JP2017025242A - Fluorosulfonyl group-containing monomer, fluorosulfonyl group polymer, sulfonic acid group-containing polymer, liquid composition, membrane electrode conjugate and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorosulfonyl group-containing monomer capable of providing a sulfonic acid group-containing polymer high in ion exchange capacity and being manufactured with less synthetic step, a fluorosulfonyl group-containing polymer using the same as a raw material, a sulfonic acid group-containing polymer, a liquid composition, a membrane electrode conjugate and a manufacturing method therefor.SOLUTION: There is provided a fluorosulfonyl group-containing monomer represented by the following formula (m1), in which n:0 or 1, R:perfluoroalkylene group or the like, X:a fluorine atom or a fluorosulfonyl group.SELECTED DRAWING: None

Description

  The present invention relates to a fluorosulfonyl group-containing monomer, a fluorosulfonyl group-containing polymer, a sulfonic acid group-containing polymer, a liquid composition, a membrane electrode assembly, and methods for producing them.

  Polymers contained in catalyst layers, solid polymer electrolyte membranes, cation exchange membranes used for alkaline chloride electrolysis, etc. in membrane electrode assemblies for polymer electrolyte fuel cells are desired to have a high ion exchange capacity. . When the ion exchange capacity is high, the ion conductivity is improved, and therefore, practical advantages such as improvement in power generation performance of the polymer electrolyte fuel cell and reduction in overvoltage in alkali chloride electrolysis can be expected.

As a polymer having a high ion exchange capacity, a fluorosulfonyl group of a fluorosulfonyl group-containing polymer having a structural unit derived from a fluorosulfonyl group-containing monomer represented by the following formula (m2) and a structural unit derived from tetrafluoroethylene ( A sulfonic acid group-containing polymer obtained by converting —SO ₂ F) into a sulfonic acid group (—SO ₃ H) has been proposed (Patent Document 1).

However, m is 0 or 1, and R ^F1 is a single bond, a linear perfluoroalkylene group having 1 to 6 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of the perfluoroalkylene group. R ^F2 is a linear perfluoroalkylene group having 1 to 6 carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of the perfluoroalkylene group.

Japanese Patent No. 5141251

However, in manufacturing the fluorosulfonyl group-containing monomer represented by the formula (m2) is synthesized until a _{CF 2 = CFCF 2 OCF 2 CF} 2 SO 2 F , which is the starting material in Example 2 of Patent Document 1 In addition to the need for two steps (such as US Pat. No. 4,273,729), in Example 2 of Patent Document 1, further synthesis is performed from CF ₂ = CFCF ₂ OCF ₂ CF ₂ SO ₂ F to the target fluorosulfonyl group-containing monomer. There are 4 steps, 6 steps in total. Therefore, the fluorosulfonyl group-containing monomer represented by the formula (m2) takes time to manufacture.

  The present invention can provide a sulfonic acid group-containing polymer having a high ion exchange capacity and a fluorosulfonyl group-containing monomer that can be produced with few synthesis steps, and a sulfonyl group-containing polymer having a high ion exchange capacity. Provided are a group-containing polymer, a sulfonic acid group-containing polymer capable of increasing ion exchange capacity, a liquid composition capable of forming a film containing a polymer having high ion exchange capacity, a membrane electrode assembly excellent in power generation performance, and a method for producing them.

ただし、ｎは０または１であり、Ｒ^ｆ１はペルフルオロアルキレン基、またはペルフルオロアルキレン基の炭素−炭素原子間にエーテル性酸素原子を有する基であり、Ｘはフッ素原子またはフルオロスルホニル基である。
［２］前記Ｘがフルオロスルホニル基である、［１］のフルオロスルホニル基含有モノマー。
［３］前記ｎが１である、［１］または［２］のフルオロスルホニル基含有モノマー。
［４］前記Ｒ^ｆ１が−ＣＦ_２ＣＦ_２−である、［１］〜［３］のいずれかのフルオロスルホニル基含有モノマー。
［５］前記［１］〜［４］のいずれかのフルオロスルホニル基含有モノマーに由来する構成単位を有する、フルオロスルホニル基含有ポリマー。
［６］テトラフルオロエチレンに由来する構成単位をさらに有する、［５］のフルオロスルホニル基含有ポリマー。
［７］前記［５］または［６］のフルオロスルホニル基含有ポリマーのフルオロスルホニル基をスルホン酸基に変換した、スルホン酸基含有ポリマー。
［８］前記［７］のスルホン酸基含有ポリマーと、液状媒体とを含む、液状組成物。
［９］触媒層を有するアノードと、触媒層を有するカソードと、前記アノードと前記カソードとの間に配置された固体高分子電解質膜とを備えた固体高分子形燃料電池用膜電極接合体であって、前記カソードの触媒層、前記アノードの触媒層および前記固体高分子電解質膜からなる群から選ばれる少なくとも１つが、［７］のスルホン酸基含有ポリマーを含む、膜電極接合体。
［１０］下式（１４）で表される化合物とペルフルオロアリル化剤とをあらかじめ混合した液にフッ化物塩を添加して下式（ｍ１）で表される化合物を得る、フルオロスルホニル基含有モノマーの製造方法。

ただし、ｎは０または１であり、Ｒ^ｆ１はペルフルオロアルキレン基、またはペルフルオロアルキレン基の炭素−炭素原子間にエーテル性酸素原子を有する基であり、Ｘはフッ素原子またはフルオロスルホニル基である。
［１１］前記ペルフルオロアリル化剤が、下式（１２）で表される化合物である、［１０］のフルオロスルホニル基含有モノマーの製造方法。
ＣＦ_２＝ＣＦＣＦ_２−Ｚ （１２）
ただし、Ｚは−ＯＳＯ_２Ｆ、−ＯＳＯ_２Ｒ^ｆ２、塩素原子、臭素原子またはヨウ素原子であり、Ｒ^ｆ２はペルフルオロアルキル基である。
［１２］前記Ｘがフルオロスルホニル基である、［１０］または［１１］のフルオロスルホニル基含有モノマーの製造方法。
［１３］前記ｎが１である、［１０］〜［１２］のいずれかのフルオロスルホニル基含有モノマーの製造方法。
［１４］前記Ｒ^ｆ１が−ＣＦ_２ＣＦ_２−である、［１０］〜［１３］のいずれかのフルオロスルホニル基含有モノマーの製造方法。
［１５］前記［１０］〜［１４］のいずれかの製造方法によってフルオロスルホニル基含有モノマーを製造し、該フルオロスルホニル基含有モノマーを含むモノマー成分を重合して前記フルオロスルホニル基含有モノマーに由来する構成単位を有するフルオロスルホニル基含有ポリマーを得る、フルオロスルホニル基含有ポリマーの製造方法。
［１６］前記モノマー成分が、テトラフルオロエチレンをさらに含む、［１５］のフルオロスルホニル基含有ポリマーの製造方法。
［１７］前記［１５］または［１６］の製造方法によってフルオロスルホニル基含有ポリマーを製造し、該フルオロスルホニル基含有ポリマーのフルオロスルホニル基をスルホン酸基に変換することによってスルホン酸基含有ポリマーを得る、スルホン酸基含有ポリマーの製造方法。
［１８］前記［１７］の製造方法によってスルホン酸基含有ポリマーを製造し、該スルホン酸基含有ポリマーと、液状媒体とを混合して液状組成物を得る、液状組成物の製造方法。
［１９］触媒層を有するアノードと、触媒層を有するカソードと、前記アノードと前記カソードとの間に配置された固体高分子電解質膜とを備えた固体高分子形燃料電池用膜電極接合体を製造する方法であって、［１８］の製造方法によって液状組成物を製造し、該液状組成物と触媒とを混合して触媒層形成用塗工液を調製し、該塗工液を用いて前記カソードおよび前記アノードのいずれか一方または両方の触媒層を形成する、膜電極接合体の製造方法。
［２０］触媒層を有するアノードと、触媒層を有するカソードと、前記アノードと前記カソードとの間に配置された固体高分子電解質膜とを備えた固体高分子形燃料電池用膜電極接合体を製造する方法であって、［１８］の製造方法によって液状組成物を製造し、該液状組成物を用いて前記固体高分子電解質膜を形成する、膜電極接合体の製造方法。 The present invention has the following aspects.
[1] A fluorosulfonyl group-containing monomer represented by the following formula (m1).

