JP6524835B2 - Method for producing fluorosulfonyl group-containing monomer, fluorosulfonyl group-containing polymer, sulfonic acid group-containing polymer, liquid composition and membrane electrode assembly - Google Patents

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 a method for producing them.

  High ion exchange capacity is desired for the polymer contained in the catalyst layer, the solid polymer electrolyte membrane, the cation exchange membrane used for alkaline chloride electrolysis, etc. in the membrane electrode assembly for a polymer electrolyte fuel cell . When the ion exchange capacity is high, the conductivity of the ions is improved, so that practical advantages such as improvement of the power generation performance of the polymer electrolyte fuel cell and reduction of 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 constitutional unit derived from a fluorosulfonyl group-containing monomer represented by the following formula (m2) and a constitutional unit derived from tetrafluoroethylene ( sulfonic acid group-containing polymer obtained by converting the -SO ₂ F) to 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. And 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.

Patent No. 5141251 gazette

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 two-step process (US Pat. No. 4,273,729) and the like, in Example 2 of Patent Document 1, CF ₂ CFCFCF ₂ OCF ₂ CF ₂ SO ₂ F is further synthesized to the target fluorosulfonyl group-containing monomer. Four steps are required, for a total of six steps. Therefore, the fluorosulfonyl group-containing monomer represented by the formula (m2) takes time to produce.

  INDUSTRIAL APPLICABILITY The present invention can obtain a sulfonic acid group-containing polymer having a high ion exchange capacity, and can produce a fluorosulfonyl group-containing monomer which can be produced in a small number of synthesis steps, and a fluorosulfonyl group containing a sulfonic acid 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 membrane 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 a 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 the R ^f1 is —CF ₂ CF ₂ —.
[5] A fluorosulfonyl group-containing polymer having a structural unit derived from the fluorosulfonyl group-containing monomer according to any one of the above [1] to [4].
[6] The fluorosulfonyl group-containing polymer of [5], further having a constitutional unit derived from tetrafluoroethylene.
[7] A sulfonic acid group-containing polymer obtained by converting the fluorosulfonyl group of the fluorosulfonyl group-containing polymer of the above [5] or [6] into a sulfonic acid group.
[8] A liquid composition comprising the sulfonic acid group-containing polymer of the above [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 the catalyst layer, and a solid 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 catalyst layer of the cathode, the catalyst layer of the anode, and the solid polymer electrolyte membrane contains a sulfonic acid group-containing polymer of [7].
[10] A fluorosulfonyl group-containing monomer obtained by adding a fluoride salt 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) 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 a perfluoroalkylene group, and X is a fluorine atom or a fluorosulfonyl group.
[11] A method for producing a fluorosulfonyl group-containing monomer according to [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 according to [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 the R ^f1 is —CF ₂ CF ₂ —.
[15] A fluorosulfonyl group-containing monomer is produced by the production method of any of the above [10] to [14], and a monomer component containing the fluorosulfonyl group-containing monomer is polymerized to derive from the fluorosulfonyl group-containing monomer The manufacturing method of the fluorosulfonyl group containing polymer which obtains the fluorosulfonyl group containing polymer which has a structural unit.
[16] The method for producing a fluorosulfonyl group-containing polymer of [15], wherein the monomer component further comprises tetrafluoroethylene.
[17] A fluorosulfonyl group-containing polymer is produced by the production method of the above [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 , And a method of producing a sulfonic acid group-containing polymer.
[18] A method for producing a liquid composition, wherein a sulfonic acid group-containing polymer is produced by the production method of the above [17], and the sulfonic acid group-containing polymer and a liquid medium are mixed 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 solid polymer electrolyte membrane disposed between the anode and the cathode. It is a method of manufacturing, and a liquid composition is manufactured by the manufacturing method of [18], the liquid composition and a catalyst are mixed to prepare a coating liquid for forming a catalyst layer, and the coating liquid is used. A method of producing a membrane electrode assembly, wherein a catalyst layer of 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 the catalyst layer, and a solid polymer electrolyte membrane disposed between the anode and the cathode. A method for producing a membrane electrode assembly, comprising producing a liquid composition according to the production method of [18], and forming the solid polymer electrolyte membrane 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. In addition, 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 membrane 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 a small number of 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, it is possible to produce a sulfonic acid group-containing polymer having a high ion exchange capacity.
According to the method for producing a liquid composition of the present invention, it is possible to produce a liquid composition capable of forming a membrane containing a polymer having a high ion exchange capacity.
According to the method for producing a membrane electrode assembly of the present invention, a membrane electrode assembly having excellent 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, the compound represented by the formula (m1) is referred to as a compound (m1). The compounds represented by other formulas are similarly described.
In the present specification, the constituent unit represented by the formula (u1) is referred to as a constituent unit (u1). The constituent units represented by other formulas are similarly described.
The following definitions of terms apply throughout the specification and claims.
"Polymer" means a compound having a structure composed of a plurality of constituent units.
The "constituent unit" means a unit derived from the 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 to another structure by treating a polymer.
The term "monomer" means a compound having a polymerizable carbon-carbon double bond.
The "perfluoroallyl agent", CF 2 ₌ CFCF 2 _- means a compound capable of introducing the structure represented by the other compounds.

