WO2005037879A1

WO2005037879A1 - Method for producing perfluorocarbon polymer

Info

Publication number: WO2005037879A1
Application number: PCT/JP2004/015243
Authority: WO
Inventors: Katsuya Ueno; Nobuyuki Kasahara; Shin Tatematsu
Original assignee: Asahi Glass Company, Limited
Priority date: 2003-10-15
Filing date: 2004-10-15
Publication date: 2005-04-28
Also published as: JPWO2005037879A1

Abstract

Disclosed is a method for producing a perfluorocarbon polymer wherein a perfluorocarbon monomer (which may contain an ether linkage oxygen atom) having an -SO2X group (wherein X represents a fluorine atom or a chlorine atom) and an ethylene double bond and a perhalogeno monomer having a double bond and contains no atom other than carbon atoms, halogen atoms and oxygen atoms are copolymerized in a polymerization medium using a radical polymerization initiator composed of a fluorine-containing compound and a chain-transfer agent composed of hydrogen or a saturated hydrocarbon having 1-2 carbon atoms wherein a part of hydrogen atoms may be substituted by fluorine atoms, and then the resulting is subjected to fluorination. A perfluorocarbon polymer having an -SO2X group which is obtained by such a method has few labile end groups in a molecule and thus is excellent in stability.

Description

Specification

Method for producing perfluorocarbon polymer

Technical field

The present invention relates to a method for producing a sulfonic acid type perfluorocarbon polymer having excellent stability.

Background art

[0002] A perfluorocarbon polymer having a sulfonic acid group (hereinafter, referred to as a sulfonic acid type perfluorocarbon polymer) is widely used as a base material for a cation exchange membrane for salt electrolysis or a diaphragm for a fuel cell. I have. In recent years, fuel cells have attracted attention as a power generation system whose reaction product is water in principle and has almost no adverse effect on the global environment. In particular, polymer electrolyte fuel cells have attracted attention. The reasons are as follows. (1) A highly conductive membrane was developed as a solid polymer electrolyte. (2) By supporting the catalyst used for the gas diffusion electrode layer on carbon, and coating this with an ion-exchange resin, an extremely large activity can be obtained. And as a proton conductive resin for polymer electrolyte fuel cells, sulfonic acid type perfluorocarbon polymer is used because of its heat resistance, chemical resistance, durability, long-term stability, etc. .

[0003] However, it is known that the sulfonic acid type perfluorocarbon polymer deteriorates when exposed to a long-term electrode reaction, and thus it is difficult to maintain the output as a fuel cell. . The cause of the deterioration of the polymer is that at least a part of the terminal group of the polymer main chain is an unstable COOH group or COF group, and the main chain is decomposed from the unstable terminal group in a chain. Can be As a method for stabilizing the terminal group of the polymer, there is a method of fluorinating the polymer (for example, see Patent Document 1). It is difficult to completely stabilize this.

[0004] Patent Document 1: Japanese Patent Publication No. 46-23245 (Claims)

Disclosure of the invention

Problems the invention is trying to solve [0005] In view of the above-mentioned problems of the prior art, the present invention selects a radical initiator and a chain transfer agent, conducts polymerization, and then conducts polymerization so that unstable terminals which are hardly fluorinated are formed in the polymer. It is an object of the present invention to efficiently obtain a sulfonic acid-type perfluorocarbon polymer having a stable terminal group by carrying out the conversion.

Means for solving the problem

[0006] The present invention provides a radical polymerization initiator comprising a fluorine-containing compound, a saturated hydrocarbon having 1 to 12 carbon atoms, which may be partially substituted with a fluorine atom or a chain transfer agent comprising a hydrogen atom. And SO X (X

2 groups are a fluorine atom or a chlorine atom) and a perfluorocarbon monomer having an ethylenic double bond (which may contain an oxygen atom having an ether bond); A method for producing a perfluorocarbon polymer, comprising co-polymerizing at least one perhalogenocarbon monomer containing no atom other than atoms, halogen atoms and oxygen atoms, followed by fluorination treatment. I will provide a.