However, n is 0 or 1, R ^f1 is a perfluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of the perfluoroalkylene group, and X is a fluorine atom or a fluorosulfonyl group.
[2] The fluorosulfonyl group-containing monomer of [1], wherein X is a fluorosulfonyl group.
[3] The fluorosulfonyl group-containing monomer of [1] or [2], wherein n is 1.
[4] The fluorosulfonyl group-containing monomer according to any one of [1] to [3], wherein R ^f1 is —CF ₂ CF ₂ —.
[5] A fluorosulfonyl group-containing polymer having a structural unit derived from the fluorosulfonyl group-containing monomer of any one of [1] to [4].
[6] The fluorosulfonyl group-containing polymer according to [5], further comprising a structural unit derived from tetrafluoroethylene.
[7] A sulfonic acid group-containing polymer obtained by converting the fluorosulfonyl group of the fluorosulfonyl group-containing polymer of [5] or [6] into a sulfonic acid group.
[8] A liquid composition comprising the sulfonic acid group-containing polymer of [7] and a liquid medium.
[9] A membrane electrode assembly for a polymer electrolyte fuel cell comprising an anode having a catalyst layer, a cathode having a catalyst layer, and a polymer electrolyte membrane disposed between the anode and the cathode. A membrane electrode assembly, wherein at least one selected from the group consisting of the cathode catalyst layer, the anode catalyst layer, and the solid polymer electrolyte membrane comprises the sulfonic acid group-containing polymer of [7].
[10] Fluorosulfonyl group-containing monomer for obtaining a compound represented by the following formula (m1) by adding a fluoride salt to a liquid obtained by mixing a compound represented by the following formula (14) and a perfluoroallylating agent in advance Manufacturing method.

However, n is 0 or 1, R ^f1 is a perfluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of the perfluoroalkylene group, and X is a fluorine atom or a fluorosulfonyl group.
[11] The method for producing a fluorosulfonyl group-containing monomer of [10], wherein the perfluoroallylating agent is a compound represented by the following formula (12).
_{CF 2 = CFCF 2 -Z (12} )
However, Z is ^{_{-OSO 2 F, -OSO 2 R f2}} , a chlorine atom, a bromine atom or an iodine ^{atom, R f2} is a perfluoroalkyl group.
[12] The method for producing a fluorosulfonyl group-containing monomer of [10] or [11], wherein X is a fluorosulfonyl group.
[13] The method for producing a fluorosulfonyl group-containing monomer according to any one of [10] to [12], wherein n is 1.
[14] The method for producing a fluorosulfonyl group-containing monomer according to any one of [10] to [13], wherein R ^f1 is —CF ₂ CF ₂ —.
[15] A fluorosulfonyl group-containing monomer is produced by the production method of any one of [10] to [14], and a monomer component containing the fluorosulfonyl group-containing monomer is polymerized to derive from the fluorosulfonyl group-containing monomer. A method for producing a fluorosulfonyl group-containing polymer, wherein a fluorosulfonyl group-containing polymer having a structural unit is obtained.
[16] The method for producing a fluorosulfonyl group-containing polymer according to [15], wherein the monomer component further contains tetrafluoroethylene.
[17] A fluorosulfonyl group-containing polymer is produced by the production method of [15] or [16], and the fluorosulfonyl group of the fluorosulfonyl group-containing polymer is converted into a sulfonic acid group to obtain a sulfonic acid group-containing polymer. The manufacturing method of a sulfonic acid group containing polymer.
[18] A method for producing a liquid composition, comprising producing a sulfonic acid group-containing polymer by the production method of [17], and mixing the sulfonic acid group-containing polymer and a liquid medium to obtain a liquid composition.
[19] A membrane electrode assembly for a polymer electrolyte fuel cell comprising an anode having a catalyst layer, a cathode having a catalyst layer, and a polymer electrolyte membrane disposed between the anode and the cathode A liquid composition is produced by the production method of [18], a liquid composition and a catalyst are mixed to prepare a coating solution for forming a catalyst layer, and the coating solution is used. A method for producing a membrane electrode assembly, wherein the catalyst layer of any one or both of the cathode and the anode is formed.
[20] A membrane electrode assembly for a polymer electrolyte fuel cell, comprising: an anode having a catalyst layer; a cathode having a catalyst layer; and a solid polymer electrolyte membrane disposed between the anode and the cathode. A method for producing a membrane / electrode assembly, wherein a liquid composition is produced by the production method of [18], and the solid polymer electrolyte membrane is formed using the liquid composition.

According to the fluorosulfonyl group-containing monomer of the present invention, a sulfonic acid group-containing polymer having a high ion exchange capacity can be obtained. Further, the fluorosulfonyl group-containing monomer of the present invention can be produced with few synthesis steps.
According to the fluorosulfonyl group-containing polymer of the present invention, a sulfonic acid group-containing polymer having a high ion exchange capacity can be obtained.
The sulfonic acid group-containing polymer of the present invention can increase the ion exchange capacity.
According to the liquid composition of the present invention, a film containing a polymer having a high ion exchange capacity can be formed.
The membrane electrode assembly of the present invention is excellent in power generation performance.
According to the method for producing a fluorosulfonyl group-containing monomer of the present invention, a fluorosulfonyl group-containing monomer capable of obtaining a sulfonic acid group-containing polymer having a high ion exchange capacity can be produced with few synthesis steps.
According to the method for producing a fluorosulfonyl group-containing polymer of the present invention, a fluorosulfonyl group-containing polymer capable of obtaining a sulfonic acid group-containing polymer having a high ion exchange capacity can be produced.
According to the method for producing a sulfonic acid group-containing polymer of the present invention, a sulfonic acid group-containing polymer having a high ion exchange capacity can be produced.
According to the method for producing a liquid composition of the present invention, a liquid composition capable of forming a film containing a polymer having a high ion exchange capacity can be produced.
According to the method for producing a membrane electrode assembly of the present invention, a membrane electrode assembly excellent in power generation performance can be produced.

It is sectional drawing which shows an example of the membrane electrode assembly of this invention. It is sectional drawing which shows the other example of the membrane electrode assembly of this invention.

In the present specification, a compound represented by the formula (m1) is referred to as a compound (m1). The same applies to compounds represented by other formulas.
In this specification, the structural unit represented by the formula (u1) is referred to as a structural unit (u1). The structural units represented by other formulas are also described in the same manner.
The following definitions of terms apply throughout this specification and the claims.
“Polymer” means a compound having a structure composed of a plurality of structural units.
“Structural unit” means a unit derived from a monomer formed by polymerization of the monomer. The structural unit may be a unit directly formed by a polymerization reaction of monomers, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
“Monomer” means a compound having a polymerization-reactive carbon-carbon double bond.
The “perfluoroallylating agent” means a compound that can introduce a structure represented by CF ₂ ═CFCF ₂ — into another compound.

<Compound (m1)>
The fluorosulfonyl group-containing monomer of the present invention is the compound (m1).

  n is 0 or 1, and 1 is preferable from the viewpoint that synthesis in a shorter step is possible.

R ^f1 is a perfluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of the perfluoroalkylene group.
The _{^{R f1, -CF 2 CF 2 -}} , - CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 CF 2 CF 2 CF 2 -, - CF 2 CF (CF 3) OCF 2 CF 2 CF _2- , —CF ₂ CF (CF ₃ ) — and the like are mentioned, and —CF ₂ CF ₂ — is preferable from the viewpoint that synthesis in a shorter step is possible and higher ion exchange capacity is obtained.

  X is a fluorine atom or a fluorosulfonyl group, and a fluorosulfonyl group is preferable because a polymer having a high ion exchange capacity can be obtained.

  The compound (m1) is preferably a compound (m1-1) to a compound (m1-10) from the viewpoint of availability of raw materials, ease of distillation purification of the compound (m1), and molecular weight of the compound (m1). The compound (m1-1) is more preferable. However, x is an integer of 1 or more.