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

  n is preferably 0 or 1, from the viewpoint of enabling synthesis in shorter steps.

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, it can be synthesized in a shorter step, from the viewpoint of higher ion-exchange capacity can be obtained, _-CF 2 CF ₂ - is preferred.

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

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

<Method for producing compound (m1)>
The production method of the compound (m1) is a method of obtaining a 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 embodiments are also the same. MF is a fluoride salt.
In the reaction of a compound having a conventional perfluoro-β-sultone skeleton with 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, applying this procedure the compound (14) in the reaction with perfluoroallyl _{agent, MO-CF 2 -CF (SO} 2 F) - decomposition of the structure occurs, it is impossible to obtain the compound (m1) at all. In the present invention, the compound (m1) can be obtained by adding a fluoride salt to a solution in which the compound (14) and the perfluoroallylating agent are mixed in advance.

It is preferable that the liquid which mixed the compound (14) and the perfluoro allylating agent contains an aprotic polar solvent.
Examples of the aprotic polar solvent include monoglyme, diglyme, triglyme, tetraglyme, acetonitrile, propionitrile, adiponitrile, adiponitrile, benzonitrile, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, 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 from the viewpoint of reactivity and cost, cesium fluoride and potassium fluoride are preferable.
The fluoride salt may be added all at once to the mixed solution of 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.

(Perfluoro allylation agent)
As the perfluoroallylating agent, compound (12) is preferred 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 in terms of availability of raw materials, reactivity of perfluoro allylation, and ease of synthesis.
_{CF 2 = CFCF 2 -OSO 2 F} (12-1)
The manufacturing method of a compound (12-1) is mentioned later.

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

However, n, R ^f1 and X are as described above, and preferred embodiments are also the same.
As the compound (14), the compounds (14-1) to (14-10) are preferable in terms of availability of raw materials, ease of purification by distillation of the compound (14), ease of synthesis and cost. Compound (14-1) is more preferred. However, x is an integer of 1 or more.

(Compound (13))
As the compound (13), the compounds (13-1) to (13-10) are preferable in terms of availability of raw materials, ease of purification by distillation of the 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.

The compound (13-1) can be produced by the method described in U.S. Pat. No. 4,273,729, U.S. Patent Application Publication No. 2005/0037265, JP-A No. 2010-018674 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. obtained by reacting a _{FC (= O) CF 2 SO} 2 F and.

FC (= O) CF ₂ SO ₂ F is reacted with tetrafluoroethylene and sulfur trioxide to obtain tetrafluoro-β-sultone, which is opened by adding a fluoride salt to tetrafluoro-β-sultone It is obtained by

A compound (13-2) can be manufactured by the method similar to the method as described in Example 10 of Unexamined-Japanese-Patent No. 2004-26800. Specifically, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ I is obtained by dehalogenation in the presence of a metal having reducibility such as magnesium. CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ I is obtained by telomerization of CF ₃ I with tetrafluoroethylene.

In the telomerization of CF ₃ CF ₂ I with tetrafluoroethylene, the compound (13-3) is an iodinated compound CF ₃ CF _2- (with different numbers of carbon atoms, by appropriately selecting the preparation equivalent of tetrafluoroethylene). After CF ₂ CF ₂ ) _x -I is obtained, it is obtained by dehalogenating the iodinated compound.

Compound (13-4) can be produced by the method described in Example 1 of JP-A-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 sulfinized in the presence of sodium adithionite to CF ₂ ClCFClCF ₂ CF ₂ SO _{2 2} Na is obtained and reacted with chlorine in water to obtain CF ₂ ClCF ClCF ₂ CF ₂ SO ₂ Cl, and halogen exchanged in the presence of potassium fluoride to obtain CF ₂ ClCFClCF ₂ CF ₂ SO ₂ F Finally, it is obtained by dechlorination in the presence of zinc.

