CN100336860C - Nano-emulsified fluorine containing ion exchange resin and its preparation method and application - Google Patents
Nano-emulsified fluorine containing ion exchange resin and its preparation method and application Download PDFInfo
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- CN100336860C CN100336860C CNB031418678A CN03141867A CN100336860C CN 100336860 C CN100336860 C CN 100336860C CN B031418678 A CNB031418678 A CN B031418678A CN 03141867 A CN03141867 A CN 03141867A CN 100336860 C CN100336860 C CN 100336860C
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Abstract
The present invention discloses nanometer emulsifying fluorinion containing exchange resin and a preparation method thereof and the application thereof. The fluorinion containing exchange resin is water dispersion of nanometer particles with diameter ranges from 10 to 200 nanometers and wide molecular weight distribution range. The fluorinion containing exchange resin is composed of fluorine containing olefine monomers and perfluoro vinyl ether monomers or monomers containing carboxylic acid and carboxylic acid ester. Each molecule generates various ion exchanging functional groups, or primary base groups of a molecule body are converted to the ion exchanging functional groups. The present invention also relates to a preparation method for nanometer emulsion fluoropolymer. Each fluoropolymer ion has a core structure and a shell structure, wherein a shell layer has a composite structure; a core layer has another structure. The obtained fluoropolymer emulsion has favorable stability and simultaneously has the core structure and the shell structure; the emulsion has favorable ionic conductivity or protonic conductivity and also has favorable mechanical strength. The polymerization method of the nanometer emulsion is used for producing the fluoropolymer under various conditions and has wide significance for widening the application of the fluoropolymer.
Description
Technical field
The present invention relates to a kind of ion exchange fluoro resin preparation method and application, more specifically to nanometer emulsified ion exchange fluoro resin preparation method and application.
Background technology
E.I.Du Pont Company and some Japanese firms are commercialization of production ion exchange fluoro resin all.According to reports, they adopt the method production of fluorine-containing solution or conventional emulsion polymerization.Nanometer emulsified method also of no use is produced the relevant report of this kind fluoropolymer now.The nanoemulsions quite stable, the colloid particle diameter is in 300 nanometers.The colloid particle diameter is more little, and emulsion is stable more.Therefore, preferably control the colloid particle diameter in 100 nanometers.Because this emulsion has goodish stable, the prepared product of nanoemulsions polymerization has better commercial promise than conventional emulsion polymerization.
Usually find that solution polymerization or conventional emulsion polymerization are difficult to produce the ion exchange fluoro resin of low equivalent number.The ion exchange fluoro resin of low equivalent number has ionic conducting property preferably, can more effectively be used for fuel cell and chlorine industry.Therefore, the nanoemulsions polymeric method that we invent out this novelty helps producing the ion exchange fluoro resin of low equivalent number most, to the widespread use of expanding fluoropolymer highly significant.
Summary of the invention
The purpose of this invention is to provide a kind of nanometer emulsified ion exchange fluoro resin preparation method and application.
Nanometer emulsified ion exchange fluoro resin preparation method comprises the steps:
(1) add entry, tensio-active agent and contain the monomer of ion exchange functional groups in reaction system, stir through suitable mechanical external force, form nanoemulsions, its size droplet diameter on average at 10～300nm (nanometer), is preferably in 30～200nm.The tensio-active agent weight percent that adds is 0.1～5%, and the weight percent monomer that contains ion exchange functional groups is 1～30%.
The above-mentioned tensio-active agent that adds in reaction system is fluorochemical surfactant preferably, and the monomer that contains ion exchange functional groups can be sulphonyl halogenation group (SO
2Y) or ester (COOR), wherein Y is a halogen element, as F, Cl, Br, R are the alkyl of carbonatoms from 1-20, contain in the monomer of ion exchange functional groups, preferably contain following a kind of monomer at least:
CF
2＝CFOCF
2[CF(CF
3)OCF
2]n-(CF
2)m-SO
2F
CF
2＝CFOCF
2[CF(CF
3)OCF
2]n-(CF
2)m-COOR
N=0,1,2; M=1,2,3; R is the alkyl of 1～15 carbon
Above-mentionedly can add or not add the fluorine-containing liquid of inertia in reaction system, as adding the fluorine-containing liquid of inertia, the weight percent of adding is 1～10%.