The invention's effect

[0007] According to the present invention, a polymer having a terminal group which is easily fluorinated is polymerized and further subjected to fluorination treatment, so that the obtained polymer is highly perfluorinated. A perfluorocarbon polymer having a sulfonic acid group obtained by hydrolysis and acidification using this polymer has excellent stability and is suitable for an electrolyte of a polymer electrolyte fuel cell.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] In the method for producing a perfluorocarbon polymer of the present invention, an ethylene having a SO X group

2

A perfluorocarbon monomer having a reactive double bond and at least one perhalogenocarbon monomer having a double bond and containing no atoms other than carbon atoms, halogen atoms and oxygen atoms. Copolymerizes as a monomer of Here, the perfluorocarbon monomer may contain an oxygen atom having an ether bond.

[0009] Examples of the perhalogenocarbon monomer having a double bond and containing no atoms other than a carbon atom, a halogen atom and an oxygen atom include the following. Perfluoro compounds such as tetrafluoroethylene, hexahenoleopropylene, and perphnolerobutynoleethylene Oloflefin. Perfluoronorethone ethers such as perfluoroethyl vinyl ether, perfluoropropylvinyl ether, and perphnolerobutene-norevi-noreeteneole. Cyclic perfluoro compounds such as nofluoro (1,3 diquinol), perfluoro (2,2 dimethyl-1,3 diquinol), perfluoro (2-methylene 4-methyl-1,3-dioxolan). Non-perfluoroolefin monomers such as trifluoroethylene. Fluoroacrylic monomers such as 1,1-dihydroperfluorophenol phthalate acrylate and 1,1-dihydroperfluorophenol methacrylate.

[0010] Above all, perhalogenoolefins such as tetrafluoroethylene, chloro opening trifluoroethylene, hexafluoropropylene, etc., and having an SO X group and having an ethylenic double bond

2

The production method of the present invention in the production of a copolymer with a perfluorocarbon monomer, or a multi-component copolymer of these monomers and at least one perhalogeno monomer having a double bond other than the above-mentioned perhydrogenoolefins The adoption of, has a remarkable effect and is preferred. Among the perhalogeno olefins, tetrafluoroethylene is particularly preferred! /.

[0011] —Perfluorocarbon monomers having a SO X group include CF = CFO (CF CF (

2 2 2

CF) 0) a monomer represented by (CF) SO F (where m is an integer of 2-4, and n is 0

3 n 2 m 2

It is an integer of two. Is preferred. Specifically, CF = CFO (CF) SO F, CF two CF

2 2 2 2 2

0 (CF) SO F, CF = CFOCF CF (CF) 0 (CF) SO F, CF = CFOCF CF (

2 3 2 2 2 3 2 2 2 2 2

CF) 0 (CF) SO F ゝ CF = CFO (CF CF (CF) 0) (CF) SO F ゝ CF = CFO (

3 2 3 2 2 2 3 2 2 2 2 2

CF CF (CF) 0) (CF) SO F and the like.

2 3 2 2 3 2

[0012] In the production method of the present invention, known polymerization methods such as suspension polymerization, solution polymerization, emulsion polymerization, and bulk polymerization can be used as the polymerization method for copolymerizing the above-mentioned monomers without limitation. Is preferred. Since water is used as a polymerization medium in suspension polymerization and emulsion polymerization, it is difficult to stably perform polymerization in which the perfluorocarbon monomer is hardly dissolved in the polymerization medium. In addition, in bulk polymerization, it is difficult to stably perform polymerization in which it is difficult to efficiently remove heat generated by polymerization.

[0013] As a polymerization medium in the case of solution polymerization, a chain transfer coefficient is small! A fluorine-containing organic solvent is preferable. In particular, perfluorocarbons having 3 to 10 carbon atoms, hydrofluorocarbons having 3 to 10 carbon atoms, hide-opening fluorocarbons having 3 to 10 carbon atoms, and 3 to 10 carbon atoms A group consisting of black and white fluorocarbons. These halogenocarbons may preferably have any of a linear, branched or cyclic structure and may contain an etheric oxygen atom in the molecule, but are preferably saturated compounds.

[0014] Specific polymerization media include the following. Examples of the perfluorocarbon include perfluorocyclobutane, perfluorohexane, perfluoro (dipropyl ether), perfluorocyclohexane, perfluoro (2-butyltetrahydrofuran) and the like. It is preferable that the number of fluorine atoms in the molecule is larger than the number of hydrogen atoms in the fluoridated carbon. CH OC F OC F F

3 2 5, CH

3 3 7, C F H

5 10 2, C F H

6 13, C

6 12

H and the like. Hydrochloride Fluorocarbon has less than 3 hydrogen atoms

2

CHC1FCF CF C1 and the like. With black mouth fluorocarbon

twenty two

Examples thereof include 1,1,2-trifluorotrifluoroethane.

