CN102633688A - Perfluorovinyl ether sulfonate as well as preparation method and application thereof - Google Patents
Perfluorovinyl ether sulfonate as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to perfluorovinyl ether sulfonate as well as a preparation method and application thereof. Perfluorovinyl ether sulfonate is a compound shown in a formula I, and is prepared by reacting corresponding sulfuryl fluoride with inorganic aqueous alkali. Perfluoroethylene ether sulfonate provided by the invention is a reaction type surfactant and is environment-friendly. In the formula I, M is Na<+1>, K<+1> or NH<4+>, X is an integer of 0-2 and Y is an integer of 2-6.
Description
Technical field
The present invention relates to a kind of perfluorovinyl sulfide ether sulfonate.
Background technology
Fluorochemical surfactant has high surface, high thermal stability and high chemical stability, not only hydrophobic but also lipophobic characteristics, is widely used in a plurality of fields such as chemistry, chemical industry, weaving, leather, building, oil, fire-fighting.Fluorine resin, rubber, coating, fabric finishing agent etc. all need use the emulsifying agent of fluorochemical surfactant as letex polymerization when producing, be perfluorinated sulfonate (PFOS) and perfluorooctanoic acid salt (PFOA) and use the widest fluorochemical surfactant at present.
Research shows; PFOS and PFOA are difficult in physical environment, degrade; Essential characteristic with persistence environmental organic pollutant accumulates in gathering and human body and the animal tissues in environment, and HUMAN HEALTH and environment are produced potential danger; Therefore PFOS and PFOA have been forbidden by European Union, the U.S. and a plurality of countries and regions or have limited use at present, and the novel fluorine tensio-active agent of exploitation compliance with environmental protection requirements is extremely urgent.
Response type surfactant active in recent years; Particularly polymerisable emulsifier more and more causes people's interest; But they are the one type of emulsifying agents that contains the polymerization reaction take place group in the molecular structure, when carrying out letex polymerization can with the polymerization single polymerization monomer copolymerization, thereby for good and all be bonded to polymer surfaces; Become the part of polymkeric substance, can solve the deficiency of many conventional surfactants.
When the fluorochemical monomer letex polymerization; Use polymerisable fluorochemical surfactant as emulsifying agent, this tensio-active agent can with the fluorochemical monomer copolymerization, thereby key is connected in the fluoropolymer surface of generation; Can not get in occurring in nature or the human body, avoid environment and people's health is threatened.
Therefore, the polymerisable fluorochemical surfactant of developing a kind of environmental protection is the problem that the present invention need solve.
Summary of the invention
Perfluoroalkyl vinyl ether sulfonic acid fluoride or perfluoroalkyl vinyl ether sulphonate are the important monomers of preparation perfluorinated sulfonic resin, and its contained pair of key can make itself and all kinds of fluorine-containing and non-fluorine monomer carry out copolymerization.
Disclosed a kind of perfluorovinyl sulfide ether sulfonate, it not only contains polymerizable functional group (unsaturated link(age)), and contains hydrophilic and hydrophobic group, can be used as the letex polymerization that response type surfactant active is used for fluorochemical monomer.
One object of the present invention is, a kind of novel perfluorovinyl sulfide ether sulfonate is provided.Perfluorovinyl sulfide ether sulfonate of the present invention has structure shown in the formula I:
Among the formula I, M is Na
+, K
+Or NH
4 +, X is 0～2 integer, Y is 2～6 integer.
Another object of the present invention is, a kind of method for preparing compound shown in the above-mentioned formula I is provided, and the key step of said method is: by compound shown in the formula II and corresponding mineral alkali (like NaOH, KOH or NH
3H
2O) reactant aqueous solution makes.
Another object of the present invention is, discloses a kind of purposes of compound shown in the formula I, promptly can be used as the application (concrete as be used for the letex polymerization etc. of fluorochemical monomer) of response type surfactant active.