(2) from the reaction system gas phase, add fluorine-containing but do not contain the monomer of ion exchange functional groups, tetrafluoroethylene (TFE) for example, R 1216 (HFP), fluorine-containing alkyl vinyl ether monomer, trifluorochloroethylene (CFCl=CF
2), vinylidene (CH
2=CF
2) etc., this moment, the pressure range of reaction system was 100～2500kPa.
(3) in reaction system, add radical polymerization initiator, carry out the free radical high molecular polymerization, obtain nanometer emulsified ion exchange fluoro resin.Initiator can adopt water soluble starter such as ammonium persulphate, or fluorine-containing organo-peroxide is as (C
7F
15COO)
2(annotate: this thing can be made by Perfluorocaprylic Acid halogenide and peralcohol).Range of reaction temperature can be preferably in 65～100 ℃ at 35～150 ℃, and reaction time range can be at 5 minutes～24 hours.
Nanometer emulsified ion exchange fluoro resin of the present invention can be scattered in ethanol aqueous solution, and can be applicable to make film, and the thickness range of film is 15～1000 μ m (micrometer), and this film can be used for the application of fuel cell, chlorine industry and gas delivery.Made film can be a composite membrane, is the matrix material of ion exchange resin and microporous membrane.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but the present invention is not limited to these embodiment.
Nanometer emulsified ion exchange fluoro resin, the median size of resin particle (number average) is 10～300nm in its emulsion, better between 30～200nm, preferably be in 40～100nm, the ion exchange fluoro resin molecular weight is 1,000～10, and 000, between 000, each copolymerization molecule contains ion exchange functional groups or the elementary group of its first body can be transformed into ion exchange functional groups.This ion-exchange group comprises that sulfonic acid or sulfonate form are as (SO
3X), thionamic acid (SO
2NHSO
2-Rf), carboxylic acid (COOX) etc., wherein X is H or metal ion.The elementary group of this first body comprises sulfuryl halide (SO
2Y), (COOR), wherein Y is F to ester, and Cl or Br, R are the alkyl of carbonatoms from 1 to 20.The ion-exchange equivalent number is between 500 to 1500.
Nanometer emulsified ion exchange fluoro resin has two kinds of structures, a kind ofly is
The wherein wt percentage composition:
l＝0-90％；m＝0-20％；n＝0-20％；p＝0-70％；q＝0-70％；r＝10-70％；
l+m+n+p+q+r＝100％
Rf:1-15 carbon perfluoroalkyl or perfluoroalkyl ethers
A:-SO
3X;-SO
2NHSO
2Rf;-SO
2Y; Wherein X is hydrogen or metal ion, and Y is a halogen element, as F, and Cl, Br etc.
Another kind is
The wherein wt percentage composition:
l＝0-90％；m＝0-20％；n＝0-20％；p＝0-70％；q＝0-70％；r＝10-70％；
l+m+n+p+q+r＝100％
Rf:1-15 carbon perfluoroalkyl or perfluoroalkyl ethers
M:-CH
2CH (COOZ)-or-CF
2CF (ORfCOOZ)-; Wherein Z is the alkyl of hydrogen or metal ion or 1-10 carbon.
Nanometer emulsified ion exchange fluoro resin, wherein each resin particle can have core/shell structure, and shell is by a kind of structure of forming, and sandwich layer is another kind of the composition, the composition of its core/shell contains different ion-exchange equivalent numbers, and it form to change progressively or certain gradient arranged.It is formed the control that changes and mainly changes decision by reaction pressure, and the ion exchange resin of low equivalent number has ion or proton conductive preferably, but easily suction in air has inferior mechanical intensity in humidity environment.Therefore, there is core/shell structure polymkeric substance in humidity environment, not only to have preferably ion or proton conductive that better physical strength is arranged again.