<Method for Producing Compound (m1)>
The method for producing the compound (m1) is a method for obtaining the compound (m1) by adding a fluoride salt to a liquid in which the compound (14) and the perfluoroallylating agent are mixed in advance.

However, n, R ^f1 and X are as described above, and preferred forms are also the same. MF is a fluoride salt.
In the reaction of a conventional compound having a perfluoro-β-sultone skeleton and a perfluoroallylating agent, first, a compound having a perfluoro-β-sultone skeleton and a fluoride salt (MF) are mixed to obtain perfluoro-β-sultone. skeleton by ring-opening a by _{MO-CF 2 -CF (SO 2} F) - and is, then, was added perfluoroallyl agent. However, when this procedure is applied to the reaction between the compound (14) and the perfluoroallylating agent, the MO—CF ₂ —CF (SO ₂ F) — structure is decomposed, and the compound (m1) cannot be obtained at all. In the present invention, compound (m1) can be obtained by adding a fluoride salt to a liquid in which compound (14) and a perfluoroallylating agent are mixed in advance.

The liquid in which the compound (14) and the perfluoroallylating agent are mixed preferably contains an aprotic polar solvent.
Examples of the aprotic polar solvent include monoglyme, diglyme, triglyme, tetraglyme, acetonitrile, propionitrile, adiponitrile, benzonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, nitroethane and the like.

Examples of the fluoride salt include potassium fluoride, cesium fluoride, silver fluoride, quaternary ammonium fluoride, and the like, and cesium fluoride and potassium fluoride are preferable from the viewpoint of reactivity and cost.
The fluoride salt may be added all at once to the mixture of the compound (14) and the perfluoroallylating agent, or may be added intermittently or continuously.
The reaction temperature is preferably −70 to 0 ° C., more preferably −50 to −20 ° C., from the viewpoint that the yield of the compound (m1) is relatively good.

(Perfluoroallylating agent)
As the perfluoroallylating agent, compound (12) is preferable from the viewpoint of availability of raw materials and reactivity of perfluoroallylation.
_{CF 2 = CFCF 2 -Z (12} )
However, Z is ^{_{-OSO 2 F, -OSO 2 R f2}} , a chlorine atom, a bromine atom or an iodine ^{atom, R f2} is a perfluoroalkyl group.

As the compound (12), the compound (12-1) is preferable from the viewpoint of availability of raw materials, reactivity of perfluoroallylation, and ease of synthesis.
_{CF 2 = CFCF 2 -OSO 2 F} (12-1)
A method for producing compound (12-1) will be described later.

(Compound (14))
Compound (14) can be obtained, for example, by reacting compound (13) with sulfur trioxide. As sulfur trioxide, for example, fuming sulfuric acid in which sulfur trioxide is absorbed in concentrated sulfuric acid is used. In addition, commercially available stabilized sulfuric anhydride, fuming sulfuric acid, or sulfur trioxide obtained by distillation of stabilized sulfuric anhydride is also used.

However, n, R ^f1 and X are as described above, and preferred forms are also the same.
Compound (14) is preferably Compound (14-1) to Compound (14-10) from the viewpoint of availability of raw materials, ease of distillation purification of Compound (14), ease of synthesis, and cost. Compound (14-1) is more preferred. However, x is an integer of 1 or more.

(Compound (13))
Compound (13) is preferably Compound (13-1) to Compound (13-10) from the viewpoint of availability of raw materials, ease of distillation purification of Compound (13), ease of synthesis, and cost. Compound (13-1) is more preferred.
_{CF 2 = CF-CF 2 -O} -CF 2 CF 2 -SO 2 F (13-1)
_{CF 2 = CF-CF 2 -CF} 2 CF 2 -F (13-2)
_{CF 2 = CF- (CF 2 CF} 2) x -F (13-3)
_{CF 2 = CF-CF 2 -CF} 2 -SO 2 F (13-4)
_{CF 2 = CF-CF 2 -CF} 2 CF 2 CF 2 -SO 2 F (13-5)
_{CF 2 = CF-CF 2 -O} -CF 2 -F (13-6)
_{CF 2 = CF-CF 2 -O} -CF 2 CF 2 -F (13-7)
_{CF 2 = CF-CF 2 -O} -CF 2 CF 2 CF 2 -F (13-8)
_{CF 2 = CF-CF 2 -O} -CF 2 CF (CF 3) OCF 2 CF 2 CF 2 -F (13-9)
_{CF 2 = CF-CF 2 -O} -CF 2 CF (CF 3) -SO 2 F (13-10)
However, x is an integer of 1 or more.

Compound (13-1) can be produced by the methods described in US Pat. No. 4,273,729, US Patent Application Publication No. 2005/0037265, JP 2010-018674 A, and the like. Specifically, compound (12-1) is obtained by reacting compound (11) with sulfur trioxide in the presence of boron trifluoride, and compound (12-1) in the presence of a fluoride salt. And FC (═O) CF ₂ SO ₂ F.

FC (= O) CF ₂ SO ₂ F reacts with tetrafluoroethylene and sulfur trioxide to obtain tetrafluoro-β-sultone, and adds a fluoride salt to tetrafluoro-β-sultone to open the ring. To obtain.

Compound (13-2) can be produced by a method similar to the method described in Example 10 of JP-A-2004-26800. Specifically, it can be obtained by dehalogenating CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ I in the presence of a reducing metal such as magnesium. CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ I is obtained by telomerization of CF ₃ I with tetrafluoroethylene.

Compound (13-3) is an iodinated compound having a different carbon number, CF ₃ CF ₂ — (() by appropriately selecting the charged equivalent of tetrafluoroethylene in the telomerization of CF ₃ CF ₂ I and tetrafluoroethylene. after obtaining the CF ₂ CF _{2) x} -I, obtained by dehalogenation the iodinated compound.

Compound (13-4) can be produced by the method described in Example 1 of JP-T-2002-528433. Specifically, CF ₂ ClCFClCF ₂ CF ₂ I synthesized by the method described in Example 1 of US Pat. No. 5,350,821 is sulfinated in the presence of sodium azionate to form CF ₂ ClCFClCF ₂ CF ₂ SO. ₂ Na is obtained, and CF ₂ ClCFClCF ₂ CF ₂ SO ₂ Cl is obtained by reacting with chlorine in water, and CF ₂ ClCFClCF ₂ CF ₂ SO ₂ F is obtained by halogen exchange in the presence of potassium fluoride. And finally by dechlorination in the presence of zinc.

Compound (13-5) was prepared in the same manner as Compound (13-4) using CF ₂ ClCFClCF ₂ CF ₂ CF ₂ CF ₂ I synthesized by the method described in Example 1 of US Pat. No. 5,350,821. Obtained by. In order to obtain CF ₂ ClCFClCF ₂ CF ₂ CF ₂ CF ₂ I with high selectivity, it is necessary to increase the equivalent of tetrafluoroethylene used in the conditions of Example 1 of US Pat. No. 5,350,821. It can be easily recalled by the contractor.

  Compound (13-6) to Compound (13-8) are described in Molecules, 2011, 16, p. It can be produced by the method described in 6512-6540. Specifically, it can be obtained by adding a perfluoroallylating agent to a mixture of a perfluoroalkylcarboxylic acid fluoride having various carbon numbers and a fluoride salt and reacting them.

  Compound (13-9) can be produced by the method described in Example 16 of US Pat. No. 4,273,729. Specifically, it can be obtained by adding and reacting a perfluoroallylating agent to a mixture of hexafluoropropene oxide dimer and fluoride salt.

Compound (13-10) can be produced by the method described in Example 9 of US Pat. No. 4,273,729. Specifically, a perfluoropropane-2,3-sultone obtained by the reaction of hexafluoropropene and sulfur _{trioxide, MO-CF 2 -CF (CF} 3) obtained by mixing a fluoride salt -SO It is obtained by adding a perfluoroallylating agent to ₂ F and reacting it.

