flask under stirring at 0℃and reacted at 25℃for 16 hours after the addition was completed. After the reaction is finished, removing the organic solvent methylene dichloride through rotary evaporation, extracting the product for a plurality of times by using ethyl acetate and water, collecting an organic layer, and removing the ethyl acetate through rotary evaporation again to obtain a brown black oily liquid which is the target product alpha, omega-unconjugated diene monomer A-COOH.
FIG. 2 is an alpha, omega-nonconjugated diene prepared by the above methodMonomers A to COOH 1 H NMR chart.
Y-type fluorine-containing amphiphilic polymer F 6 EG 13 F 6 -synthesis of I: the above-synthesized A-COOH (1.0 g,1.0 eq), polyethylene glycol monomethyl ether 550 (1.96 g,1.1 eq), 4-dimethylaminopyridine (0.082 g,0.2 eq), dicyclohexylcarbodiimide (1.06 g,1.5 eq) and 20mL of methylene chloride were weighed into a 50mL three-necked round bottom flask equipped with a magnetic stirrer and reacted at 25℃for 12 hours. After the reaction is finished, removing salt by suction filtration, collecting filtrate and removing organic solvent by rotary evaporation to obtain a crude product B.
The crude product B (1.43 g,1.0 eq) obtained above was weighed into a 5mL ampoule with a magnetic stirrer and 2.24mL of perfluorohexyl iodoalkane (6.0 eq), 0.13mL of TMEDA (0.5 eq) and 8mL of chloroform were added. According to the polymerization procedure of chapter two, the ampoule is removed of oxygen by three freeze-vacuum-thaw cycles and immediately sealed with flame. The ampoule is placed in a light source (lambda) consisting of a violet LED max ＝403nm，29.7mW cm -2 ) The polymerization temperature was controlled at 25℃by 14℃circulating water and an electric fan on an enclosed magnetic stirrer. After 12h of reaction, the ampoule was removed and broken, insoluble material was removed by suction filtration, chloroform was removed by rotary evaporation to give a reddish brown oil which was dissolved in water and stirred overnight. Then dialyzing with dialysis bag with molecular weight cut-off of 3500Da, replacing deionized water every 6h, and freeze drying the aqueous solution obtained by dialysis to obtain target polymer F 6 EG 13 F 6 -I。
FIG. 3 is a Y-type fluorine-containing amphiphilic polymer F prepared by the above method 6 EG 13 F 6 -I (a) 1 H NMR spectrum, (b) 19 F NMR spectrum, (c) matrix assisted laser desorption time of flight mass spectrometry.
Y-type fluorine-containing amphiphilic polymer F 6 EG 13 F 6 Is synthesized by the following steps: weigh 0.28g of synthesized F 6 EG 13 F 6 -I (1.0 eq), 0.085g azobisisobutyronitrile (5.0 eq), 0.42mL tributyltin hydride (15.0 eq) and 8mL toluene were placed in an ampoule with a magnetic stirrer through three freeze-vacuum-thaw cyclesThe ampoule was purged of oxygen and immediately flame sealed and placed in an oil bath at 85 ℃ for 23h. And taking out the ampoule after the reaction is finished, cooling to room temperature, breaking the tube, and removing toluene by rotary evaporation to obtain a crude product. A small amount of water was added to dissolve the crude product and stirred overnight. Then dialyzing with dialysis bag with molecular weight cut-off of 3500Da, replacing deionized water every 6h, and freeze drying the aqueous solution obtained by dialysis to obtain target polymer F 6 EG 13 F 6 。
FIG. 4 is a Y-type fluorine-containing amphiphilic polymer F prepared by the above method 6 EG 13 F 6 (a) 1 H NMR spectrum, (b) 19 F NMR spectrum, (c) matrix assisted laser desorption time of flight mass spectrometry.
Example 2: surface activity research of Y-type fluorine-containing amphiphilic polymer
The present invention performed a static surface tension test on a series of Y-type fluorine-containing amphiphilic polymers obtained, FIG. 5 is F containing-CHI-bonds m EG n F m -I amphiphilic compound, FIG. 6 is F obtained by reductive iodination thereof m EG n F m . The static surface tension test data shows that the static surface tension value rapidly decreases along with the increase of the concentration and then becomes stable, and the surfactant molecules saturate at the gas-liquid interface and start to spontaneously form aggregates in the aqueous solution, and the turning point of the curve corresponds to the critical micelle concentration. The critical micelle concentration and the corresponding minimum surface tension data are summarized in table 1.
TABLE 1F at 25℃ m EG n F m (n=8, 13; m=4, 6) surface properties in aqueous solution
The CMC of the synthesized fluorine-containing surfactant molecules in the aqueous solution is very low, can reach 0.69mmol/L, is far lower than CMC (10 mmol/L) of PFOA, and can reach 18.5mN/m of the lowest surface tension value. This is mainly due to the molecules we synthesizeThe water molecules are more easily and tightly arranged on the surface of the water molecules in a Y shape, and occupy a certain area at the gas-liquid interface, so that the water molecules have smaller critical micelle concentration. From F 4 EG 8 F 4 -I and F 6 EG 8 F 6 As can be seen from the comparison of the data of the formula I, the adsorption quantity gamma of the surfactant at the gas-liquid interface is increased along with the increase of the length of the fluorine chain max Increased average minimum area a per surfactant molecule min And (3) reducing. These phenomena may be due to the fact that lengthening the fluorocarbon chain (increasing the size of the hydrophobic tail) may increase the steric effect, the interaction between F-F is enhanced, leading to an increase in the number of aggregates, the smaller the minimum surface tension value. And F (F) 6 EG 13 F 6 -I and F 6 EG 8 F 6 Comparison of I shows that as the hydrophilic chain length increases, the adsorption of surfactant at the gas-liquid interface decreases, correspondingly the average minimum area A per surfactant molecule min The increase, i.e., the more loosely arranged surfactant molecules at the gas-liquid interface. After reduction of the carbon-iodine bond to a hydrocarbon bond, the hydrophobicity is stronger. With increasing concentration, the minimum surface tension of the surfactant is obviously reduced, compared with the adsorption amount of the surfactant at the gas-liquid interface is reduced when iodine is not extracted, and accordingly the average minimum area A of each surfactant molecule is correspondingly reduced min And (3) increasing.