Embodiment 1 (TFE and CF
2=CFOCF
2CF (CF
3) OCF
2SO
2The F multipolymer)
In one 2 boosts the power reactor, add 900g deionized water and 30g ammonium perfluorocaprylate (ammonium salt of Perfluorocaprylic Acid) in reactor, vacuumize and fill TFE each three times, the oxygen level that makes the aqueous solution is less than 25ppm, and then band is pressed and is added 10g CF
3CHFCHFCF
2CF
3With 80g CF
2=CFOCF
2CF (CF
3) OCF
2SO
2F, stirring velocity is controlled at 900rpm, water temperature is controlled at 75 ℃ by the chuck heating, then fills TFE and makes reactor pressure reach 300kpa, and the 0.3g persulfuric acid is begun reaction by being dissolved in advance to be pressed in the 100ml deionized water in the reactor, temperature of reaction is constant, TFE pressure maintains 300kpa and compensates the TFE that copolymerization consumes, and reaction continues 60 minutes, and then temperature of reaction is reduced to room temperature, reactor row atmosphere gets multipolymer weight and accounts for 8.3% of emulsion gross weight greatly.It is 66nm that particulate is measured particle with light scattering technique, multipolymer composition F
19NMR directly measures emulsion: contain the TFE of 60%mol in the multipolymer, so the multipolymer equivalents is 600.
Embodiment 2 (TFE and CF
2=CFOCF
2CF (CF
3) OCF
2SO
2The F multipolymer)
With example together step except replacing original 0.3g ammonium persulfate initiator with the 0.1g ammonium persulphate, temperature of reaction is controlled at 90 ℃, TFE pressure maintains 100kpa, reaction continues 5 minutes, then temperature of reaction is reduced to room temperature, and reactor leads to atmosphere, 1.7% of copolymer comprised emulsion gross weight, it is 46nm that particulate is measured particle with light scattering technique, multipolymer composition F
19NMR surveys:: contain the TFE of 30%mol in the multipolymer, so the multipolymer equivalents is 500.
Embodiment 3 (TFE and CF
2=CFOCF
2CF (CF
3) OCF
2SO
2The F copolymerization is made initiator with the perfluor organo-peroxide)
In one 2 boosts the power reactor, add in 900g deionized water, the 30g ammonium perfluorocaprylate reactor, vacuumize and fill TFE three times, the oxygen level that makes the aqueous solution then adds 10gCF with pump less than 25ppm
3CHFCHFCF
2CF
3With 80g CF
2=CFOCF
2CF (CF
3) OCF
2SO
2F.Stirring velocity is controlled at 800rpm, and water temperature, is then filled TFE and made reactor pressure reach 300kpa at 35 ℃ by chuck control heating, and 1g perfluor organic peroxide evocating agent is dissolved in 10g PFO (C in advance
8F
18) join with pump and to begin reaction in the reactor, the perfluor organo-peroxide is with following structure (CF
3CF
2CF
2CF
2CF
2CF
2COO)
2, this compound is made by the Perfluorocaprylic Acid muriate, and temperature of reaction maintains 35 ℃, TFE pressure rises to 600kpa and keeps and compensate the TFE that copolymerization consumes, reaction continues 138 minutes, and then temperature of reaction rises to 150 ℃, and TFE pressure is raised to 2500kpa, continue reaction totally 24 hours again, then temperature of reaction is reduced to room temperature, and reactor leads to atmosphere, 6.8% of copolymer comprised gross weight, it is 128nm that particulate is measured particle with light scattering technique, and the multipolymer composition is surveyed with IR: the multipolymer equivalents is approximately 1100.
Embodiment 4 (TFE, HFP and CF
2=CFOCF
2CF (CF
3) OCF
2SO
2The F tripolymer)
In one 2 boosts the power reactor, add the 900g deionized water and the 30g ammonium perfluorocaprylate is gone in the reactor, vacuumize to fill TFE three times, the oxygen level that makes the aqueous solution is less than 25ppm, and then band is pressed and is added 10gCF
3CHFCHFCF
2CF
3With 80g CF
2=CFOCF
2CF (CF
3) OCF
2SO
2F, stirring velocity is controlled at 800rpm, water temperature is by 75 ℃ of chuck control Heating temperatures, then charge into gaseous mixture, weight is 80% TFE and 20% HFP, make reactor pressure reach 700kpa, the 0.3g ammonium persulphate is dissolved in the 100ml deionized water in advance with beginning reaction in the pump adding reactor, temperature of reaction is controlled at 100 ℃, TFE pressure maintains 700kpa, reaction continues 168 minutes, and then temperature of reaction is reduced to room temperature, and reactor leads to atmosphere, 13.6% of copolymer comprised gross weight, it is 72nm that particulate is measured length with light scattering technique, and the multipolymer composition is surveyed with IR: perfluor sulfonyl monomer mole accounted for 16% greatly during trimer was formed, so the multipolymer equivalents approximately is 1000.