(Mechanism of action)
Since the compound (m1) described above is a compound having a relatively low molecular weight, a sulfone obtained by converting a fluorosulfonyl group of a fluorosulfonyl group-containing polymer having a structural unit derived from the compound (m1) into a sulfonic acid group. In the acid group-containing polymer, the molecular weight per sulfonic acid group can be lowered. In particular, when X of the compound (m1) is a fluorosulfonyl group, the molecular weight per sulfonic acid group in the sulfonic acid group-containing polymer can be further reduced. Therefore, a sulfonic acid group-containing polymer having a high ion exchange capacity can be obtained.
Moreover, in the manufacturing method of the compound (m1) demonstrated above, the compound (14) obtained by a comparatively few synthesis step is used. For example, the synthesis step from compound (11) to compound (14-1) is 3 steps. Therefore, the compound (m1-1) can be produced with few synthesis steps (four steps).

<Polymer (F)>
The fluorosulfonyl group-containing polymer of the present invention (hereinafter also referred to as polymer (F)) has a structural unit (u1) derived from the compound (m1).

However, n, R ^f1 and X are as described above, and preferred forms are also the same.
As the structural unit (u1), from the viewpoint of availability of raw materials, ease of distillation purification of the compound (m1), ease of synthesis, and cost, the structural unit (u1-1) to the structural unit (u1-10). Is preferable, and the structural unit (u1-1) is more preferable. However, x is an integer of 1 or more.

  The polymer (F) preferably further has a structural unit derived from tetrafluoroethylene (hereinafter also referred to as TFE). Since TFE has high crystallinity, it has an effect of suppressing swelling when the sulfonic acid group-containing polymer described later contains water, and the water content of the sulfonic acid group-containing polymer can be reduced.

The polymer (F) may further have a structural unit derived from a monomer other than the compound (m1) and TFE.
Other monomers include chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, ethylene, propylene, perfluoro (3-butenyl vinyl ether), perfluoro (allyl vinyl ether), perfluoro α-olefin (hexafluoropropylene) Etc.), (perfluoroalkyl) ethylene ((perfluorobutyl) ethylene etc.), (perfluoroalkyl) propene (3-perfluorooctyl-1-propene etc.), perfluoro (alkyl vinyl ether), described in WO 2011/013578 Examples include perfluoropolymers having a 5-membered ring.

  The proportion of the structural unit (u1), the structural unit derived from TFE, and the structural unit derived from other monomers out of 100 mol% of all the structural units constituting the polymer (F) is required for the sulfonic acid group-containing polymer. What is necessary is just to determine suitably according to the characteristic (ion exchange capacity, mechanical strength, etc.) to be.

The TQ value of the polymer (F) is preferably 200 to 330 ° C. When the TQ value of the polymer (F) is at least the lower limit, the sulfonic acid group-containing polymer has a sufficient molecular weight and is excellent in mechanical strength. When the TQ value of the polymer (F) is not more than the above upper limit value, the solubility or dispersibility of the sulfonic acid group-containing polymer is improved, and a liquid composition described later can be easily prepared.
The TQ value is an index of the molecular weight of the polymer. The extrusion amount when the polymer (F) is melt-extruded under the condition of the extrusion pressure of 2.94 MPa using a nozzle having a length of 1 mm and an inner diameter of 1 mm is 100 mm ³ / This is the temperature in seconds.

<Method for producing polymer (F)>
The polymer (F) is produced by producing the compound (m1) by the above-described method for producing the compound (m1), and polymerizing the compound (m1) and, if necessary, monomer components including TFE and other monomers. This is a method for obtaining (F).

Examples of the polymerization method include known polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Moreover, you may superpose | polymerize in a liquid or supercritical carbon dioxide.
Polymerization is performed under conditions where radicals occur. Examples of the method for generating radicals include a method of irradiating radiation such as ultraviolet rays, γ rays, and electron beams, a method of adding a radical initiator, and the like.
The polymerization temperature is usually 10 to 150 ° C.

  Examples of radical initiators include bis (fluoroacyl) peroxides, bis (chlorofluoroacyl) peroxides, dialkyl peroxydicarbonates, diacyl peroxides, peroxyesters, azo compounds, persulfates, etc. Perfluoro compounds such as bis (fluoroacyl) peroxides are preferred from the viewpoint of obtaining a polymer (F) having few stable end groups.

As the solvent used in the solution polymerization method, a solvent having a boiling point of 20 to 350 ° C is preferable, and a solvent having a boiling point of 40 to 150 ° C is more preferable. As a solvent, perfluorotrialkylamines (perfluorotributylamine etc.), perfluorocarbons (perfluorohexane, perfluorooctane etc.), hydrofluorocarbons (1H, 4H-perfluorobutane, 1H-perfluorohexane etc.), hydrochlorofluorocarbons (3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, etc.), hydrofluoroethers (CF ₃ CH ₂ OCF ₂ CF ₂ H, etc.).

  In the solution polymerization method, a monomer, a radical initiator or the like is added to a solvent, and radicals are generated in the solvent to polymerize the monomer. The monomer and initiator may be added all at once, sequentially, or continuously.

In the suspension polymerization method, water is used as a dispersion medium, a monomer, a nonionic radical initiator or the like is added to the dispersion medium, and radicals are generated in the dispersion medium to polymerize the monomer.
Nonionic radical initiators include bis (fluoroacyl) peroxides, bis (chlorofluoroacyl) peroxides, dialkyl peroxydicarbonates, diacyl peroxides, peroxyesters, dialkyl peroxides, bis (fluoroalkyl) Examples thereof include peroxides and azo compounds.
The dispersion medium may contain the above-mentioned solvent as an auxiliary agent; a surfactant as a dispersion stabilizer that prevents aggregation of suspended particles; and a hydrocarbon compound (hexane, methanol, etc.) as a molecular weight regulator.

(Mechanism of action)
The polymer (F) described above has a structural unit (u1) derived from the compound (m1) having a relatively low molecular weight. Moreover, in the manufacturing method of the polymer (F) demonstrated above, the monomer component containing the compound (m1) with comparatively low molecular weight is superposed | polymerized, and the polymer (F) is obtained. Therefore, in the sulfonic acid group-containing polymer obtained by converting the fluorosulfonyl group of the polymer (F) into a sulfonic acid group, the molecular weight per sulfonic acid group can be lowered. In particular, when X of the compound (m1) is a fluorosulfonyl group, the molecular weight per sulfonic acid group in the sulfonic acid group-containing polymer can be further reduced. Therefore, a sulfonic acid group-containing polymer having a high ion exchange capacity can be obtained.

<Polymer (H)>
The sulfonic acid group-containing polymer of the present invention (hereinafter also referred to as polymer (H)) is a polymer obtained by converting a fluorosulfonyl group of polymer (F) into a sulfonic acid group, and has a structural unit (u′1).

However, n and R ^f1 are as described above, and preferred forms are also the same. X ′ is a fluorine atom or a sulfonic acid group.
As the structural unit (u′1), from the viewpoint of availability of raw materials, ease of distillation purification of the compound (m1), ease of synthesis, and cost, the structural unit (u′1-1) to the structural unit ( u′1-10) is preferable, and the structural unit (u′1-1) is more preferable. However, x is an integer of 1 or more.

  The polymer (H) preferably further has a structural unit derived from TFE, and may further have a structural unit derived from a monomer other than the compound (m1) and TFE.

  The ion exchange capacity of the polymer (H) is preferably 0.5 to 2.5 meq / g dry resin, more preferably 1.3 to 2.3 meq / g dry resin. If the ion exchange capacity is at least the lower limit of the above range, the conductivity of the polymer (H) will be high, so that sufficient battery output can be obtained when used in the catalyst layer of a polymer electrolyte fuel cell. When the ion exchange capacity is equal to or less than the upper limit of the above range, swelling when the polymer (H) contains water is suppressed.

<Manufacture of polymer (H)>
The method for producing the polymer (H) is a method for producing the polymer (F) by the method for producing the polymer (F) and obtaining the polymer (H) by converting the fluorosulfonyl group of the polymer (F) into a sulfonic acid group. It is.

  Examples of the method for converting a fluorosulfonyl group into a sulfonic acid group include a method in which the fluorosulfonyl group of the polymer (F) is hydrolyzed to form a sulfonate, and the sulfonate is converted into an acid form to convert it into a sulfonic acid group. .