Description of drawings
Fig. 1 is by the concentration and the surface tension curve of the perfluorovinyl sulfide ether sulfonate of embodiment 1 preparation
Fig. 2 is by the concentration and the surface tension curve of the perfluorovinyl sulfide ether sulfonate of embodiment 2 preparations
Fig. 3 is contrasted with Comparative Examples 2 prepared particle size of emulsion by embodiment 10
Fig. 4 is contrasted with Comparative Examples 3 prepared particle size of emulsion by embodiment 13
Embodiment
The method for preparing compound shown in the formula I provided by the present invention; More concrete step is: under room temperature (5 ℃～35 ℃) and stirring condition, in perfluoroalkyl vinyl ether sulfonic acid fluoride (compound shown in the formula II), drip the aqueous solution of alkali, to the pH value of reaction solution be 7～10 (preferred 8～9); Stop to drip the aqueous solution of alkali; Filter, filter cake after washing, recrystallization (the preferred acetone of the solvent of recrystallization) and drying, obtains target compound (compound shown in the formula I) successively;
Wherein, the aqueous solution of said alkali is the aqueous solution or the ammoniacal liquor of sodium hydroxide or Pottasium Hydroxide, and its concentration is preferably 1wt%～52wt%, and preferred concentration is 10wt%～30wt%.
Perfluorovinyl sulfide ether sulfonate provided by the present invention (compound shown in the formula I) is as the application of response type surfactant active, specifically as: compound shown in the formula I can be used as emulsifying agent and is used for gathering the monomer letex polymerization of (comprising fluorine-containing or not fluorine-containing gathered monomer).Because compound shown in the formula I is a response type surfactant active, its with can gather monomer radical copolymerization can take place, thereby " key connects " on polymkeric substance, avoided the pollution to environment.
In concrete method of use be, compound shown in the formula I and/or other auxiliary agent (like stablizer paraffin etc.) are scattered in the water that under agitation, adding can gather monomer and carry out emulsification, adds initiator again, aggregate number hour obtains polymerization (thing) emulsion under certain condition,
Wherein, (more preferably 1wt%～3wt%), the described monomer that gathers is selected from the consumption of compound shown in the formula I: perfluorinated monomer or partially fluorinated monomers such as tetrafluoroethylene, vinylidene, R 1216, trifluorochloroethylene, trifluorostyrene, perfluoroalkyl vinyl ether, fluorinated acrylate for the 0.1wt%～10wt% that can gather total monomer weight; Or ethene, propylene, vinylchlorid, vinylbenzene, vinyl acetate, esters of acrylic acid and other contain a kind of or two kinds of (containing two kinds) above mixtures in the hydrocarbon monomer that can gather functional group etc.
In addition; Perfluorovinyl sulfide ether sulfonate provided by the invention (compound shown in the formula I) can use as emulsifying agent separately; Or use with the composite back of other existing emulsifying agent (fluorine-containing or not fluorine-containing emulsifying agent); Perfluorovinyl sulfide ether sulfonate provided by the invention (compound shown in the formula I) is when using as emulsifying agent, and its suitable use temperature is 30 ℃～130 ℃.
Of the present inventionly mainly contain following advantage:
1, perfluoroalkyl vinyl ether sulphonate involved in the present invention effect with good reduction water surface tension, it reduces the capillary maximum capacity of the aqueous solution and can reach about 20mN/m;
2, perfluoroalkyl vinyl ether sulphonate involved in the present invention contains polymerisable double bonds; Can carry out radical copolymerization with monomer when using as emulsifying agent; " thereby key connects " in polymkeric substance, thoroughly avoided the pollution of small molecules fluorine-containing emulsifier to environment.
When 3, perfluoroalkyl vinyl ether sulphonate involved in the present invention used as emulsifying agent, its TR that is suitable for was wide, and the monomer scope that is suitable for is wide, has a good application prospect.
Through embodiment the present invention is done further elaboration below.Should understand; Following examples only are used for better understanding content of the present invention; Can not be interpreted as the restriction to protection domain of the present invention, the professional in this field content is made according to the present invention some nonessential improvement and adjustment still belong to protection scope of the present invention.
Embodiment 1
The preparation of compound shown in the formula I a
In the round-bottomed flask of 250mL, add 22.3g perfluor-4-methyl-6-vinyl-3 in advance, 6-two oxygen-butyl sulfonic acid fluoride stir under the room temperature; In system, drip 10% the about 44mL of aqueous sodium hydroxide solution gradually, reach 8～9, stopped reaction to the pH of system; Mixture is filtered, and the white solid of gained is transferred in the beaker, adds the 100mL acetone solution; The white solid that is insoluble to acetone is filtered out, and rotary evaporation falls acetone, drying; Obtain white solid product 21.2g (title compound), productive rate is 90.9%.
19F?NMR(D
2O，400M?Hz)：δppm-81，-82，-87，-116.5，-119.5，-138.5，-147。The surface tension data of title compound are seen accompanying drawing 1.