Compound (13-5) was prepared by the same method 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 possible 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.

  Compounds (13-6) to (13-8) are described in Molecules, 2011, 16, p. It can manufacture by the method as described in 6512-6540. Specifically, it is obtained by adding a perfluoroallylizing agent to a mixture of perfluoroalkylcarboxylic acid fluorides of various carbon numbers and fluoride salts and reacting them.

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

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

(Mechanism of action)
Since the compound (m1) described above is a compound having a relatively low molecular weight, a sulfone obtained by converting the fluorosulfonyl group of the 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 in the compound (m1) is a fluorosulfonyl group, the molecular weight per sulfonic acid group in the sulfonic acid group-containing polymer can be further lowered. Therefore, a sulfonic acid group-containing polymer having a high ion exchange capacity can be obtained.
Further, in the method for producing the compound (m1) described above, the compound (14) obtained by a relatively small number of synthesis steps is used. For example, the synthesis step from compound (11) to compound (14-1) is three steps. Therefore, a compound (m1-1) can be manufactured by few synthetic | combination steps (4 steps).

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

However, n, R ^f1 and X are as described above, and preferred embodiments are also the same.
As the structural unit (u1), structural unit (u1-1) to structural unit (u1-10) from the viewpoint of availability of raw materials, ease of purification by distillation of compound (m1), simplicity of synthesis, and cost Are preferred, and structural unit (u1-1) is more preferred. 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 a sulfonic acid group-containing polymer to be described later is hydrated, 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 compound (m1) and another monomer other than 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), as described in WO 2011/013578 The perfluoropolymer etc. which have a 5 membered ring are mentioned.

  The proportion of the structural unit (u1), the structural unit derived from TFE, and the structural unit derived from another monomer out of 100 mol% of the total structural units constituting the polymer (F) is required for the sulfonic acid group-containing polymer It may be determined appropriately according to the characteristics (ion exchange capacity, mechanical strength, etc.).

The TQ value of the polymer (F) is preferably 200 to 330 ° C. If the TQ value of the polymer (F) is not less than the above lower limit value, the sulfonic acid group-containing polymer has a sufficient molecular weight and is excellent in mechanical strength. If the TQ value of the polymer (F) is not more than the above upper limit, the solubility or dispersibility of the sulfonic acid group-containing polymer is improved, and it is easy to prepare a liquid composition described later.
The TQ value is an index of the molecular weight of the polymer, and the amount of extrusion when melt extruding the polymer (F) under the conditions of an extrusion pressure of 2.94 MPa using a nozzle with a length of 1 mm and an inner diameter of 1 mm is 100 mm ³ / It is the temperature which becomes a second.

<Method of producing polymer (F)>
The polymer (F) is produced by producing the compound (m1) according to the method for producing the compound (m1) described above, and polymerizing a monomer component containing the compound (m1), and optionally TFE and other monomers. It is a method to obtain (F).

Examples of the polymerization method include known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. The polymerization may also be carried out in liquid or supercritical carbon dioxide.
The polymerization is carried out under conditions that give rise to radicals. Examples of a method of generating a radical include a method of irradiating radiation such as ultraviolet light, γ-ray and electron beam, and a method of adding a radical initiator.
The polymerization temperature is usually 10 to 150 ° C.

  Examples of the radical initiator include bis (fluoroacyl) peroxides, bis (chlorofluoroacyl) peroxides, dialkylperoxydicarbonates, diacylperoxides, peroxyesters, azo compounds, persulfates, etc. Perfluoro compounds such as bis (fluoroacyl) peroxides are preferred from the viewpoint of obtaining a polymer (F) having a small number of stable end groups.

As a solvent used by a solution polymerization method, the solvent which has a boiling point of 20-350 degreeC is preferable, and the solvent which has a boiling point of 40-150 degreeC is more preferable. As the 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, monomers, radical initiators and the like are added to a solvent, and radicals are generated in the solvent to polymerize the monomers. The addition of the monomer and the initiator may be simultaneous addition, sequential addition, or continuous addition.

In the suspension polymerization method, water is used as a dispersion medium, and a monomer, a nonionic radical initiator and the like are added to the dispersion medium to generate radicals in the dispersion medium to polymerize the monomer.
Nonionic radical initiators include bis (fluoroacyl) peroxides, bis (chlorofluoroacyl) peroxides, dialkylperoxydicarbonates, diacylperoxides, peroxyesters, dialkylperoxides, bis (fluoroalkyl) Peroxides, azo compounds and the like can be mentioned.
The dispersion medium may be added with the above-described solvent as an auxiliary agent; a surfactant as a dispersion stabilizer to prevent aggregation of suspended particles; a hydrocarbon compound (hexane, methanol, etc.) as a molecular weight modifier.