Hydrolysis is performed, for example, by contacting the polymer (F) with a basic compound in a solvent. Examples of the basic compound include sodium hydroxide and potassium hydroxide. Examples of the solvent include water, a mixed solvent of water and a polar solvent, and the like. Examples of the polar solvent include alcohol (methanol, ethanol, etc.), dimethyl sulfoxide and the like.
The acidification is performed, for example, by bringing a polymer having a sulfonate into contact with an aqueous solution such as hydrochloric acid or sulfuric acid.
Hydrolysis and acidification are usually performed at 0 to 120 ° C.

(Mechanism of action)
Since the polymer (H) described above is a polymer obtained by converting the fluorosulfonyl group of the polymer (F) into a sulfonic acid group, the ion exchange capacity can be increased.
Moreover, in the manufacturing method of the polymer (H) demonstrated above, since the fluorosulfonyl group of the polymer (F) is converted into the sulfonic acid group, the polymer (H) with a high ion exchange capacity can be manufactured.

<Liquid composition>
The liquid composition of the present invention contains a polymer (H) and a liquid medium.
The liquid composition of the present invention may be one in which the polymer (H) is dispersed in the liquid medium, or may be one in which the polymer (H) is dissolved in the liquid medium.

(Liquid medium)
The liquid medium preferably contains water and an organic solvent.
Water improves the dispersibility or solubility of the polymer (H) in the liquid medium.
The organic solvent makes it easy to form a catalyst layer and a solid polymer electrolyte membrane that are difficult to break.

As the organic solvent, at least one kind of alcohol having 1 to 4 carbon atoms is preferable from the viewpoint of easily forming a catalyst layer and a solid polymer electrolyte membrane which are not easily broken.
Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro- 1-propanol, 2,2,3,3-tetrafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 3,3,3-trifluoro-1-propanol Etc.

10-99 mass% is preferable among the sum (100 mass%) of water and an organic solvent, and, as for the ratio of water, 20-99 mass% is more preferable.
The ratio of the organic solvent is preferably 1 to 90% by mass and more preferably 1 to 80% by mass in the total (100% by mass) of water and the organic solvent.
If the ratio of water and the organic solvent is within the above range, it is easy to form a catalyst layer and a solid polymer electrolyte membrane that are excellent in dispersibility of the polymer having an ion exchange group with respect to the dispersion medium and are difficult to break.

  1-50 mass% is preferable in a liquid composition (100 mass%), and, as for the density | concentration of a polymer (H), 3-30 mass% is more preferable. If the concentration of the polymer (H) is not less than the lower limit of the above range, a thick film can be stably obtained during film formation. Moreover, the adjustment of the coating liquid for forming the catalyst layer when preparing the catalyst layer is facilitated. If the density | concentration of a polymer (H) is below the upper limit of the said range, it can suppress that the viscosity of a liquid composition becomes high too much.

(Use of liquid composition)
The liquid composition of the present invention is suitably used for forming a catalyst layer or a solid polymer electrolyte membrane in a membrane / electrode assembly. In addition, other membranes (electrolysis used for water electrolysis, hydrogen peroxide production, ozone production, waste acid recovery, proton selective permeation membranes, cation exchange membranes for alkaline chloride electrolysis, redox flow battery membranes, desalting or salt production) It can also be used to form a cation exchange membrane for dialysis.

<Method for producing liquid composition>
The method for producing a liquid composition of the present invention is a method for producing a polymer (H) by a method for producing a polymer (H), and mixing the polymer (H) and a liquid medium to obtain a liquid composition.

Examples of the mixing method include a method in which shearing such as stirring is applied to the polymer (H) in the liquid medium under atmospheric pressure or in a state sealed with an autoclave or the like.
0-250 degreeC is preferable and the temperature at the time of stirring has more preferable 20-150 degreeC. You may provide shearing, such as an ultrasonic wave, as needed.

  When applying shear such as stirring to the mixed liquid in which the polymer (H) and the liquid medium are mixed, shearing such as stirring may be added to the mixed liquid in which the liquid medium is added to the polymer (H) all at once, The liquid medium may be mixed with the polymer (H) in a plurality of times, and shearing such as stirring may be applied between them. For example, a mixture such as a polymer (H) with a part of the liquid medium is subjected to shearing such as stirring, and then the remaining liquid medium is added to the mixed liquid and then shearing such as stirring is applied again. Good. Alternatively, only an organic solvent may be added to the liquid medium and shearing such as stirring may be applied, and then only water may be added and shearing such as stirring may be applied again.

(Mechanism of action)
Since the liquid composition of the present invention described above includes the polymer (H) that can increase the ion exchange capacity, a film including a polymer having a high ion exchange capacity can be formed.
Moreover, in the manufacturing method of the liquid composition of this invention demonstrated above, in order to obtain a liquid composition by mixing the polymer (H) which can raise ion exchange capacity, and a liquid medium, ion exchange capacity is high. A liquid composition capable of forming a film containing a polymer can be produced.

<Membrane electrode assembly>
FIG. 1 is a cross-sectional view showing an example of the membrane electrode assembly of the present invention. The membrane electrode assembly 10 is in contact with the catalyst layer 11 between the anode 13 having the catalyst layer 11 and the gas diffusion layer 12, the cathode 14 having the catalyst layer 11 and the gas diffusion layer 12, and the anode 13 and the cathode 14. And a solid polymer electrolyte membrane 15 arranged in the above state.

  In the membrane electrode assembly 10, at least one selected from the group consisting of the catalyst layer 11 of the cathode 14, the catalyst layer 11 of the anode 13, and the solid polymer electrolyte membrane 15 contains a polymer (H). When the catalyst layer 11 contains a polymer (H), it is preferable that at least the catalyst layer 11 of the cathode 14 contains a polymer (H).

(Catalyst layer)
The catalyst layer is a layer containing a catalyst and a polymer having an ion exchange group.
Examples of the catalyst include a supported catalyst in which platinum or a platinum alloy is supported on a carbon support.
Examples of the carbon carrier include carbon black powder.
Examples of the polymer having an ion exchange group include a polymer (H) and a perfluoropolymer having a known ion exchange group.

(Gas diffusion layer)
The gas diffusion layer has a function of uniformly diffusing gas in the catalyst layer and a function as a current collector.
Examples of the gas diffusion layer include carbon paper, carbon cloth, carbon felt and the like.
The gas diffusion layer is preferably subjected to water repellent treatment with polytetrafluoroethylene or the like.

(Carbon layer)
As shown in FIG. 2, the membrane electrode assembly 10 may have a carbon layer 16 between the catalyst layer 11 and the gas diffusion layer 12.
By disposing the carbon layer, the gas diffusibility on the surface of the catalyst layer is improved, and the power generation performance of the polymer electrolyte fuel cell is greatly improved.
The carbon layer is a layer containing carbon and a nonionic fluorine-containing polymer.
Examples of carbon include carbon particles and carbon fibers, and carbon nanofibers having a fiber diameter of 1 to 1000 nm and a fiber length of 1000 μm or less are preferable.
Examples of the nonionic fluorine-containing polymer include polytetrafluoroethylene.

(Solid polymer electrolyte membrane)
The solid polymer electrolyte membrane is a membrane containing a polymer having an ion exchange group.
Examples of the polymer having an ion exchange group include a polymer (H) and a perfluoropolymer having a known ion exchange group.

  The solid polymer electrolyte membrane may be reinforced with a reinforcing material. Examples of the reinforcing material include porous bodies, fibers, woven fabrics, and nonwoven fabrics. Examples of the reinforcing material include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, polyethylene, polypropylene, polyphenylene sulfide, and the like.

  The solid polymer electrolyte membrane may contain one or more atoms selected from the group consisting of cerium and manganese in order to further improve the durability. Cerium and manganese decompose hydrogen peroxide, which is a causative substance that causes deterioration of the solid polymer electrolyte membrane. Cerium and manganese are preferably present as ions in the solid polymer electrolyte membrane, and as long as they are present as ions, they may be present in any state in the solid polymer electrolyte membrane.

