JP2002212234A - Production method for fluorine-containing sulfonimide polymer - Google Patents
Production method for fluorine-containing sulfonimide polymerInfo
- Publication number
- JP2002212234A JP2002212234A JP2001013464A JP2001013464A JP2002212234A JP 2002212234 A JP2002212234 A JP 2002212234A JP 2001013464 A JP2001013464 A JP 2001013464A JP 2001013464 A JP2001013464 A JP 2001013464A JP 2002212234 A JP2002212234 A JP 2002212234A
- Authority
- JP
- Japan
- Prior art keywords
- represented
- formula
- fluorine
- monomer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、スルホンイミド構
造を有する含フッ素スルホンイミドポリマーの製造方法
に関する。[0001] The present invention relates to a method for producing a fluorine-containing sulfonimide polymer having a sulfonimide structure.
【０００２】[0002]
【従来の技術】従来、燃料電池等の電気化学セルの電解
質膜や電極を構成材料としてスルホン酸基を有する含フ
ッ素ポリマーが使用されている。このポリマーはその耐
熱性の観点から使用可能な温度範囲が約１５０℃以下に
制限されており、それに伴いこれを電解質膜や電極の構
成材料とする燃料電池等の電気化学セルの作動温度も上
記範囲に制限されている。そこで、従来のスルホン酸基
を有する含フッ素ポリマーよりも耐熱性の優れたポリマ
ーの開発が期待されており、様々な検討がなされてい
る。2. Description of the Related Art Conventionally, a fluorine-containing polymer having a sulfonic acid group has been used as a constituent material of an electrolyte membrane or an electrode of an electrochemical cell such as a fuel cell. From the viewpoint of the heat resistance of this polymer, the usable temperature range is limited to about 150 ° C. or less, and accordingly, the operating temperature of an electrochemical cell such as a fuel cell using the polymer as a constituent material of an electrolyte membrane or an electrode is also described above. Limited to range. Therefore, development of a polymer having better heat resistance than a conventional fluorinated polymer having a sulfonic acid group is expected, and various studies have been made.
【０００３】例えば、燃料電池等の電気化学セルに有用
なポリマーとして米国特許5,463,005号公報には、下記
式（８）で表される基を側鎖に有する含フッ素ポリマー
が提案されている。ただし、下記式（８）中、Ｊは水
素、アルカリ金属及びアルカリ土類金属から選択される
いずれかを示し、Ｒf3はパーフルオロアルキル基であっ
て、−ＳＯ2ＮＪＳＯ2−で表される基を含んでいてもよ
い。 −ＳＯ2ＮＪＳＯ2−Ｒf3 …（８）For example, US Pat. No. 5,463,005 proposes a fluorine-containing polymer having a group represented by the following formula (8) in a side chain as a polymer useful for an electrochemical cell such as a fuel cell. However, in the following formula (8), J represents any one selected from hydrogen, an alkali metal and an alkaline earth metal, and R f3 is a perfluoroalkyl group and is represented by —SO 2 NJSO 2 —. It may contain a group. -SO 2 NJSO 2 -R f3 (8)
【０００４】更に、最近、この含フッ素スルホンイミド
ポリマーを燃料電池に適用した例も報告されている(The
3rd International Fuel Cell Conference, Nagoya, P
roceedings, p129-p132,(1999))。Further, recently, there has been reported an example in which the fluorine-containing sulfonimide polymer is applied to a fuel cell (The Thermistor).
3rd International Fuel Cell Conference, Nagoya, P
roceedings, p129-p132, (1999)).
【０００５】なお、本明細書においては、上記式（８）
中及び後述の式（１）中に記載されているような、−Ｓ
Ｏ2ＮＨＳＯ2−で表される基及び該−ＳＯ2ＮＨＳＯ2−
で表される基の水素原子が１価の陽イオンで置換された
基を「スルホンイミド基」とよぶ。In this specification, the above equation (8)
-S, as described in formula (1) below and
A group represented by O 2 NHSO 2 — and the —SO 2 NHSO 2 —
The group in which the hydrogen atom of the group represented by is replaced with a monovalent cation is referred to as a “sulfonimide group”.