(Mechanism of action)
The polymer (F) described above has a structural unit (u1) derived from the compound (m1) having a relatively low molecular weight. Further, in the method for producing the polymer (F) described above, the polymer component (F) is obtained by polymerizing monomer components including the compound (m1) having a relatively low molecular weight. 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 one sulfonic acid group can be lowered. In particular, when X in the compound (m1) is a fluorosulfonyl group, the molecular weight per sulfonic acid group in the sulfonic acid group-containing polymer can be further lowered. Therefore, a sulfonic acid group-containing polymer having a high ion exchange capacity can be obtained.

<Polymer (H)>
The sulfonic acid group-containing polymer (hereinafter also referred to as polymer (H)) of the present invention is a polymer obtained by converting a fluorosulfonyl group of the 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 embodiments are also the same. X 'is a fluorine atom or a sulfonic acid group.
As the structural unit (u′1), from the viewpoint of the availability of raw materials, the ease of purification by distillation of the compound (m1), the simplicity of synthesis, and the cost, structural unit (u′1-1) to 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 constituent unit derived from TFE, and may further contain a constituent unit derived from the compound (m1) and another monomer other than 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. When the ion exchange capacity is at least the lower limit value of the above range, the conductivity of the polymer (H) becomes high, and therefore, when used in the catalyst layer of the polymer electrolyte fuel cell, a sufficient cell output can be obtained. When the ion exchange capacity is not more than the upper limit value of the above range, the swelling when the polymer (H) is hydrated can be suppressed.

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

  As a method of converting a fluorosulfonyl group to a sulfonic acid group, there is mentioned a method of hydrolyzing a fluorosulfonyl group of a polymer (F) to form a sulfonic acid salt and converting the sulfonic acid salt to an acid form to convert it to a sulfonic acid group .

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

(Mechanism of action)
In the polymer (H) described above, since it 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.
Further, in the method for producing the polymer (H) described above, since the fluorosulfonyl group of the polymer (F) is converted to a sulfonic acid group, the polymer (H) having a high ion exchange capacity can be produced.

<Liquid composition>
The liquid composition of the present invention comprises 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 a liquid medium, or one in which the polymer (H) is dissolved in a 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 facilitates the formation of a catalyst layer and a solid polymer electrolyte membrane that are resistant to cracking.

The organic solvent is preferably at least one alcohol having a carbon number of 1 to 4 from the viewpoint of easily forming a catalyst layer and a solid polymer electrolyte membrane that are resistant to cracking.
As the alcohol having 1 to 4 carbon atoms, 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 total (100 mass%) of water and an organic solvent, and, as for the ratio of water, 20-99 mass% is more preferable.
1-90 mass% is preferable among the sum total (100 mass%) of water and an organic solvent, and, as for the ratio of the organic solvent, 1-80 mass% is more preferable.
If the ratio of water and the organic solvent is in the above range, the dispersibility of the polymer having an ion exchange group in the dispersion medium is excellent, and a catalyst layer and a solid polymer electrolyte membrane which are hard to break are easily formed.

  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 at least the lower limit value of the above range, a thick film can be stably obtained at the time of film formation. Moreover, adjustment of the coating liquid for catalyst layer formation at the time of producing a catalyst layer becomes easy. If the concentration of the polymer (H) is equal to or less than the upper limit value of the above range, it is possible to suppress the viscosity of the liquid composition from becoming excessively high.

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

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

Examples of the mixing method include a method of applying shear such as stirring to the polymer (H) in the liquid medium under atmospheric pressure or in a closed state with an autoclave or the like.
0-250 degreeC is preferable and, as for the temperature at the time of stirring, 20-150 degreeC is more preferable. If necessary, shearing such as ultrasonic waves may be applied.

  When applying shear such as stirring to a mixture obtained by mixing the polymer (H) and the liquid medium, shearing such as stirring may be added to the mixture obtained by adding all the liquid medium to the polymer (H) at one time, The liquid medium may be mixed with the polymer (H) in multiple portions, and shear such as stirring may be applied between the portions. For example, shear such as stirring is added to a mixture obtained by adding a part of the liquid medium to the polymer (H), and then the remaining liquid medium is added to the mixture and shear such as stirring is added again. Good. Alternatively, only the organic solvent may be added to the liquid medium and shear such as stirring may be added, and then only water may be added and shear such as stirring may be added again.