[0015] The amount of the polymerization medium used is preferably 10 to 90% by volume relative to the volume of the polymerization reactor, and more preferably 30 to 70%. When the amount of the polymerization medium is small, the amount of the perfluorocarbon monomer that can be dissolved in the polymerization medium is also small, and the amount of the obtained polymer is small, so that the production efficiency is low and industrially disadvantageous. On the other hand, if the amount of the polymerization medium is too large, it is difficult to uniformly stir the whole. In the case of suspension polymerization and emulsion polymerization, a substantial polymerization medium includes water.

[0016] As the chain transfer agent in the present invention, hydrogen, a saturated hydrocarbon having 112 carbon atoms, a fluorocarbon having a saturated hydride having 112 carbon atoms and the like are used. Specifically preferred are methane, ethane and CH F

2 2, CH F

3, CH F

3, CH CF H

32, CF CH F etc.

3 2

. With the use of this chain transfer agent, the terminal group has an SO X group that can be easily fluorinated.

2

A perfluorocarbon polymer is formed. In addition, the molecular weight of the polymer obtained by using the chain transfer agent can be controlled. Among the chain transfer agents, methane is particularly useful because it has a high chain transfer property, it is easy to control the molecular weight of the polymer, and the terminal group of the polymer is CH.

Three

It is preferred because it can be easily fluorinated and converted to a -CF group.

Three

[0017] The amount of the chain transfer agent used is such that the perfluorocarbon monomer having a SO X group is

2

The mass ratio is preferably 0.1 to 50% based on the total amount of the mixture with the halogenocarbon monomer. If the amount of the chain transfer agent is too small, it is difficult to control the molecular weight of the polymer by the chain transfer. It is difficult. If the amount of the chain transfer agent is too large, the production amount of the perfluorocarbon monomer and the perhalogenocarbon monomer is reduced, so that the production efficiency is lowered and this is industrially disadvantageous. The optimum amount of the chain transfer agent varies depending on the type of the chain transfer agent used, and 0.1 to 10% is preferable for methane, and 10 to 50% is preferable for CHF.

twenty two

As the polymerization initiator in the present invention, a radical polymerization initiator which also has a fluorine-containing compound power is employed, but this polymerization initiator is preferable because it forms a copolymer having a stable terminal group. In particular, a compound represented by any of the following formulas 17 is preferable. Wherein R ⁿ is a perfluoroalkyl group having 11 to 10 carbon atoms, R ⁱ² and R ⁱ³ are polyfluoroalkyl groups having 3 or more carbon atoms, X is a halogen atom, and R ^M Is a fluorine atom or a perfluoroalkyl group having 12 to 12 carbon atoms, and nl, n2 and n3 are each independently an integer of 1 or more.

[0019] [Formula 1] Formula 1

Equation 2

Equation 3

Equation 4

Equation 5

Equation 6

Equation 7

Among them, bis (fluoroacyl) peroxides represented by the formula 1 are preferred! / ヽ. Specifically, (CF COO), (CF CF COO), (CF CF CF COO), (HCF CF COO

3 2 3 2 2 3 2 2 2 2 2

O), (HCF CF CF COO) and the like.

2 2 2 2 2

[0021] The amount of the polymerization initiator to be used is preferably 0.01-1% by mass with respect to the mass of the perhalogenocarbon monomer, and more preferably 0.01-0.5%. If the amount of the polymerization initiator is too small, the molecular weight of the produced polymer becomes too large, resulting in poor processability and the possibility of using as an electrolyte material. If the amount of the polymerization initiator is too large, the molecular weight of the generated polymer will be reduced, for example, the electrolyte material of a polymer electrolyte fuel cell When used as a material, there is a possibility that strength sufficient for use may not be obtained.

[0022] The polymerization temperature in the present invention is selected based on the 10-hour half-life temperature of the polymerization initiator in the solvent used (the temperature at which the amount of the initiator becomes half after 10 hours from the start of polymerization). 75 ° C or lower is preferable. If the temperature is higher than 75 ° C., not only does the economy become poor, but also the number of generated COF terminal groups tends to increase.

[0023] The polymerization pressure in the present invention is preferably 0.1-lOMPa. If the polymerization pressure is too low, the content of COF terminal groups in the obtained polymer tends to increase, and if the polymerization pressure is too high, it is not preferable in terms of production equipment. More preferably, 0.3 to 5 MPa is employed.