Embodiment 5 (TFE, CF
2=CH
2And CF
2=CFOCF
2CF (CF
3) OCF
2SO
2The F tripolymer)
In one 2 boosts the power reactor, add 900g deionized water and 30g ammonium perfluorocaprylate in reactor, vacuumize and fill TFE three times, the oxygen level that makes the aqueous solution then adds 10gCF with pump less than 25ppm
3CHFCHFCF
2CF
3With 80g CF
2=CFOCF
2CF (CF
3) OCF
2SO
2F, stirring velocity is controlled at 800rpm, and water temperature at 80 ℃, then charges into gaseous mixture by chuck control heating, and 70% is TFE in the 1mol gas, and 30% is CF
2=CH
2, make reactor pressure reach 500kpa.The 0.2g ammonium persulphate be dissolved in advance be pressed in the 100ml deionized water begin in the reactor reaction, temperature of reaction control is constant, TFE pressure maintains 500kpa, reaction continues 58 minutes, then temperature of reaction is reduced to room temperature, and reactor leads to atmosphere, 13.8% of copolymer comprised emulsion gross weight, it is 42nm that particulate is measured particle with light scattering technique, and the multipolymer composition is surveyed with IR: the multipolymer equivalents approximately is 850.
The composition particulate of core/shell or gradient-structure
In following test, prepare the microemulsified fluoropolymer, each micelle has core/shell structure, and shell is made up of a kind of compound structure, and core is made up of another kind of compound structure.The main variation that relies on two step control of polymerization TFE pressure of its preparation.Usually low TFE pressure produces the multipolymer of low equivalent number, and high TFE pressure produces the multipolymer of high equivalent weight number.With low TFE pressure, just 400kpa produces low equivalent and counts particulate as core during the reaction beginning; Then carry out high pressure polymerisation, just use 800kpaTFE pressure, the generation high equivalent weight is counted the multipolymer shell and is covered on the low equivalent multipolymer core.Same explanation is steady as the TFE pressure change, thereby the copolymer structure variation also is progressively.
Embodiment 6 (TFE and CF
2=CFOCF
2CF (CF
3) OCF
2SO
2F interpolymer-its SMIS equivalents of particulate core/shell polymerization is less than shell)
In one 2 boosts the power reactor, add the 900g deionized water and the 30g ammonium perfluorocaprylate is gone in the reactor, vacuumize to fill TFE three times, the oxygen level that makes the aqueous solution is less than 25ppm, and then band is pressed and is added 10gCF
3CHFCHFCF
2CF
3With 80g CF
2=CFOCF
2CF (CF
3) OCF
2SO
2F, stirring velocity is controlled at 800rpm, water temperature heats at 80 ℃ by chuck control, TFE adds in the reactor, make reactor pressure reach 400kpa, the 0.2g persulfuric acid is begun reaction by being dissolved in advance to be pressed in the 100ml deionized water in the reactor, temperature of reaction control is constant, TFE pressure maintains 400kpa and is used for keeping the first step copolyreaction, react after 30 minutes, then TFE pressure rises to 800kpa, and pressure maintains 800kpa and continues 30 minutes, comes stopped reaction by reducing temperature of reaction then, reactor leads to atmosphere, 15.1% of copolymer comprised emulsion gross weight, it is 38nm that particulate is measured particle with light scattering technique, the multipolymer composition is surveyed with IR: particulate core/shell average equivalent number is 1050.Shell copolymers F
19NMR surveys and contains 88%TFE mole number, so multipolymer shell equivalents is 1200.