(Mechanism of action)
In the liquid composition of the present invention described above, since the polymer (H) capable of increasing the ion exchange capacity is contained, a membrane containing a polymer having a high ion exchange capacity can be formed.
Further, in the method for producing the liquid composition of the present invention described above, the polymer (H) capable of increasing the ion exchange capacity and the liquid medium are mixed to obtain the liquid composition, so the 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 disposed in the closed 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 ion exchange groups.
The catalyst includes 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.
As a polymer which has an ion exchange group, polymer (H), the perfluoro polymer which has a well-known ion exchange group, etc. are mentioned.

(Gas diffusion layer)
The gas diffusion layer has a function to diffuse the gas uniformly to 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 treated to be water repellent by 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 arranging the carbon layer, the gas diffusibility of 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 the carbon include carbon particles and carbon fibers, and carbon nanofibers with 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.
As a polymer which has an ion exchange group, polymer (H), the perfluoro polymer which has a well-known ion exchange group, etc. are mentioned.

  The solid polymer electrolyte membrane may be reinforced with a reinforcing material. The reinforcing material may, for example, be a porous body, a fiber, a woven fabric or a non-woven fabric. Examples of the material 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 causing deterioration of the solid polymer electrolyte membrane. The cerium and manganese are preferably present as ions in the solid polymer electrolyte membrane, and may be present in any state in the solid polymer electrolyte membrane if they are present as ions.

<Method of manufacturing membrane electrode assembly>
When the membrane electrode assembly does not have a carbon layer, the membrane electrode assembly is manufactured, for example, by the following method.
A method of forming a catalyst layer on a solid polymer electrolyte membrane to form a membrane catalyst layer assembly, and sandwiching the membrane catalyst layer assembly with a gas diffusion layer.
A method of forming a catalyst layer on a gas diffusion layer to form an electrode (anode, cathode) and sandwiching a solid polymer electrolyte membrane 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 coated on a substrate film and dried to form a carbon layer, a catalyst layer is formed on the carbon layer, and a catalyst layer and a solid polymer electrolyte membrane And a base film is peeled off to form a membrane catalyst layer assembly having a carbon layer, and the membrane catalyst layer assembly is sandwiched between the gas diffusion layers.
A membrane-catalyst layer assembly in which a dispersion containing carbon and a nonionic fluorine-containing polymer is applied onto a gas diffusion layer and dried to form a carbon layer, and a catalyst layer is formed on a solid polymer electrolyte membrane , A method of sandwiching with a gas diffusion layer having a carbon layer.

(Method of forming catalyst layer)
The following method is mentioned as a formation method of a catalyst layer.
-A method of applying a coating solution for forming a catalyst layer on a solid polymer electrolyte membrane, a gas diffusion layer, or a carbon layer and drying it.
A method of applying a coating solution for forming a catalyst layer on a substrate film, drying it to form a catalyst layer, and transferring the catalyst layer 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 solution for forming a catalyst layer can be prepared, for example, by mixing the liquid composition of the present invention with a dispersion of a catalyst.

(Formation method of solid polymer electrolyte membrane)
The solid polymer electrolyte membrane can be formed, for example, by a method of applying a liquid composition on a base film or a catalyst layer and drying it (cast method).
The liquid composition is a dispersion liquid in which a polymer having ion exchange groups is dispersed in a dispersion medium containing water and an organic solvent. The liquid composition of the present invention may be used as a liquid composition.

  In order to stabilize the solid polymer electrolyte membrane, annealing is preferably performed. 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 annealing temperature is 130 ° C. or higher, the polymer having ion exchange groups will not be excessively hydrated. When the temperature of the annealing treatment is 200 ° C. or less, the thermal decomposition of the ion exchange group is suppressed.

(Mechanism of action)
In the membrane electrode assembly of the present invention described above, a polymer (H) in which at least one selected from the group consisting of a catalyst layer of a cathode, a catalyst layer of an anode and a solid polymer electrolyte membrane can increase ion exchange capacity Power generation performance.
Further, in the method of manufacturing a membrane electrode assembly according to the present invention described above, at least one ion selected from the group consisting of a catalyst layer of a cathode, a catalyst layer of an anode and a solid polymer electrolyte membrane. 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.