[0024] In the present invention, a specific polymerization initiator and a specific chain transfer agent are selected respectively, so that the polymer obtained by polymerization has a terminal group which is easily fluorinated and a terminal group which is perfluorinated, Few unstable terminal groups. Examples of the terminal group which is easily fluorinated include -CFH, -CFH, -CH and the like. Unstable end groups include COF, -COOH

2 2 3

, One CF = CF, -CH OH. COF, one COOH, -CH OH decomposes

2 2 2

Very unstable, -CF = CF easily becomes -COOH in air.

2

[0025] In the present invention, after polymerizing a polymer having an easily fluorinated terminal group as described above, the obtained polymer is subjected to a fluorination treatment. The method of the fluorination treatment is not particularly limited, and a known method of replacing a hydrogen atom with a fluorine atom is employed. From the viewpoint of reaction efficiency, a fluorination treatment using a fluorine gas is preferably employed. The method of fluorination treatment with fluorine gas involves suspending or dissolving the fluorinated copolymer in a solvent such as carbon tetrachloride, black fluorocarbon, and perfluorocarbon having low reactivity with fluorine.

And a gas-Z method in which the polymer is directly fluorinated with fluorine gas diluted with an inert gas, if necessary, or a gas-Z solid method in which the polymer is directly exposed to fluorine gas and fluorinated. In either case, it is preferable to use a reactor made of a material having corrosion resistance to fluorine gas to improve the contact between the polymer to be fluorinated and the fluorine gas. Specifically, in the gas-Z liquid method, the reaction is preferably performed with stirring or vibration. Q Z-solid method, soful with X group

2

It is preferable to carry out the reaction by increasing the surface area of the fluorocarbon polymer exposed to fluorine gas.

[0026] As a reaction method, a predetermined concentration of fluorine is placed in a reactor in which the polymer to be fluorinated is present. A circulating method in which a raw gas is circulated to perform a fluorination treatment, a Notch method in which a predetermined concentration of a fluorinated gas is sealed and fluorinated, and the like are exemplified.

[0027] Thus, the polymer obtained by the method of the present invention is highly fluorinated. By subjecting this polymer to hydrolysis and acidification, the SO X group becomes a sulfonic acid group.

2

(One SOH group) and the resulting sulfonic acid type perfluorocarbon polymer is

Three

Excellent qualitative. A polymer electrolyte fuel cell using this sulfonic acid type perfluorocarbon polymer as an electrolyte material has excellent durability because the electrolyte material has excellent stability.

The sulfonic acid-type perfluorocarbon polymer electrolyte material according to the present invention has a number of COF end groups of preferably 20 or less per 10 ⁶ carbon atoms, more preferably 16 or less. .

Example

[0028] Examples and comparative examples are shown below to explain the present invention in further detail, but the present invention is not limited thereto.

In this example, quantification of unstable terminal groups was performed as follows. That is, the polymer having a SO F group obtained in this example and the number of unstable terminal groups for comparison were

2

Known standard (CF = CF / CF = CFOCF CF (CF) OCF CF SO F copolymer)

2 2 2 2 3 2 2 2

Were melted at a temperature of about 250 ° C., and then cooled under pressure to produce films each having a thickness of about 0.3 mm. The difference spectrum was measured by FT-IR. Then, was calculated by the following equation, the number of unstable terminal groups of the carbon atoms 10 ⁶ equivalents have enough.

[0029] N = f X A / t

N: the number of unstable terminal groups (number Z carbon atoms 10 ^6), A: absorbance, f: factor, t: thickness of the film (mm).

However, the value in Table 1 below was used for the coefficient f. The numerical value of f is, for example, ^ Journal of Fluorine Chemistry 95 (1999) 71-84.

[Table 1] Unstable end group Absorption frequency (cm- ¹ ) coefficient

One COF 1883 2 1 5

-COOH 1813 230

-CH ₂ OH 3648 4600

— CF = CF ₂ 1 784 455

[Example 1]

In a 1L stainless steel reactor equipped with a stirrer,

219.4g CF = CFOCF CF (CF) 0 (CF) SO F (hereafter, P

2 2 3 2 2 2

602. Og was added and the inside was evacuated. Then, CF H (hereinafter referred to as a chain transfer agent)

2 2 Below, R-32) was charged with 64. Og, and tetrafluoroethylene (hereinafter referred to as TFE) was charged at an internal temperature of 40 ° C until the pressure reached 1.30 MPaG. Then (FCF as initiator

2

(CF CF COO) at a concentration of 3% by mass in CHFC1CF CF C1

2 2 2 2 2

And polymerization was started. During the polymerization, the initiator solution was charged intermittently, and a total of 45 mL was charged. Since the pressure decreases as the polymerization progresses, TFE was continuously charged so that the pressure became constant. When the amount of TFE charged later reached 150 g, the internal temperature was cooled to 10 ° C, unreacted TFE was released, and the pressure vessel was opened.