<Method for producing membrane electrode assembly>
When the membrane / electrode assembly does not have a carbon layer, the membrane / electrode assembly is produced, for example, by the following method.
A method in which a catalyst layer is formed on a solid polymer electrolyte membrane to form a membrane catalyst layer assembly, and the membrane catalyst layer assembly is sandwiched between gas diffusion layers.
A method in which a catalyst layer is formed on a gas diffusion layer to form electrodes (anode, cathode), and a solid polymer electrolyte membrane is sandwiched between the electrodes.

When the membrane / electrode assembly has a carbon layer, the membrane / electrode assembly is produced, for example, by the following method.
-A dispersion containing carbon and a nonionic fluorine-containing polymer is applied on a base film, dried to form a carbon layer, a catalyst layer is formed on the carbon layer, and the catalyst layer and the solid polymer electrolyte membrane And the base film is peeled to form a membrane catalyst layer assembly having a carbon layer, and the membrane catalyst layer assembly is sandwiched between gas diffusion layers.
A membrane / catalyst layer assembly in which a dispersion containing carbon and a nonionic fluoropolymer is applied on a gas diffusion layer and dried to form a carbon layer, and a catalyst layer is formed on a solid polymer electrolyte membrane. And sandwiching with a gas diffusion layer having a carbon layer.

(Method for forming catalyst layer)
Examples of the method for forming the catalyst layer include the following methods.
A method in which a coating liquid for forming a catalyst layer is applied on a solid polymer electrolyte membrane, a gas diffusion layer, or a carbon layer and dried.
A method in which a catalyst layer forming coating solution is applied on a substrate film, dried to form a catalyst layer, and the catalyst layer is transferred onto a solid polymer electrolyte membrane.

  The coating liquid for forming a catalyst layer is a liquid in which a polymer having an ion exchange group and a catalyst are dispersed in a dispersion medium. The coating liquid for forming a catalyst layer can be prepared, for example, by mixing the liquid composition of the present invention and a catalyst dispersion.

(Method for forming solid polymer electrolyte membrane)
The solid polymer electrolyte membrane can be formed, for example, by a method (cast method) in which a liquid composition is applied on a substrate film or a catalyst layer and dried.
The liquid composition is a dispersion liquid in which a polymer having an ion exchange group is dispersed in a dispersion medium containing water and an organic solvent. As the liquid composition, the liquid composition of the present invention may be used.

  In order to stabilize the solid polymer electrolyte membrane, it is preferable to perform an annealing treatment. The temperature of the annealing treatment is preferably 130 to 200 ° C., although it depends on the type of fluorine-containing polymer having an ion exchange group. If the temperature of annealing treatment is 130 degreeC or more, the polymer which has an ion exchange group will not contain water excessively. If the temperature of annealing treatment is 200 degrees C or less, the thermal decomposition of an ion exchange group will be suppressed.

(Mechanism of action)
In the membrane electrode assembly of the present invention described above, at least one selected from the group consisting of a cathode catalyst layer, an anode catalyst layer and a solid polymer electrolyte membrane is a polymer (H) capable of increasing the ion exchange capacity. Power generation performance is excellent.
In the method for producing a membrane electrode assembly of the present invention described above, at least one selected from the group consisting of a cathode catalyst layer, an anode catalyst layer, and a solid polymer electrolyte membrane is used for ion exchange capacity. Since the liquid composition of the present invention capable of forming a film containing a high polymer is used, a membrane electrode assembly excellent in power generation performance can be produced.

<Solid polymer fuel cell>
A polymer electrolyte fuel cell can be obtained by disposing separators in which grooves serving as gas flow paths are formed on both surfaces of the membrane electrode assembly of the present invention.
Examples of the separator include a separator made of various conductive materials such as a metal separator, a carbon separator, and a separator made of a material in which graphite and a resin are mixed.
In a polymer electrolyte fuel cell, power generation is performed by supplying a gas containing oxygen to the cathode and a gas containing hydrogen to the anode. The membrane electrode assembly can also be applied to a methanol fuel cell that generates power by supplying methanol to the anode.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Examples 1 and 2 are production examples, Examples 3, 4, and 10 to 12 are examples, Example 5 is a reference example, and Examples 6 to 9 are comparative examples.

⁽¹⁹ F-NMR)
¹⁹ F-NMR was measured under the conditions of 282.7 MHz, solvent: CDCl ₃ , chemical shift standard: CFCl ₃ . The product was quantitatively determined from the analysis result of ¹⁹ F-NMR and the amount of internal standard sample (1,3-bis (trifluoromethyl) benzene) added.

(Ion exchange capacity of polymer (H))
The polymer (H) film was vacuum-dried at 120 ° C. for 12 hours to remove moisture from the polymer (H) film. The polymer (H) membrane was immersed in a 0.85 mol / g sodium hydroxide solution (solvent: water / methanol = 10/90 (mass ratio)) to neutralize the sulfonic acid groups of the polymer (H). Converted to sulfonic acid sodium salt. The ion exchange capacity of the polymer (H) was determined by back titrating the neutralized sodium hydroxide solution with 0.1 mol / L hydrochloric acid.

(Example 1)
Production of Compound (12-1) and Compound (13-1):

  Compound (12-1) and Compound (13-1) were obtained according to the method described in Examples of US Pat. No. 4,273,729.

(Example 2)
Production of compound (14-1):

A 500 mL four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 235 g of 60% fuming sulfuric acid under a nitrogen seal. The flask was set in an oil bath, and 291 g of the compound (13-1) was added dropwise over 20 minutes while maintaining the internal temperature at 35 to 40 ° C. A mild exotherm was observed after completion of the dropping, and the internal temperature rose to 50 ° C. Thereafter, stirring was continued for 28 hours while maintaining the internal temperature at 40 ° C. After cooling the reaction solution to room temperature, the reaction solution was transferred to a 500 mL separatory funnel and allowed to stand to separate into a white turbid upper layer and an orange transparent lower layer. After extracting the lower layer, 157 g of concentrated sulfuric acid was added, and after shaking well, the mixture was allowed to stand and then the lower layer was extracted. 31 g of concentrated sulfuric acid was added again, the mixture was shaken well and allowed to stand, and then the lower layer was extracted. The upper layer of 266 g remaining in the separatory funnel was recovered. The recovered upper layer was analyzed by ¹⁹ F-NMR and quantified from the amount of the internal standard sample added. As a result, it was confirmed that the target compound (14-1) was produced in a yield of 69%. Residual compound (13-1) was not confirmed.

  The recovered upper layer was transferred to a 1 L four-necked flask equipped with a stirrer, a thermometer, and a distillation column (inner diameter 3 cm × column length 50 cm, packing length 36 cm) packed with irregular packing, and vacuum distillation was performed. As a result of distillation, 540 g of a colorless and transparent compound (14-1) was obtained. The distillation temperature of the compound (14-1) was 57.1 ° C. under a pressure of 25 mmHg (absolute pressure).

¹⁹ F-NMR spectrum of the compound (14-1): 45.80 ppm (SO ₂ F, 1F, p, J = 6.1 Hz), −76.30 ppm and −77.00 ppm (CF—CF ₂ —O, 2F) M), −81.70 (annular portion CF ₂ , 1F, dd, J = 107, 7.6 Hz), −88.46 ppm (annular portion CF ₂ , 1F, dt, J = 107, 13.0 Hz), −81.85 ppm (O—CF ₂ —CF ₂ , 2F, m), −112.50 ppm (CF ₂ —SO ₂ F, 2F, m), −151.51 ppm (annular portion CF, 1F, p, J = 7.6 Hz).

(Example 3)
Production of compound (m1-1):

In a 50 mL four-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel, under a nitrogen seal, 3.93 g of compound (12-1), 6.98 g of compound (14-1), 9 of diglyme .65 g was charged. The flask was cooled with a refrigerant, and after the internal temperature dropped to −50 ° C., 1.00 g of potassium fluoride was added over 10 minutes. Exotherm was confirmed at the time of dropping. After the addition, stirring was continued for 9 hours while maintaining the internal temperature at −40 to −30 ° C., then cooling was stopped and the temperature was raised to room temperature. When the reaction solution was transferred to a 50 mL separatory funnel and allowed to stand, the phase was separated into a pale yellow upper layer and a colorless lower layer. 8.95 g of the recovered lower layer was analyzed by ¹⁹ F-NMR and quantified from the amount of the internal standard sample added. As a result, it was confirmed that the target compound (m1-1) was produced in a yield of 16%. did. The main product was the compound (13-1) (yield 36%). The results are shown in Table 1.