【０００６】このスルホンイミド基を有する含フッ素ポ
リマー（以下、含フッ素スルホンイミドポリマーとい
う）は従来のスルホン酸基を有する含フッ素ポリマーよ
りも耐熱性が高いという特徴を有しており、これを燃料
電池等の電気化学セルの電解質膜や電極の構成材料とし
て使用することにより、これらの電気化学セルの耐久性
を従来よりも向上させることや、作動温度を従来よりも
高くして該電気化学セルを含む複合システム全体のエネ
ルギー変換効率を高くできること等を期待することがで
きる。そして、従来、上記の含フッ素スルホンイミドポ
リマーはスルホンイミド基を側鎖に有するモノマーと、
テトラフルオロエチレンとの重合によって合成されてい
る。[0006] The fluorine-containing polymer having a sulfonimide group (hereinafter referred to as fluorine-containing sulfonimide polymer) has a feature that its heat resistance is higher than that of a conventional fluorine-containing polymer having a sulfonic acid group. By using as a constituent material of an electrolyte membrane or an electrode of an electrochemical cell such as a battery, the durability of the electrochemical cell can be improved as compared with the conventional one, or the operating temperature can be increased to increase the electrochemical cell. It can be expected that the energy conversion efficiency of the entire complex system including the above can be increased. And conventionally, the above-mentioned fluorine-containing sulfonimide polymer has a monomer having a sulfonimide group in a side chain,
It is synthesized by polymerization with tetrafluoroethylene.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、高分子
量の含フッ素スルホンイミドポリマーを高収率で再現性
良く得るためには高純度のモノマーを使用し重合反応さ
せる必要があるが、原料の一つであるスルホンイミド基
を有するモノマーは、−ＳＯ2Ｆ基を有するモノマーを
出発原料として合成されているので、多段の合成反応の
組み合わせが必要となっていた。そのため、その製造工
程が煩雑で手間がかかるうえに高純度かつ高収率で得る
ことが困難であるという問題があった。また、スルホン
イミド基を有するモノマーは沸点が高く蒸留精製する際
に不利であり、この点においてもスルホンイミド基を有
するモノマーを高純度かつ高収率で再現性よく得ること
が困難であった。However, in order to obtain a high-molecular-weight fluorine-containing sulfonimide polymer with high yield and good reproducibility, it is necessary to use a high-purity monomer for the polymerization reaction. Since the monomer having a sulfonimide group is synthesized using a monomer having a —SO 2 F group as a starting material, a combination of multistage synthesis reactions is required. Therefore, there is a problem that the production process is complicated and troublesome, and it is difficult to obtain a high purity and a high yield. Further, a monomer having a sulfonimide group has a high boiling point and is disadvantageous in distillation purification. In this respect, it is also difficult to obtain a monomer having a sulfonimide group with high purity and high yield with good reproducibility.
【０００８】例えば、スルホンイミド基を有するモノマ
ーとして、ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（Ｃ
Ｆ2）2ＳＯ2ＮＨＳＯ2ＣＦ3を合成する場合には、ＣＦ2
＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）Ｏ（ＣＦ2）2ＳＯ2Ｆを出
発原料とし、下記のスキームＡに示すような多段の合成
反応を必要としていた。For example, as a monomer having a sulfonimide group, CF 2 ＣＦCFOCF 2 CF (CF 3 ) O (C
When synthesizing F 2 ) 2 SO 2 NHSO 2 CF 3 , CF 2
= CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 2 F was used as a starting material, and a multi-stage synthesis reaction as shown in the following scheme A was required.
【化３】 Embedded image
【０００９】また、−ＳＯ2Ｆ基を有するポリマーを出
発原料とした下記のスキームＢに示すような合成方法も
考えられるが、この方法においては多段の高分子反応を
必要とし、スルホンイミド基を高純度で導入することは
困難である。なお、下記のスキームＢにおいては、−Ｓ
Ｏ2Ｆ基を有するポリマーの−ＳＯ2Ｆ基以外の分子構造
をＰとし、Ｐ−ＳＯ2Ｆとして示す。Further, a synthesis method as shown in the following scheme B using a polymer having a —SO 2 F group as a starting material is also conceivable. However, this method requires a multistage polymer reaction and requires a sulfonimide group. It is difficult to introduce with high purity. In the following scheme B, -S
O 2 F molecular structure other than -SO 2 F groups in the polymer having a group a is P, shown as a P-SO 2 F.
【化４】 Embedded image
【００１０】更に、スルホンイミド基を有するモノマー
はパーフルオロの非極性部位と極性の大きい官能基とを
有するため溶液重合のための適当な溶媒を見出すのが困
難である。乳化重合が報告されているが、再現性に課題
がある(Polym. Mater. Sci.Eng, (1999) 80 598-599)。Further, since a monomer having a sulfonimide group has a non-polar part of perfluoro and a highly polar functional group, it is difficult to find a suitable solvent for solution polymerization. Although emulsion polymerization has been reported, there is a problem in reproducibility (Polym. Mater. Sci. Eng, (1999) 80 598-599).