The preparation of compound shown in the formula I b
In the round-bottomed flask of 250mL, add 22.3g perfluor-4-methyl-6-vinyl-3 in advance, 6-two oxygen-butyl sulfonic acid fluoride stir under the room temperature; The pH that in system, drips 10% potassium hydroxide aqueous solution to system gradually reaches 8～9, and stopped reaction places round-bottomed flask with mixture; Rotary evaporation is removed the half the solvent of former approximately quantity of solvent, filters the gained solids washed with acetone then; Collect acetone soln, with solvent evaporation, drying; Obtain white solid product 22.5g (title compound), productive rate is 93.4%, and the surface tension data are seen accompanying drawing 2.Nuclear magnetic data (fluorine spectrum) is with identical described in the embodiment 1.
The preparation of compound shown in the formula I c
In the round-bottomed flask of 250mL, add 22.3g perfluor-4-methyl-6-vinyl-3 in advance, 6-two oxygen-butyl sulfonic acid fluoride stir under the room temperature, and the pH that in system, drips 10% ammoniacal liquor to system gradually reaches 8～9; Stopped reaction places round-bottomed flask with mixture, and rotary evaporation is removed whole solvents; The gained solids washed with acetone is collected acetone soln, with solvent evaporation; Drying obtains white solid product 20.615g (title compound), and productive rate is 89.44%.Nuclear magnetic data (fluorine spectrum) is with identical described in the embodiment 1.
The preparation of compound shown in the formula I d
In the round-bottomed flask of 250mL, add 14.0g perfluor 2-vinyl oxygen ethyl sulfonic acid fluoride in advance, stir under the room temperature, the pH that in system, drips 20% potassium hydroxide aqueous solution to system gradually reaches 8～9, stopped reaction; Mixture is placed round-bottomed flask, and rotary evaporation is removed the half the solvent of former quantity of solvent, filters then; Solid is used acetone solution, filter insolubles, evaporating solvent; Drying gets solid product 14.9g (title compound), productive rate 94.3%.
19F?NMR(D
2O，400MHz)：δppm-138.7，-123.76，-116.38，-114.23，-86.06。
The preparation of compound shown in the formula I e
In the round-bottomed flask of 250mL, add 19.0g perfluor 4-vinyl oxygen-butyl sulfonic acid fluoride in advance, stir under the room temperature, the pH that in system, drips 10% aqueous sodium hydroxide solution to system gradually reaches 8～9; Stopped reaction filters mixture, and the white solid of gained is transferred in the beaker; Add the 100mL acetone solution, the white solid that is insoluble to acetone is filtered out, rotary evaporation falls acetone; Drying gets solid product 18.4g (title compound) productive rate 92.0%.
The vinylidene polyreaction
In 10L horizontal reacting still, add 6L ionized water and 12g perfluor-4-methyl-6-vinyl-3,6-dioxy butyl sulfonic acid sodium (compound shown in the formula I a).Reaction kettle sealing back is with nitrogen replacement still air, treat that oxygen level is less than 50ppm after, temperature of reaction kettle is risen to 130 ℃, pumping into vinylidene fluoride monomers to reaction kettle pressure afterwards is 5MPa, adds the 420g vinylidene fluoride monomers altogether.Add 1.5g 2 after the reaction kettle pressure-stabilisation; 5-dimethyl--2,5-di-t-butyl peroxy-3-hexin initiator is after pressure to be occurred falls; Begin to add vinylidene fluoride monomers to keep reaction pressure at 5MPa; After adding amount of monomer and reaching 1000g, stop to replenish vinylidene fluoride monomers, the emulsion of taking-up directly can obtain the 1150g polyvinylidene fluoride polymer after the oven dry.
Embodiment 7
The vinylidene polyreaction
In 10L horizontal reacting still, add 5L ionized water and 6g perfluor-4-methyl-6-vinyl-3,6-dioxy butyl sulfonic acid sodium (compound shown in the formula I a).Reaction kettle sealing back is with nitrogen replacement still air, treat that oxygen level is less than 50ppm after, temperature of reaction kettle is risen to 70 ℃, pumping into vinylidene fluoride monomers to reaction kettle pressure afterwards is 4.5MPa, adds the 530g vinylidene fluoride monomers altogether.Add 1.2g Sodium Persulfate initiator after the reaction kettle pressure-stabilisation; After pressure to be occurred falls; Begin to add vinylidene fluoride monomers to keep reaction pressure at 4.5MPa; After adding amount of monomer and reaching 800g, stop to replenish vinylidene fluoride monomers, the emulsion of taking-up directly can obtain the 950g polyvinylidene fluoride polymer after the oven dry.