Polymer Electrolyte Fuel Cell
A polymer electrolyte fuel cell can be obtained by arranging separators in which grooves serving as gas flow paths are formed on both sides of the membrane electrode assembly of the present invention.
Examples of the separator include separators made of various conductive materials such as metal separators, carbon separators, separators made of a mixture of graphite and resin, and the like.
In a polymer electrolyte fuel cell, power is generated 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 electricity by supplying methanol to the anode.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by 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 reference: CFCl ₃ . The quantification of the product was carried out from the analysis result of ¹⁹ F-NMR and the addition amount of the internal standard sample (1,3-bis (trifluoromethyl) benzene).

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

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

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

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

In a 500 mL four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 235 g of 60% fuming sulfuric acid was charged under a nitrogen seal. The flask was set in an oil bath, and 291 g of compound (13-1) was added dropwise over 20 minutes while maintaining the internal temperature at 35 to 40 ° C. After completion of the addition, a mild exotherm was observed, and the internal temperature rose to 50 ° C. Then, stirring was continued for 28 hours while maintaining the internal temperature at 40 ° C. The reaction solution was cooled to room temperature, transferred to a 500 mL separatory funnel, and allowed to stand to separate into a cloudy upper layer and an orange clear lower layer. After extracting the lower layer, 157 g of concentrated sulfuric acid was added, shaken well and allowed to stand, and then the lower layer was extracted. 31 g of concentrated sulfuric acid was added again, shaken well and allowed to stand, and then the lower layer was extracted. The upper layer of 266 g remaining in the separating funnel was recovered. The recovered upper layer was analyzed by ¹⁹ F-NMR, and quantification was performed based on the amount of the internal standard sample. As a result, it was confirmed that the target compound (14-1) was produced in a yield of 69%. Remaining of the raw material 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 compound (14-1) was 57.1 ° C. under a pressure of 25 mmHg (absolute pressure).

¹⁹ F-NMR spectrum of compound (14-1): 45.80 ppm (SO ₂ F, 1 F, p, J = 6.1 Hz), -76.30 ppm and -77.00 ppm (CF-CF ₂ -O, 2F) , m), - 81.70 (annulus _{CF 2, 1F, dd, J} = 107,7.6Hz), - 88.46ppm ( annulus _{CF 2, 1F, dt, J} = 107,13.0Hz), −81.85 ppm (O—CF ₂ —CF ₂ , 2F, m), −112.50 ppm (CF ₂ —SO ₂ F, 2F, m), −115.51 ppm (annular portion CF, 1 F, p, J = 7.6 Hz).

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

In a 50 mL four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, under a nitrogen blanket, 3.93 g of Compound (12-1), 6.98 g of Compound (14-1), 9 of diglyme I charged .65g. 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. An exotherm was observed upon dripping. After the addition, stirring was continued for 9 hours while maintaining the internal temperature at −40 to −30 ° C., then the cooling was stopped and the temperature was raised to room temperature. The reaction solution was transferred to a 50 mL separatory funnel and allowed to stand to separate 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 quantification was carried out from the amount of addition of the internal standard sample, confirming that the target compound (m1-1) was formed in a yield of 16% did. The main product was compound (13-1) (yield 36%). The results are shown in Table 1.

(Example 4)
Production of Compound (m1-1):
Using 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, using a 1 L reactor, add the internal temperature after addition The reaction was carried out in the same manner as in Example 3 except that the temperature was -50 to -30 ° C. From quantitative analysis of the lower layer (249.8 g) recovered by the liquid separation operation, it was confirmed that the target compound (m1-1) was formed at a yield of 20%. The main product was compound (13-1) (35% yield). The results are shown in Table 1.

  The lower layer collected in Example 3 and Example 4 is transferred to a 500 mL four-necked flask equipped with a stirrer, a thermometer, and a distillation column packed with irregular packing (inner diameter 3 cm × column length 50 cm, packing length 36 cm). 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 compound (m1-1): 55.37 ppm (CF-SO ₂ F, 1 F, m), 45.83 ppm (CF _2- SO ₂ F, 1 F, 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), - 71.88ppm (CF 2 = CF, 1F, ddt, J = 49,39,8Hz), - 103.65ppm (CF 2 = CF , 1F, ddt, J = 118.0, 49, 26 Hz), −112.50 ppm (CF ₂ —SO ₂ F, 2F, m), −164.83 ppm (CF—SO ₂ F, 1 F, m), − 190.83 ppm _{CF 2 = CF, 1F, ddt} , J = 118,39,14Hz).