Embodiment 7 (TFE and CF
2=CFOCF
2CF (CF
3) OCF
2SO2F interpolymer-its SMIS equivalents of particulate core/shell polymerization is greater than shell)
In one 2 boosts the power reactor, add the 900g deionized water and the 30g ammonium perfluorocaprylate is gone in the reactor, vacuumize to fill TFE three times, the oxygen level that makes the aqueous solution is less than 25ppm, and then band is pressed and is added 10gCF
3CHFCHFCF
2CF
3And 80gCF
2=CFOCF
2CF (CF
3) OCF
2SO
2F, stirring velocity is controlled at 800rpm, water temperature is controlled at 75 ℃ by the chuck heating, TFE introduces in the reactor, make reactor pressure reach 700kpa, the 0.2g persulfuric acid is begun reaction by being dissolved in advance to be pressed in the 100ml deionized water in the reactor, temperature of reaction is controlled at 85 ℃, TFE pressure maintains 700kpa and is used for compensating the first step copolyreaction TFE consumption, react after 30 minutes TFE pressure and reduce to 350kpa, and want to keep under the 350kpa pressure 50 minutes, coming stopped reaction by reducing temperature of reaction then, reactor leads to atmosphere, 17.8% of copolymer comprised emulsion gross weight, it is 48nm that particulate is measured particle with light scattering technique, and the multipolymer composition is surveyed with IR: particulate core/shell average equivalent number is 950, shell copolymers F
19NMR surveys: the shell copolymers equivalents is 750.
Embodiment 8 (TFE and tertiary butyl acrylate interpolymer)
In one 2 boosts the power reactor, add the 900g deionized water and the 20g ammonium perfluorocaprylate is gone in the reactor, vacuumize to fill TFE three times, the oxygen level that makes the aqueous solution is less than 25ppm, and then band is pressed and is added 10gCF
3CHFCHFCF
2CF
3With 18g tertiary butyl acrylate, stirring velocity is controlled at 800rpm, water temperature heats at 90 ℃ by chuck control, TFE introduces in the reactor, make reactor pressure reach 400kpa, the 0.5g persulfuric acid is begun reaction by being dissolved in advance to be pressed in the 100ml deionized water in the reactor, temperature of reaction control is constant, TFE pressure maintains the consumption that 400kpa is used for compensating copolyreaction, react after 101 minutes, temperature of reaction is reduced to room temperature, and reactor leads to atmosphere, and getting the solution ultimate production is 1.19kg, solids content is 15.2%, it is 45nm that particulate is measured particle with light scattering technique, and the multipolymer composition is surveyed with DSC: the multipolymer melting peak is 208 ℃, and tertiary butyl acrylate hydrolyzable becomes vinylformic acid (hydroxy-acid group) in the multipolymer.Therefore after the hydrolysis, multipolymer becomes TFE and acrylic copolymer.
Embodiment 9 (TFE and CF2=CFOCF2CF2CF2 COOCH3 interpolymer)
Except replace the original 18g tert-butyl acrylate all the other and embodiment 8 same steps with 60g CF2=CFOCF2CF2CF2COOCH3.At 95 ℃, reaction continues 88 minutes to water temperature by chuck control heating, and getting the solution ultimate production is 1.16kg, and solids content is 9.8%, and it is 58nm that particulate is measured particle with light scattering technique.
Embodiment 10 (TFE, CF2=CFCl and CF2=CFOCF2CF2CF2 COOCH3 tripolymer)
Except using gaseous mixture, promptly 50%mole is TFE in the gas, and 50%mole is that CF2=CFCl replaces outside the original T FE, all the other and example nine same steps.Reaction continues 68 minutes, and the solution ultimate production is 1.28g, and solids content is 11.8%, and it is 66nm that particulate is measured particle with light scattering technique.
Embodiment 11 (TFE and tertiary butyl acrylate superpolymer)
Reaction conditions and embodiment 8 with, but 18g tertiary butyl acrylate substituted by 90g tertiary butyl acrylate, Perfluorocaprylic Acid amine is only used 5g, the nanoemulsions particle diameter is surveyed in sampling before the reaction, measures median size and is about 300nm.In totally 115 minutes reaction times, solids content is 17.2%.
Embodiment 12 system films are used
Get the example 6 gained nanoemulsions of 200ml, put into 190 ℃ in baking oven, 3 hours, drive water and emulsifying agent away, must about 30g resin.With resin tabletting machine pressing mold, the press mold temperature is 230 ℃, pressure is 7Mpa, obtain a film thickness in 15 minutes and be about 1000 μ m, this film is immersed in 1000ml to be contained in 15% potassium hydroxide aqueous solution, be hydrolyzed under 100 ℃ 24 hours, use washed with de-ionized water then 5 times, afterwards the hydrolysis rear film is immersed in 1000ml and contains the 15%HCl aqueous solution, 90 ℃ were carried out acidifying 3 hours, used washed with de-ionized water then 5 times, and so acidification reaction need carry out 3 times repeatedly at least, to make the sulfonate resin film, be beneficial to fuel cell or chlorine industry and use.