Embodiment 8
Copolyreaction
At first that vinylidene and perfluor n-propyl vinyl ether (PPVE) is subsequent use for the 5mol% ratio is made in the mix monomer placement monomer groove according to perfluor n-propyl vinyl ether content, the temperature of mix monomer is controlled at 45 ℃.
In 10L horizontal reacting still, add 5L ionized water and 15g perfluor-4-methyl-6-vinyl-3,6-dioxy butyl sulfonic acid sodium (compound shown in the formula I a).Reaction kettle sealing back is with nitrogen replacement still air, treat that oxygen level is less than 50ppm after, temperature of reaction kettle is risen to 65 ℃, pumping into mix monomer to reaction kettle pressure afterwards is 3.8MPa, adds the 490g mix monomer altogether.Add 1.5g Potassium Persulphate initiator after the reaction kettle pressure-stabilisation; After pressure to be occurred falls; Begin to add mix monomer to keep reaction pressure at 3.8MPa; After adding amount of monomer and reaching 800g, stop to replenish vinylidene fluoride monomers, the emulsion of taking-up directly can obtain the 980g polyvinylidene fluoride polymer after the oven dry.
Embodiment 9
Copolyreaction
At first that vinylidene and R 1216 is subsequent use for the 3mol% ratio is made in the mix monomer placement monomer groove according to R 1216 (HFP) content, the temperature of mix monomer is controlled at 30 ℃.
In 10L horizontal reacting still, add 6L ionized water and 6g perfluor-4-methyl-6-vinyl-3,6-dioxy butyl sulfonic acid sodium (compound shown in the formula I a).Reaction kettle sealing back is with nitrogen replacement still air, treat that oxygen level is less than 50ppm after, temperature of reaction kettle is risen to 82 ℃, pumping into mix monomer to reaction kettle pressure afterwards is 5.2MPa, adds the 600g mix monomer altogether.Add 2g Sodium Persulfate initiator after the reaction kettle pressure-stabilisation; After pressure to be occurred falls; Begin to add mix monomer to keep reaction pressure at 5.2MPa; After adding amount of monomer and reaching 1000g, stop to replenish vinylidene fluoride monomers, the emulsion of taking-up directly can obtain the 1250g polyvinylidene fluoride polymer after the oven dry.
Comparative Examples 1
Main raw material and step are identical with embodiment 6, are emulsifying agent but wherein adopt ammonium perfluorocaprylate, add 15g altogether.Temperature of reaction is 135 ℃, and reaction adds the 400g monomer early stage altogether, and reaction obtains the 1100g polymkeric substance after finishing altogether.
Table 1
Can be known that by table 1 perfluorovinyl sulfide ether sulfonate provided by the invention is during as emulsifying agent, the emulsifying effectiveness of itself and ammonium perfluorocaprylate (existing emulsifying agent) is suitable even more excellent.
30 gram methylacrylic acid ten difluoro heptyl esters and 30 gram TEB 3Ks are restrained perfluor-4-methyl-6-vinyl-3 with 1.5 in 110 gram water; After 6-dioxy butyl sulfonic acid sodium (compound shown in the formula I a) emulsification; Under nitrogen protection, drip with 30 gram water-soluble initiators (Potassium Persulphate and sodium sulfite anhy 96); At 60 ℃ of following reaction stopped reaction after 4 hours, obtain solid content and be 30% fluorinated acrylate emulsion.Gained emulsion gel amount＜0.5% can be preserved more than 6 months and not have deposition and produces under the good stability, normal temperature, the emulsion median size is about 110nm and distributes to be concentrated.
Comparative Examples 2
Routine as a comparison with ammonium perfluorocaprylate as the prepared emulsion of emulsifying agent.The preparation of Comparative Examples is with embodiment 10, and only with perfluor-4-methyl-6-vinyl-3,6-dioxy butyl sulfonic acid sodium changes ammonium perfluorocaprylate into.The emulsion particle diameter of embodiment 10 and Comparative Examples 2 is seen accompanying drawing 3.Can know from accompanying drawing 3, perfluor-4-methyl-6-vinyl-3, the emulsifying effectiveness and the ammonium perfluorocaprylate of 6-dioxy butyl sulfonic acid sodium are suitable, even slightly excellent.