(Example 5)
Isomerized form of 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 blanket. 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 with stirring using a stirrer. No exotherm was observed at the time of dropping. The cooling was stopped and the internal temperature was returned to room temperature. The inner solution was analyzed by ¹⁹ F-NMR to find that Compound (14-1) was hardly reacted. The flask was heated, and reacted at 100 ° C. for 5 hours. As a result, it was confirmed that Compound (15-1), which is an isomer of Compound (14-1), was formed.

¹⁹ F-NMR spectrum of compound (15-1): 54.3 ppm (CF-SO ₂ F, 1 F, m), 45.6 ppm (CF _2- SO ₂ F, 1 F, 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, also in the compound (14-1) which is a relatively large β-sultone compound having a substituent, the ring-opening reaction occurs similarly to tetrafluoro-β-sultone, and the compound (15-1) is formed. I understand that. That is, even on a substrate having a relatively large substituent, the ring opening reaction itself occurs without any problem.
The reason why the yield of the desired compound (m1-1) is significantly improved by the present invention is considered to be as follows.
The reaction of the compound (14-1) or the compound (15-1) with the fluoride salt (MF) produces an MO-CF ₂ -CF (SO ₂ F) -structure which is an active species in perfluoro allylation. An active species derived from compound (14-1) or compound (15-1) having a relatively large substituent is considered to be poorly stable. 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 is decomposed before the addition of the perfluoroallylating agent to obtain the desired compound (m1-1). It can be considered impossible. On the other hand, as shown in the present invention, when a fluoride salt is added in a state in which compound (14-1) and the perfluoroallylating agent are mixed in advance, the generated active species can be reacted with the perfluoroallylating agent rapidly. It is considered that the yield of the target compound (m1-1) is remarkably improved.

  (Example 6)

In a 50 mL four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 1.05 g of potassium fluoride and 10.52 g of diglyme were charged under a nitrogen seal. The flask was cooled with a refrigerant, and after the internal temperature dropped to -20 ° C, 6.96 g of the compound (14-1) was dropped. An exotherm was observed upon dripping. After continuing stirring at -30 to -10 ° C for 1 hour, 3.93 g of compound (12-1) was added dropwise. After stirring at −20 to −10 ° C. for 1 hour, the cooling was stopped and the internal temperature was allowed to rise to room temperature. After stirring at room temperature for 16 hours, the stirring was stopped. The reaction solution was transferred to a 50 mL separatory funnel and allowed to stand to separate 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 quantification was carried out from the addition amount of the internal standard sample, and it was confirmed that the target compound (m1-1) was formed in a 1% yield. did. The main product was compound (13-1) (50% yield). The results are shown in Table 2.

(Example 7)
The reaction was carried out 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 separation operation, only trace amounts of the target compound (m1-1) could be confirmed. The results are shown in Table 2.

(Example 8)
A reaction was performed 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 separation operation, only trace amounts of the target compound (m1-1) could be confirmed. The results are shown in Table 2.

(Example 9)
In a 50 mL four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 0.77 g of sodium fluoride and 4.06 g of diglyme were charged under a nitrogen seal. The flask was cooled with a refrigerant, and 6.98 g of the compound (14-1) was dropped after the internal temperature dropped to -20 ° C. The 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. No fever was noted. Thereafter, the reaction solution was heated to 70 ° C. while confirming by gas chromatography analysis, but generation 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 (inner volume: 30 mL, manufactured by Hastelloy), 23.0 g of the compound (m1-1) was placed, and the mixture was cooled with liquid nitrogen and degassed. 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 solution of 0.017 g of perfluoro-di-tert-butyl peroxide as a polymerization initiator and 0.921 g of the compound (m1-1) was injected into the autoclave. Furthermore, 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 dilution of TFE in the gas phase by this operation, the pressure increased to 0.90 MPaG. Polymerization was carried out by continuously adding TFE while maintaining the pressure at 0.90 MPaG. When the addition amount of TFE reached 4.2 g in 6.5 hours, the inside of the autoclave was cooled to terminate the polymerization, and the gas in the system was purged. After dilution with a reaction mixture _{HFC-52-13p (CF 3 (CF} 2) 5 H), was added _{HFE-347pc-f (CF 3} CH 2 OCF 2 CF 2 H), and filtered by agglomerating polymer. Thereafter, the polymer was stirred in HFC-52-13p, and the operation of reaggregation with HFE-347pc-f was repeated twice. It vacuum-dried at 120 degreeC, and obtained 7.7 g of polymers (F-1) which are copolymers of TFE and a compound (m1-1).