Embodiment 13 sulfonate resin solution
The sulfonate film 10g of gained among the embodiment 12 is put into 70g ethanol and 20g deionized water, and put into the 500ml autoclave together, heat to 180 ℃, 8 hours, obtain transparent sulfonate resin solution, solid content 10%, resin median size in solution records with laser scattering technology and is about 176nm.
Embodiment 14 sulfonate resin laminated films
Gained sulfonate resin solution among the embodiment 13 is carried out coating on the expanded microporous polytetra fluoroethylene-EPTEE film, twice, one side once, in baking oven 170 ℃ at every turn, after the oven dry in 5 minutes, then obtain a laminated film, film thickness is about 15 μ m.
Claims (7)
1. the preparation method of an ion exchange fluoro resin, it is characterized in that: this method may further comprise the steps:
(1) in reaction system, adds entry, tensio-active agent and contain the monomer of ion exchange functional groups, stir through suitable mechanical external force, form nanoemulsions, its size droplet diameter is on average at 10～300nm, the tensio-active agent weight percent that adds is 0.1～5%, and the weight percent monomer that contains ion exchange functional groups is 1～30%;
(2) add fluorine-containing from the reaction system gas phase but do not contain the monomer of ion exchange functional groups, this moment, the pressure range of reaction system was 100～2500kPa;
(3) add radical polymerization initiator in reaction system, carry out the free radical high molecular polymerization, obtain ion exchange fluoro resin, temperature of reaction is at 35～150 ℃, and the reaction times was at 5 minutes～24 hours.
2. the preparation method of a kind of ion exchange fluoro resin according to claim 1, it is characterized in that: the tensio-active agent in the said step (1) is a fluorochemical surfactant, the monomer that contains ion exchange functional groups is sulphonyl halogenation group-SO
2Y or ester-COOR, wherein Y is a halogen element, R is the alkyl of carbonatoms from 1-20; In the monomer that contains ion exchange functional groups in the step (1), contain following a kind of monomer at least:
CF
2＝CFOCF
2[CF(CF
3)OCF
2]n-(CF
2)m-SO
2F
CF
2＝CFOCF
2[CF(CF
3)OCF
2]n-(CF
2)m-COOR
N=0,1,2; M=1,2,3; R is the alkyl of 1～15 carbon.
3. the preparation method of a kind of ion exchange fluoro resin according to claim 1 is characterized in that: add the fluorine-containing liquid of inertia in the reaction system of said step (1), the fluorine-containing liquid weight per-cent of the inertia of adding is 1～10%; Wherein the fluorine-containing liquid of inertia is CF
3CHFCHFCF
2CF
3
4. the preparation method of a kind of ion exchange fluoro resin according to claim 1, it is characterized in that: fluorine-containing but monomer that do not contain ion exchange functional groups is a tetrafluoroethylene, R 1216, fluorine-containing alkyl vinyl ether monomer in the said step (2), trifluorochloroethylene, vinylidene.
5. the preparation method of a kind of ion exchange fluoro resin according to claim 1, it is characterized in that: the initiator in the said step (3) is an ammonium persulphate, or (C
7F
15COO)
2, the temperature of reaction in the step (3) is 65～100 ℃.
6. application of ion exchange fluoro resin according to claim 1, it is characterized in that: ion exchange fluoro resin is used to make fuel cell, chlorine industry and gas separation membrane.
7. the application of a kind of ion exchange fluoro resin according to claim 6 is characterized in that: the film forming average thickness range of said resin system is 15～1000 μ m.
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| TWI447151B (en) | 2008-04-28 | 2014-08-01 | Asahi Glass Co Ltd | Production method of fluorine-containing polymer and fluorine-containing ion exchange membrane |
| JP7549973B2 (en) | 2020-05-19 | 2024-09-12 | Ａｇｃエンジニアリング株式会社 | Composite particles, molded body, hollow fiber membrane manufacturing method, ion exchange membrane manufacturing method |
| CN114835842B (en) * | 2022-06-15 | 2024-04-12 | 浙江巨化技术中心有限公司 | Polymerization method of perfluorosulfonyl fluoride resin |
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| CN1513601A (en) | 2004-07-21 |
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