Embodiment 11
30 gram methylacrylic acid ten difluoro heptyl esters and 30 gram TEB 3Ks are restrained emulsifying agent (perfluors-4-methyl-6-vinyl-3 with 1.5 in 110 gram water; 6-dioxy butyl sulfonic acid sodium (compound shown in the formula I a) and each 0.75g of sodium lauryl sulphate) after the emulsification; Under nitrogen protection, drip with 30 gram water-soluble initiators (Potassium Persulphate and sodium sulfite anhy 96); At 60 ℃ of following reaction stopped reaction after 4 hours, obtain solid content and be 30% fluorinated acrylate emulsion.Gained emulsion gel amount＜0.5% can be preserved more than 6 months and not have deposition and produces under the good stability, normal temperature, the emulsion median size is about 96nm and distributes to be concentrated.
With 20 gram vinylformic acid perfluor alkyl ethide esters; 20 gram TEB 3Ks and 20 gram NSC 20956s restrain emulsifying agent (perfluors-4-methyl-6-vinyl-3 with 1.5 in 110 gram water; 6-dioxy butyl sulfonic acid potassium (compound shown in the formula I b) and each 0.75g of sodium lauryl sulphate) emulsification; Under nitrogen protection, drip the Potassium Persulphate initiator be dissolved in the 10 gram water,, obtain solid content and be 33% fluorinated acrylate emulsion in 70 ℃ of following polymerizations 4 hours.Gained emulsion gel amount＜0.5% can be preserved more than 6 months and not have deposition and produces under the good stability, normal temperature, the emulsion median size is about 90nm and distributes to be concentrated.
Embodiment 13
With the end capped urethane of Rocryl 400 as macromonomer; Carry out emulsion copolymerization with fluorinated acrylate and methacrylic ester; Concrete grammar is following: in the four-hole boiling flask that whisking appliance, reflux condensing tube, TM and nitrogen interface are housed, add polyurethane aqueous dispersion (containing polyurethane macromolecular monomer 30 grams); Nitrogen protection contains 0.2 gram perfluor-4-methyl-6-vinyl-3 with stirring to add down; The aqueous solution of 6-dioxy butyl sulfonic acid sodium (compound shown in the formula I a) and 0.2 gram sodium lauryl sulphate; Be heated to 65 ℃, in system, drip comonomer (mixed solutions of 10 gram methylacrylic acid ten difluoro heptyl esters and 10 gram TEB 3Ks) and initiator simultaneously, polymerization obtained fluorochemical urethane-acrylic ester emulsion after 4 hours.
Comparative Examples 3
Routine as a comparison with ammonium perfluorocaprylate as the prepared emulsion of emulsifying agent.The preparation of Comparative Examples is with embodiment 13, and only with perfluor-4-methyl-6-vinyl-3,6-dioxy butyl sulfonic acid sodium changes ammonium perfluorocaprylate into.The emulsion particle diameter of embodiment 13 and Comparative Examples 3 is seen accompanying drawing 4.
Can know that from accompanying drawing 4 emulsifying effectiveness and the ammonium perfluorocaprylate of perfluoroalkyl vinyl ether sulphonate are suitable, even slightly excellent.
30 gram methylacrylic acid ten difluoro heptyl esters and 30 gram TEB 3Ks are restrained perfluor-2-vinyl oxygen ethylsulfonic acid potassium (compound shown in the formula I d) emulsifications with 1.5 in 110 gram water after; Under nitrogen protection, drip with 30 gram water-soluble initiators (Potassium Persulphate and sodium sulfite anhy 96); At 60 ℃ of following reaction stopped reaction after 4 hours, obtain solid content and be 30% fluorinated acrylate emulsion.Gained emulsion gel amount＜0.5% can be preserved more than 6 months and not have deposition and produces under the good stability, normal temperature, the emulsion median size is about 102nm and distributes to be concentrated.