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

(Example 11)
Production of Polymer (H):
Hydrolysis of the fluorosulfonyl group (-SO ₂ F) in the polymer (F-1) by immersing the film of the polymer (F-1) in a 20% by mass aqueous potassium hydroxide solution at 80 ° C. for 20 hours and it was converted to -SO ₃ K. Furthermore, the membrane of the polymer was immersed in a 3 mol / L aqueous hydrochloric acid solution for 1 hour at room temperature, and then immersed in ultrapure water at room temperature for 30 minutes. The cycle of dipping and immersion in ultra pure water to the aqueous hydrochloric acid solution was performed five times in total, it was converted to -SO 3 _K sulfonic acid group (-SO 3 _H). Thereafter, the ultrapure water washing was repeated until the pH of the water in which the polymer membrane was immersed became 7. Finally, the polymer membrane was sandwiched between filter paper and air dried to obtain a polymer (H) membrane.
The ion exchange capacity of the polymer (H) membrane was determined to be 1.55 meq / g dry resin. The proportions of the constituent unit derived from TFE and the constituent unit derived from the compound (m1-1) in the polymer (F-1) calculated from the ion exchange capacity are 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) membrane and 49.9 g of a mixed solvent (24/33/43 (mass ratio)) of 1-propanol, 1-butanol and water added. The autoclave was heated while 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 27 hours in total. After cooling, pressure filtration (filter paper: PF100, manufactured by Advantec Toyo Kaisha, Ltd.) was performed to obtain a liquid composition in which the polymer (H) was dispersed in a 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 300 μm thick solid polymer electrolyte membrane made of polymer (H).

The fluorosulfonyl group-containing monomer of the present invention can be used as a catalyst layer or a solid polymer electrolyte membrane in a solid polymer fuel cell or a membrane electrode assembly for solid polymer type water electrolysis, or a positive electrode used in alkaline chloride electrolysis or It is useful as a raw material of the polymer contained in an ion exchange membrane etc.
The fluorosulfonyl group-containing monomer of the present invention is also useful as a raw material of a polymer contained in a diaphragm for a redox flow secondary battery.

  10 membrane electrode assembly, 11 catalyst layer, 12 gas diffusion layer, 13 anode, 14 cathode, 15 solid polymer electrolyte membrane, 16 carbon layer.

Claims (11)

A method for producing a fluorosulfonyl group-containing monomer, which adds a fluoride salt 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 a perfluoroalkylene group, and X is a fluorine atom or a fluorosulfonyl group. The method for producing a fluorosulfonyl group-containing monomer according to claim 1 , wherein the perfluoroallylizing 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 manufacturing method of the fluoro sulfonyl group containing monomer of Claim 1 or 2 whose said X is a fluoro sulfonyl group. The method for producing a fluorosulfonyl group-containing monomer according to any one of claims 1 to 3 , 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 1 to 4. A fluorosulfonyl group-containing monomer is produced by the production method according to any one of claims 1 to 5 , and a structural unit derived from the fluorosulfonyl group-containing monomer by polymerizing a monomer component containing the fluorosulfonyl group-containing monomer. The manufacturing method of a fluoro sulfonyl group containing polymer which obtains the fluoro sulfonyl group containing polymer which has these. The method for producing a fluorosulfonyl group-containing polymer according to claim 6 , wherein the monomer component further comprises tetrafluoroethylene. A sulfonic acid group is obtained by producing a fluorosulfonyl group-containing polymer by the production method according to claim 6 or 7 , and converting the fluorosulfonyl group of the fluorosulfonyl group-containing polymer into a sulfonic acid group to obtain a sulfonic acid group-containing polymer Method for producing containing polymer. The manufacturing method of the liquid composition which manufactures a sulfonic-acid-group containing polymer by the manufacturing method of Claim 8 , 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 of manufacturing a membrane / electrode assembly for a polymer electrolyte fuel cell, comprising: a solid polymer electrolyte membrane disposed between the anode and the cathode.
A liquid composition is produced by the production method according to claim 9 , and the liquid composition and a catalyst are mixed to prepare a coating liquid for forming a catalyst layer, and the cathode and the anode are produced using the coating liquid. A method of producing a membrane electrode assembly, wherein one or both catalyst layers are formed. An anode having a catalyst layer,
A cathode having a catalyst layer,
A method of manufacturing a membrane / electrode assembly for a polymer electrolyte fuel cell, comprising: a solid polymer electrolyte membrane disposed between the anode and the cathode.
The manufacturing method of the membrane electrode assembly which manufactures a liquid composition by the manufacturing method of Claim 9 , and forms the said solid polymer electrolyte membrane using this liquid composition.

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