(Example 4)
Production of compound (m1-1):
118.0 g of compound (12-1), 210.4 g of compound (14-1), 313.0 g of diglyme and 31.3 g of potassium fluoride were used, and the internal temperature after addition was adjusted using a 1 L reactor. The reaction was performed in the same manner as in Example 3 except that the temperature was −50 to −30 ° C. From the quantitative analysis of the lower layer (249.8 g) collected by the liquid separation operation, it was confirmed that the target compound (m1-1) was produced in a yield of 20%. The main product was compound (13-1) (yield 35%). The results are shown in Table 1.

  The lower layer collected in Examples 3 and 4 was transferred to a 500 mL four-necked flask equipped with a stirrer, thermometer, and distillation column (inner diameter 3 cm × column length 50 cm, packing length 36 cm) packed with irregular packing. Vacuum distillation was performed. As a result of distillation, 70 g of a colorless and transparent compound (m1-1) was obtained. The distillation temperature of the compound (m1-1) was 60.7 ° C. under a pressure of 3.9 mmHg (absolute pressure).

¹⁹ F-NMR spectrum of the compound (m1-1): 55.37 ppm (CF—SO ₂ F, 1F, m), 45.83 ppm (CF ₂ —SO ₂ F, 1F, m), −71.88 ppm (CF _{2 = CF-CF 2 -O-,} 2F, m), - 74.04ppm and _{-74.64ppm (O-CF 2 -CF (} SO 2 F) CF 2 -O, 2F & 2F, m), - 82.12ppm (O—CF ₂ —CF ₂ —SO ₂ F, 2F, m), −71.88 ppm (CF ₂ = CF, 1F, ddt, J = 49, 39, 8 Hz), −103.65 ppm (CF ₂ = CF 1F, ddt, J = 18.0, 49, 26 Hz), −112.50 ppm (CF ₂ —SO ₂ F, 2F, m), −164.83 ppm (CF—SO ₂ F, 1F, m), − 190.83 ppm _{CF 2 = CF, 1F, ddt} , J = 118,39,14Hz).

(Example 5)
Isomerized compound (14-1):

In a 10 mL three-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 0.19 g of sodium fluoride was charged under a nitrogen seal. The flask was cooled with a refrigerant, and after the internal temperature dropped to -35 ° C, 3.04 g of the compound (14-1) was added dropwise while stirring with a stirrer. No exotherm was observed during the dropwise addition. Cooling was stopped and the internal temperature was returned to room temperature. When the internal solution was analyzed by ¹⁹ F-NMR, the compound (14-1) hardly reacted. When the flask was heated and reacted at 100 ° C. for 5 hours, it was confirmed that compound (15-1), which is an isomer of compound (14-1), was produced.

¹⁹ F-NMR spectrum of compound (15-1): 54.3 ppm (CF—SO ₂ F, 1F, m), 45.6 ppm (CF ₂ —SO ₂ F, 1F, m), 33.6 ppm (CF— _{COF, 1F, m), -} 75.4ppm (CF-CF 2 -O, 2F, m), - 82.3ppm (O-CF 2 -CF 2 -SO 2 F, 2F, m), - 112.8ppm _{(CF 2 -SO 2 F, 2F} , m), - 159.4ppm (CF, 1F, m).

From the results of Example 5, the compound (14-1), which is a β-sultone compound having a relatively large substituent, undergoes a ring-opening reaction in the same manner as tetrafluoro-β-sultone, thereby producing the compound (15-1). I understand that. That is, even with a substrate having a relatively large substituent, the ring-opening reaction itself occurs without any problem.
The reason why the yield of the target compound (m1-1) is remarkably improved by the present invention is considered as follows.
The reaction of the compound (14-1) or the compound (15-1) with a fluoride salt (MF) produces an MO—CF ₂ —CF (SO ₂ F) — structure which is an active species in perfluoroallylation. The active species derived from the compound (14-1) or the compound (15-1) having a relatively large substituent is considered to have poor stability. That is, in the case of the conventional method in which the compound (14-1) and the fluoride salt are mixed in advance, the active species are decomposed before the addition of the perfluoroallylating agent to obtain the target compound (m1-1). It is considered impossible. On the other hand, as shown in the present invention, when a fluoride salt is added in a state where the compound (14-1) and the perfluoroallylating agent are mixed in advance, the generated active species can react with the perfluoroallylating agent quickly. The yield of the target compound (m1-1) is considered to be significantly improved.

  (Example 6)

A 50 mL four-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 1.05 g of potassium fluoride and 10.52 g of diglyme under a nitrogen seal. The flask was cooled with a refrigerant, and 6.96 g of the compound (14-1) was added dropwise after the internal temperature dropped to −20 ° C. Exotherm was confirmed at the time of dropping. After stirring at -30 to -10 ° C for 1 hour, 3.93 g of the compound (12-1) was added dropwise. After stirring at -20 to -10 ° C for 1 hour, cooling was stopped and the internal temperature was raised to room temperature. After stirring for 16 hours at room temperature, stirring was stopped. When the reaction solution was transferred to a 50 mL separatory funnel and allowed to stand, the phase was separated into a pale yellow upper layer and a colorless lower layer. 7.37 g of the recovered lower layer was analyzed by ¹⁹ F-NMR, and quantified from the amount of internal standard sample added. As a result, it was confirmed that the target compound (m1-1) was produced at a yield of 1%. did. The main product was the compound (13-1) (yield 50%). The results are shown in Table 2.

(Example 7)
The reaction was performed in the same manner as in Example 6 except that 5.25 g of tetraglyme was used instead of diglyme and the temperature was changed as shown in Table 2. From the quantitative analysis after the liquid separation operation, only the trace amount of the target compound (m1-1) was confirmed. The results are shown in Table 2.

(Example 8)
The reaction was conducted in the same manner as in Example 6 except that 11.57 g of tetraglyme was used instead of diglyme, 2.27 g of silver fluoride was used instead of potassium fluoride, and the temperature was changed as shown in Table 2. From the quantitative analysis after the liquid separation operation, only the trace amount of the target compound (m1-1) was confirmed. The results are shown in Table 2.

(Example 9)
A 50 mL four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 0.77 g of sodium fluoride and 4.06 g of diglyme under a nitrogen seal. The flask was cooled with a refrigerant, and 6.98 g of the compound (14-1) was added dropwise after the internal temperature dropped to −20 ° C. Cooling was stopped and the internal temperature was raised to room temperature. After the internal temperature reached 25 ° C., 3.91 g of the compound (12-1) was added dropwise. An exotherm was not confirmed. Thereafter, the reaction solution was heated to 70 ° C. while being confirmed by gas chromatographic analysis, but formation of the target compound (m1-1) was not confirmed. The results are shown in Table 2.

(Example 10)
Production of polymer (F):
In an autoclave (internal volume: 30 mL, manufactured by Hastelloy), 23.0 g of the compound (m1-1) was placed, cooled with liquid nitrogen, and deaerated. 1.44 g of TFE was introduced into the autoclave and heated in an oil bath until the internal temperature reached 100 ° C. The pressure at this time was 0.475 MPaG (gauge pressure). A mixed liquid of 0.017 g of perfluoro-di-tert-butyl peroxide as a polymerization initiator and 0.921 g of the compound (m1-1) was press-fitted into the autoclave. Further, nitrogen gas was introduced from the press-in line, and the press-in liquid in the press-in line was completely pushed in. As a result of the dilution of TFE in the gas phase by this operation, the pressure increased to 0.90 MPaG. While maintaining the pressure at 0.90 MPaG, TFE was continuously added for polymerization. When the amount of TFE added reached 4.2 g in 6.5 hours, the inside of the autoclave was cooled to stop the polymerization, and the gas in the system was purged. The reaction solution was diluted with HFC-52-13p (CF ₃ (CF ₂ ) ₅ H), HFE-347pc-f (CF ₃ CH ₂ OCF ₂ CF ₂ H) was added, and the polymer was aggregated and filtered. Thereafter, the operation of stirring the polymer in HFC-52-13p and reaggregating with HFE-347pc-f was repeated twice. It vacuum-dried at 120 degreeC and obtained 7.7g of the polymer (F-1) which is a copolymer of TFE and a compound (m1-1).