The vinylidene polyreaction
In 10L horizontal reacting still, add 6L ionized water and 12g perfluor-2-vinyl oxygen ethylsulfonic acid potassium (compound shown in the formula I d).Reaction kettle sealing back is with nitrogen replacement still air, treat that oxygen level is less than 50ppm after, temperature of reaction kettle is risen to 130 ℃, pumping into vinylidene fluoride monomers to reaction kettle pressure afterwards is 5MPa, adds the 420g vinylidene fluoride monomers altogether.Add 1.5g 2 after the reaction kettle pressure-stabilisation; 5-dimethyl--2,5-di-t-butyl peroxy-3-hexin initiator is after pressure to be occurred falls; Begin to add vinylidene fluoride monomers to keep reaction pressure at 5MPa; After adding amount of monomer and reaching 1000g, stop to replenish vinylidene fluoride monomers, the emulsion of taking-up directly can obtain the 1132g polyvinylidene fluoride polymer after the oven dry.
Embodiment 17
With 20 gram vinylformic acid perfluor alkyl ethide esters; 20 gram TEB 3Ks and 20 gram NSC 20956s restrain emulsifying agent (perfluor-4-vinyl oxygen-butyl potassium sulfonate (compound shown in the formula I e) and each 0.75g of sodium lauryl sulphate) emulsifications with 1.5 in 110 gram water; Under nitrogen protection, drip the Potassium Persulphate initiator that is dissolved in the 10 gram water; In 70 ℃ of following polymerizations 4 hours, obtain solid content and be 33% fluorinated acrylate emulsion.Gained emulsion gel amount＜0.5% can be preserved more than 6 months and not have deposition and produces under the good stability, normal temperature, the emulsion median size is about 87nm and distributes to be concentrated.
Embodiment 18
Copolyreaction
At first that vinylidene and perfluor n-propyl vinyl ether (PPVE) is subsequent use for the 5mol% ratio is made in the mix monomer placement monomer groove according to perfluor n-propyl vinyl ether content, the temperature of mix monomer is controlled at 45 ℃.
In 10L horizontal reacting still, add 5L ionized water and 15g perfluor-4-vinyl oxygen-butyl sodium sulfonate (compound shown in the formula I e).Reaction kettle sealing back is with nitrogen replacement still air, treat that oxygen level is less than 50ppm after, temperature of reaction kettle is risen to 65 ℃, pumping into mix monomer to reaction kettle pressure afterwards is 3.8MPa, adds the 490g mix monomer altogether.Add 1.5g Potassium Persulphate initiator after the reaction kettle pressure-stabilisation; After pressure to be occurred falls; Begin to add mix monomer to keep reaction pressure at 3.8MPa; After adding amount of monomer and reaching 800g, stop to replenish vinylidene fluoride monomers, the emulsion of taking-up directly can obtain the 959g polyvinylidene fluoride polymer after the oven dry.
Claims (9)
1. perfluorovinyl sulfide ether sulfonate, it has structure shown in the formula I:
Among the formula I, M is Na
+, K
+Or NH
4 +, X is 0～2 integer, Y is 2～6 integer.
2. perfluorovinyl sulfide ether sulfonate as claimed in claim 1 is characterized in that, wherein X is 1, and Y is 2; Or X is 0, and Y is 2 or 4.
3. one kind prepares the method for perfluorovinyl sulfide ether sulfonate according to claim 1 or claim 2, and its key step is: 5 ℃～35 ℃ conditions, made by compound shown in the formula II and corresponding inorganic base aqueous solution reaction:
Wherein, the pH value of reaction solution is 7～10.
4. method as claimed in claim 3 is characterized in that, wherein the pH value of reaction solution is 8～9.
5. method as claimed in claim 4 is characterized in that, wherein used inorganic base aqueous solution is an aqueous sodium hydroxide solution, potassium hydroxide aqueous solution or ammoniacal liquor, and its concentration is 1wt%～52wt%.
6. method as claimed in claim 5 is characterized in that, the concentration of wherein said inorganic base aqueous solution is 10wt%～30wt%.
According to claim 1 or claim 2 the perfluorovinyl sulfide ether sulfonate as the application of response type surfactant active.
8. application as claimed in claim 7 is characterized in that, claim 1 or 2 said perfluorovinyl sulfide ether sulfonates are as the application that can gather monomer emulsion polymeric reactive emulsifier.
9. application as claimed in claim 8; It is characterized in that the wherein said monomer that gathers comprises: a kind of or more than two kinds in tetrafluoroethylene, vinylidene, R 1216, trifluorochloroethylene, trifluorostyrene, perfluoroalkyl vinyl ether, fluorinated acrylate, ethene, propylene, vinylchlorid, vinylbenzene, vinyl acetate or the propenoate.
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