[0032] In this way, a slurry-like content (polymer) was obtained in the pressure vessel. The methanol was put therein and stirred to precipitate the polymer by coagulation. The polymer was dried at 80 ° C. for 10 hours to obtain 119.lg of a white TFE-PSVE copolymer.

Next, 100 g of the copolymer was put into a Hastelloy reactor having an internal volume of 200 mL in order to fluorinate, and the inside of the reactor was sufficiently degassed. Introduced up to 0.3MPaG. Next, the reactor was placed in a 10 ° C oil bath, and the temperature was slowly raised to 180 ° C. After performing the reaction at 180 ° C for 4 hours, the inside was sufficiently purged with nitrogen, and 118.3 g of a white powder was taken out as a reaction product.

[0034] The white powder was a film with 240 ° C was measured IR and, as the unstable terminal groups, COF groups included 10 13 ⁶ per carbon atom, COOH group, CH OH group

2 CF = CF groups was 1 or less per 10 ⁶ carbon atoms, respectively.

2

Example 2

Performed except that the charged amount of R-32 was 46.3 g and the pressure of the reaction tank was 1.30 MPaG Polymerization was carried out in the same manner as in Example 1 to obtain 80.9 g of a TFE-PSVE copolymer. The obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 77.4 g of a white TFE-PSVE copolymer. The copolymer unstable terminal of the - COF group included 10 11 ⁶ per carbon atom, COOH group, -CH OH group, -CF = CF group carbon atom 10 ⁶ cells per

twenty two

It was less than pieces.

[Example 3]

Polymerization was carried out in the same manner as in Example 1 except that the charged amount of R-32 was 25.Og and the pressure in the reaction tank was 1.1 lOMPaG, to obtain 112.lg of a TFE-PSVE copolymer. The obtained TFE-PSVE copolymer was subjected to a fluorination treatment in the same manner as in Example 1 to obtain 11.3 g of a white TFE-PSVE copolymer. The copolymer contains 10 unstable terminal COF groups per 10 ⁶ carbon atoms, and COOH groups, -CH OH groups, -CF = CF groups per 10 ⁶ carbon atoms.

twenty two

It was less than one.

[Example 4]

Except that 1.53 g of CH was charged instead of CH F and the pressure of the reaction tank was set to 0.50 MPa

2 2 4

Polymerization was carried out in the same manner as in Example 1 to obtain 79.6 g of a TFE-PSVE copolymer. The obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 76.9 g of a white TFE-PSVE copolymer. The copolymer COF groups as unstable terminal to have been included 10 8 ⁶ per carbon atom, COOH group, -CH OH group, -CF = CF group carbon atom 10 ⁶ cells per

twenty two

It was less than pieces.

[Example 5]

75 CF Og was charged instead of CH F, and the pressure in the reaction tank was 0.90 MPa

2 2 3 2

Polymerization was carried out in the same manner as in Example 1 except for the above, to obtain 66.3 g of a TFE-PSVE copolymer. The obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 66.3 g of a white TFE-PSVE copolymer. The copolymer COF groups as unstable terminal to have been included 10 16 ⁶ per carbon atom, COOH group, -CH OH group, CF = CF2 group is carbon atom 10

2

^It was less than one out of every ^six .

[Example 6]

150. Og of CF CH F and 150.4g of R-113

2 2 3 2 Polymerization was carried out in the same manner as in Example 1 except that the charged amount of SVE was set to 512.3 g and the pressure of the reaction vessel was set to 0.80 MPa, to obtain 120.8 g of a TFE-PSVE copolymer. The obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 115.8 g of a white TFE-PSVE copolymer. The copolymer COF groups as unstable terminal to have been included 10 11 ⁶ per carbon atom, COOH group, -CH OH group, -CF = CF group carbon atom 10 ⁶ cells per

twenty two

It was less than pieces.