  The polymer (F-1) was press-molded (240 ° C., 4 MPa) to obtain a polymer (F-1) film. It was processed into a film (thickness: 125 μm).

(Example 11)
Production of polymer (H):
The polymer (F-1) membrane is immersed in a 20% by mass aqueous potassium hydroxide solution at 80 ° C. for 20 hours to hydrolyze the fluorosulfonyl group (—SO ₂ F) in the polymer (F-1). and it was converted to -SO ₃ K. Further, the polymer film was immersed in a 3 mol / L hydrochloric acid aqueous solution for 1 hour at room temperature, and then immersed in ultrapure water at room temperature for 30 minutes. A total of five cycles of immersion in an aqueous hydrochloric acid solution and immersion in ultrapure water were performed to convert —SO ₃ K into sulfonic acid groups (—SO ₃ H). Thereafter, washing with ultrapure water was repeated until the pH of the water in which the polymer film was immersed was 7. Finally, the polymer film was sandwiched between filter papers and air-dried to obtain a polymer (H) film.
The ion exchange capacity was determined from the polymer (H) membrane and found to be 1.55 meq / g dry resin. The proportions of the structural unit derived from TFE and the structural unit derived from the compound (m1-1) in the polymer (F-1) calculated from the ion exchange capacity were 88.0 mol% and 12.0 mol%, respectively. there were.

(Example 12)
Production of liquid composition:
In a 200 mL glass autoclave, 3.6 g of a finely cut polymer (H) film and 49.9 g of a mixed solvent of 1-propanol, 1-butanol and water (24/33/43 (mass ratio)) added. The autoclave was heated with stirring. The temperature was gradually raised from 100 ° C. while observing the dissolved state, and when the temperature was raised to 180 ° C., it was confirmed that the polymer (H) was dispersed in the mixed solvent. The heating time was a total of 27 hours. After cooling, pressure filtration (filter paper: manufactured by Advantech Toyo Co., Ltd., PF100) was performed to obtain a liquid composition in which the polymer (H) was dispersed in the mixed solvent at a concentration of about 7% by mass.
The liquid composition was cast on a petri dish and the solvent was volatilized in a drier to obtain a solid polymer electrolyte membrane having a thickness of 300 μm made of polymer (H).

The fluorosulfonyl group-containing monomer of the present invention is used for a catalyst layer, a solid polymer electrolyte membrane, an alkali chloride electrolysis or electrodialysis in a membrane electrode assembly for a polymer electrolyte fuel cell or a polymer electrolyte water electrolysis. It is useful as a raw material for polymers contained in ion exchange membranes and the like.
Further, the fluorosulfonyl group-containing monomer of the present invention is also useful as a raw material for a polymer contained in a diaphragm for a redox flow secondary battery.

  DESCRIPTION OF SYMBOLS 10 Membrane electrode assembly, 11 Catalyst layer, 12 Gas diffusion layer, 13 Anode, 14 Cathode, 15 Solid polymer electrolyte membrane, 16 Carbon layer

Claims (20)

A fluorosulfonyl group-containing monomer, which is a compound represented by the following formula (m1).

However, n is 0 or 1, R ^f1 is a perfluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of the perfluoroalkylene group, and X is a fluorine atom or a fluorosulfonyl group.   The fluorosulfonyl group-containing monomer according to claim 1, wherein X is a fluorosulfonyl group.   The fluorosulfonyl group-containing monomer according to claim 1 or 2, wherein n is 1. Wherein ^{R f1} is _-CF 2 CF ₂ - a, fluorosulfonyl group-containing monomer according to any one of claims 1 to 3.   The fluorosulfonyl group containing polymer which has a structural unit derived from the fluorosulfonyl group containing monomer as described in any one of Claims 1-4.   The fluorosulfonyl group-containing polymer according to claim 5, further comprising a structural unit derived from tetrafluoroethylene.   A sulfonic acid group-containing polymer obtained by converting the fluorosulfonyl group of the fluorosulfonyl group-containing polymer according to claim 5 or 6 into a sulfonic acid group.   A liquid composition comprising the sulfonic acid group-containing polymer according to claim 7 and a liquid medium. An anode having a catalyst layer;
A cathode having a catalyst layer;
A membrane electrode assembly for a polymer electrolyte fuel cell comprising a polymer electrolyte membrane disposed between the anode and the cathode,
The membrane electrode assembly, wherein at least one selected from the group consisting of the cathode catalyst layer, the anode catalyst layer, and the solid polymer electrolyte membrane comprises the sulfonic acid group-containing polymer according to claim 7. A method for producing a fluorosulfonyl group-containing monomer, wherein a fluoride salt is added to a liquid in which a compound represented by the following formula (14) and a perfluoroallylating agent are mixed in advance to obtain a compound represented by the following formula (m1) .

However, n is 0 or 1, R ^f1 is a perfluoroalkylene group or a group having an etheric oxygen atom between carbon-carbon atoms of the perfluoroalkylene group, and X is a fluorine atom or a fluorosulfonyl group. The method for producing a fluorosulfonyl group-containing monomer according to claim 10, wherein the perfluoroallylating agent is a compound represented by the following formula (12).
_{CF 2 = CFCF 2 -Z (12} )
However, Z is ^{_{-OSO 2 F, -OSO 2 R f2}} , a chlorine atom, a bromine atom or an iodine ^{atom, R f2} is a perfluoroalkyl group.   The method for producing a fluorosulfonyl group-containing monomer according to claim 10 or 11, wherein X is a fluorosulfonyl group.   The method for producing a fluorosulfonyl group-containing monomer according to any one of claims 10 to 12, wherein n is 1. Wherein ^{R f1} is _-CF 2 CF ₂ - is a method for producing a fluorosulfonyl group-containing monomer according to any one of claims 10 to 13.   A structural unit derived from the fluorosulfonyl group-containing monomer by producing a fluorosulfonyl group-containing monomer by the production method according to any one of claims 10 to 14, and polymerizing a monomer component containing the fluorosulfonyl group-containing monomer. A method for producing a fluorosulfonyl group-containing polymer, which obtains a fluorosulfonyl group-containing polymer having   The method for producing a fluorosulfonyl group-containing polymer according to claim 15, wherein the monomer component further comprises tetrafluoroethylene.   A sulfonic acid group-containing polymer is produced by the production method according to claim 15 or 16, and a sulfonic acid group-containing polymer is obtained by converting the fluorosulfonyl group of the fluorosulfonyl group-containing polymer into a sulfonic acid group. A method for producing a containing polymer.   The manufacturing method of a liquid composition which manufactures a sulfonic acid group containing polymer by the manufacturing method of Claim 17, and mixes this sulfonic acid group containing polymer and a liquid medium, and obtains a liquid composition. An anode having a catalyst layer;
A cathode having a catalyst layer;
A method for producing a membrane electrode assembly for a polymer electrolyte fuel cell comprising a polymer electrolyte membrane disposed between the anode and the cathode,
A liquid composition is produced by the production method according to claim 18, the liquid composition and a catalyst are mixed to prepare a coating solution for forming a catalyst layer, and the cathode and the anode are prepared using the coating solution. A process for producing a membrane electrode assembly, wherein either one or both of the catalyst layers are formed. An anode having a catalyst layer;
A cathode having a catalyst layer;
A method for producing a membrane electrode assembly for a polymer electrolyte fuel cell comprising a polymer electrolyte membrane disposed between the anode and the cathode,
The manufacturing method of a membrane electrode assembly which manufactures a liquid composition with the manufacturing method of Claim 18, and forms the said solid polymer electrolyte membrane using this liquid composition.

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