Example 3: influence of pH and electrolyte on surface tension
For surfactants, not only good surface activity but also stable performance under extreme conditions is important, and therefore, it is essential to conduct salt tolerance and pH tolerance tests on fluorosurfactants. In the research of the invention, we first explore the stability of the surface properties of the synthesized Y-type fluorine-containing amphiphilic polymer in the presence of electrolyte. As shown in fig. 7a, the surface tension does not substantially change as the concentration of sodium chloride in the aqueous solution increases. Subsequently, we have formulated a series of aqueous surfactant solutions of different pH (FIG. 7 b), which shows that pH changes at room temperature have little effect on surface activity, and that pH changes may have an effect on structure and properties if "ester groups" are present in the Y-type fluorine-containing amphiphilic polymer in a high temperature environment. In summary, the series of compounds has excellent salt and pH resistance at room temperature.
Example 4: wetting and spreading Property study
For some low energy solid surfaces, researchers often add surfactants to the solution to adjust the solid-liquid interface so that the solution exhibits good wetting and spreading properties on the solid surface, and contact angles are considered as criteria for evaluating such properties, with smaller contact angle values indicating better wetting properties. In this invention, the inventors formulated a range of aqueous surfactant solutions at concentrations of 0.1wt.% and 0.01wt.%, investigated their wettability on parafilm or polytetrafluoroethylene film and compared to the wettability of perfluorooctanoic acid. As shown in FIG. 8 and FIG. 9, the prepared aqueous solution of the fluorine-containing surfactant can show excellent wettability on the parafilm, and the contact angle is smaller when the concentration is higher, namely the better the wettability is, the contact angle can reach about 55.7 DEG at the lowest, and the contact angle is obviously lower than the contact angle (-83.1 DEG) of PFOA. Furthermore, the inventors have chosen polytetrafluoroethylene as the substrate (see fig. 10), and still see that the aqueous fluorosurfactant solutions of this series have better wettability (39.5 °) than perfluorooctanoic acid (64.5 °) at the same concentration. It follows that the series of surfactants can still exhibit excellent wetting properties at very low concentrations, meaning that the series of fluorosurfactants may have potential application in the textile, paper industry.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (8)

1. A Y-type fluorine-containing amphiphilic polymer is characterized by having the following structural formula:
，
wherein R is H or I, n=7-12, m=3, 5 or 7.
2. A process for preparing a Y-type fluorine-containing amphiphilic polymer as claimed in claim 1, comprising the steps of,
s1: the ring-opening reaction of 1, 12-tridecadien-7-alcohol and succinic anhydride is carried out to generate the carboxyl groupα,ω-a non-conjugated diene;
s2: the carboxyl group is containedα,ωCarrying out esterification reaction on non-conjugated diene and polyethylene glycol monomethyl ether to obtain a compound A;
s3: dissolving the compound A, perfluoroalkyl iodide and amine accelerator in an organic solvent, and carrying out an illumination reaction to obtain a Y-type fluorine-containing amphiphilic polymer with R as I;
the perfluoroalkyl iodide is perfluorohexyl iodide, perfluorooctyl iodide or perfluorobutyl iodide;
the wavelength of the light reaction is 373-403 and nm, and the time is 5-15 h;
s4: dissolving the Y-type fluorine-containing amphiphilic polymer with R as I, azodiisobutyronitrile and tributyltin hydride in toluene, and heating for reaction to obtain the Y-type fluorine-containing amphiphilic polymer with R as H.
3. The method according to claim 2, wherein in the step S2, the carboxyl group is containedα,ωThe molar ratio of non-conjugated diene to polyethylene glycol monomethyl ether is 1:1-1.5.
4. The process according to claim 2, wherein the amine promoter is selected from the group consisting ofN,N,N',N' tetramethyl ethylenediamine, triethylamine, ethylenediamine, ethylamine, diethylamine, and pyridine.
5. The method according to claim 2 or 4, wherein in the step S3, the molar ratio of the compound a, the perfluoroalkyl iodide and the amine promoter is 1.0:2.0-8.0:0.2-1.0.
6. The method of claim 2, wherein the organic solvent is selected from one or more of chloroform, dimethyl sulfoxide, dimethyl ethylenediamine, acetone, 1, 4-dioxane, and dimethyl carbonate.
7. The method according to claim 2, wherein in the step S4, the molar ratio of the Y-type fluorine-containing amphiphilic polymer having R as I, azobisisobutyronitrile, and tributyltin hydride is 1:4-8:10-20.
8. Use of a Y-type fluorine-containing amphiphilic polymer as claimed in claim 1 as a surfactant.
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