[Comparative Example 1]

The procedure was carried out except that R-32 was not used as a chain transfer agent, 223.09 mg of azoisobutyl mouth-tolyl was used as a polymerization initiator and 146.8 g of CHFC1CF CF C1 was used as a polymerization solvent.

twenty two

In the same manner as in Example 1, a white TFE-PSVE copolymer 105. Og was obtained. The obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 101.2 g of a white TFE-PSVE copolymer. The copolymer COF groups as unstable terminal to have been included 48 10 ⁶ per carbon atom, COOH group, CH OH group, -CF = CF group carbon atom 10 ⁶ Core

twenty two

It was less than one.

Industrial applicability

[0041] The perfluorocarbon polymer obtained by the present invention is highly fluorinated and has a small amount of unstable terminal groups. The sulfonic acid-type perfluorocarbon polymer obtained by hydrolyzing and acidifying this polymer is stable, and when used as an electrolyte for a polymer electrolyte fuel cell, for example, a solid polymer-type fuel having excellent durability can be obtained. A battery is obtained.

Claims

The scope of the claims

[1] Using a radical polymerization initiator having a fluorine-containing compound power and a saturated hydrocarbon having 112 carbon atoms which may be partially replaced by a fluorine atom or a chain transfer agent having a hydrogen power, In the polymerization medium, having SO X group (X is a fluorine atom or chlorine atom)

2

A perfluorocarbon monomer having a double bond (which may contain an etheric oxygen atom) and a perhalogeno having a double bond and containing no atoms other than carbon, halogen and oxygen atoms A method for producing a perfluorocarbon polymer, comprising copolymerizing at least one type of carbon monomer and then subjecting it to a fluorination treatment.

[2] The method for producing a perfluorocarbon polymer according to claim 1, wherein the perhalogenocarbon monomer is perhalogenoolefin.

[3] The perfluorocarbon monomer is CF = CFO (CF CF (CF) 0) (CF) SO

2 2 3 n 2 m 2

3. A monomer represented by F (wherein m is an integer of 2-4 and n is an integer of 0-2), and the perhalogenoolefin is tetrafluoroethylene. 3. The method for producing a perfluorocarbon polymer according to item 1.

[4] The method for producing a perfluorocarbon polymer according to any one of claims 13 to 13, wherein the copolymerization is carried out by solution polymerization.

[5] Perfluorocarbon with 3-10 carbon atoms, Fluorocarbon with 3-10 carbon atoms

5. The perfluoro according to claim 4, wherein at least one selected from the group consisting of a fluorinated fluorofluorocarbon having 3 to 10 carbon atoms and a chlorofluorocarbon having 3 to 10 carbon atoms is used as the polymerization medium. A method for producing a carbon polymer.

6. The method according to claim 15, wherein the amount of the chain transfer agent is 0.1 to 50% by mass relative to the total amount of the perfluorocarbon monomer and the perhalogenocarbon monomer. A method for producing a perfluorocarbon polymer.

[7] The radical polymerization initiator is a compound represented by the formula (17), wherein R ⁿ is a perfluoroalkyl group having a carbon number of ^110, and R ⁱ² and R ⁱ³ Is a polyfluoroalkyl group having 3 or more carbon atoms, X is a halogen atom, R ^M is a fluorine atom or a perfluoroalkyl group of carbon, and nl, n2, and n3 are each independently 1 The group transfer is at least one selected from the group consisting of methane and methane. Tan, CH F

2 2, CH F

3.Claim 1 which is CH CF H or CF CH F

3. The method for producing a perfluorocarbon polymer according to any one of (3), (2), (3) and (6).

[Formula 1] Equation 1 Equation 2 Equation 3

Equation 4

Equation 5

Equation 6

Equation 7

[8] A method for producing an electrolyte material for a solid polymer fuel cell comprising a perfluorocarbon polymer having a sulfonic acid group, comprising the steps of:

A method for producing an electrolyte material, comprising producing a perfluorocarbon polymer having two groups, followed by hydrolysis and acidification.

[9] A perfluorocarbon monomer having an SO H group and an ethylenic double bond (e)

Three

A monomer unit based on a mono-bonded oxygen atom) and a double bond. Having and a carbon atom,

Consists polymerization strength and a monomer unit based on perhalogenoacetic carbon monomer a solid polymer fuel electrolyte material for a battery, the electrolyte in the number of COF terminal groups, characterized in that it is 20 or less per 10 ⁶ carbon atoms material.