【００１１】本発明は、上記従来技術の有する課題に鑑
みてなされたものであり、高純度の含フッ素スルホンイ
ミドポリマーをシンプルな合成反応により容易にかつ高
収率で得ることのできる製造方法を提供することを目的
とする。The present invention has been made in view of the above-mentioned problems of the prior art, and provides a method for producing a high-purity fluorine-containing sulfonimide polymer easily and in a high yield by a simple synthesis reaction. The purpose is to provide.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意研究を重ねた結果、−ＳＯ2Ｆ基を有
するポリマーを原料とし、特定のスルホンアミド又はそ
の誘導体を作用させることにより、当該共重合体中の−
ＳＯ2Ｆ基をスルホンイミド基に容易にかつ高収率で変
換できることを見出し、本発明に到達した。Means for Solving the Problems The present inventors have found, after intensive studies to achieve the above object, a polymer having a -SO 2 F group as a starting material, the action of certain sulfonamide or derivative thereof By this,-in the copolymer
The present inventors have found that an SO 2 F group can be easily converted into a sulfonimide group with high yield, and have reached the present invention.
【００１３】すなわち、本発明は、下記式（１）で表さ
れるモノマー／テトラフルオロエチレン共重合体である
含フッ素スルホンイミドポリマーの製造方法であって、
下記式（２）で表されるモノマー／テトラフルオロエチ
レン共重合体と下記式（３）又は（４）で表される化合
物とを化学反応させる工程を経ることを特徴とする含フ
ッ素スルホンイミドポリマーの製造方法を提供する。 ＣＦ2＝ＣＦＲf1ＳＯ2ＮＸＳＯ2Ｒf2 …（１） ＣＦ2＝ＣＦＲf1ＳＯ2Ｆ …（２） Ｒf2ＳＯ2ＮＨ2 …（３） （Ｒf2ＳＯ2ＮＳｉＲ1Ｒ2Ｒ3）-Ｅ+ …（４）That is, the present invention provides a method for producing a fluorine-containing sulfonimide polymer which is a monomer / tetrafluoroethylene copolymer represented by the following formula (1):
A fluorine-containing sulfonimide polymer, which undergoes a step of chemically reacting a monomer / tetrafluoroethylene copolymer represented by the following formula (2) with a compound represented by the following formula (3) or (4): And a method for producing the same. CF 2 = CFR f1 SO 2 NXSO 2 R f2 (1) CF 2 = CFR f1 SO 2 F (2) R f2 SO 2 NH 2 (3) (R f2 SO 2 NSiR 1 R 2 R 3 ) - E + ... (4)
【００１４】ここで、式（１）〜（４）中、Ｘは水素原
子又はアルカリ金属原子であり、Ｒ f1は単結合若しくは
直鎖又は分岐構造を有するパーフルオロアルキレン基で
あって、エーテル結合性の酸素原子を含んでいてもよ
く、Ｒf2は直鎖又は分岐構造を有するパーフルオロアル
キル基であって、エーテル結合性の酸素原子及び／又は
−ＳＯ2ＮＸＳＯ2−で表される基を含んでいてもよく、
Ｒ1、Ｒ2及びＲ3はアルキル基であって、それぞれ同一
であっても異なっていてもよく、Ｅ+は1価の陽イオンで
ある。In the formulas (1) to (4), X is a hydrogen atom
R or an alkali metal atom; f1Is a single bond or
With a perfluoroalkylene group having a linear or branched structure
Yes, it may contain an etheric oxygen atom
K, Rf2Is a perfluoroal having a linear or branched structure
A kill group, an etheric oxygen atom and / or
-SOTwoNXSOTwoMay include a group represented by-
R1, RTwoAnd RThreeIs an alkyl group, each being the same
Or different, E+Is a monovalent cation
is there.
【００１５】なお、本明細書において、Ａ／Ｂ共重合体
とは、モノマーＡに基づく繰り返し単位とモノマーＢに
基づく繰り返し単位とからなる共重合体を示すものとす
る。In this specification, the term "A / B copolymer" refers to a copolymer composed of a repeating unit based on monomer A and a repeating unit based on monomer B.
【００１６】従来のようにスルホンイミド基を有するモ
ノマーを合成し、これとテトラフルオロエチレンを重合
させる場合と異なり、本発明においては、−ＳＯ2Ｆ基
を有するポリマーである上記（２）で表されるモノマー
／テトラフルオロエチレン共重合体を原料とし、これに
式（４）で表される化合物を作用させるか又はアミンや
アルカリ金属水酸化物等の塩基の存在下で式（３）で表
される化合物を作用させることにより、共重合体中の−
ＳＯ2Ｆ基を直接−ＳＯ2ＮＸ’ＳＯ2Ｒf2基に変換する
ことができる。ここで、Ｘ’は式（４）におけるＥ又は
共存する塩基において陽イオンとなる金属原子（アルカ
リ金属原子等）である。そのため、式（１）中の−ＳＯ
2ＮＸＳＯ2−で表されるスルホンイミド基を有する含フ
ッ素スルホンイミドポリマーを高純度な状態で然もシン
プルな合成反応により容易にかつ高収率で合成すること
ができる。なお、ＸとＸ’とが異なる場合はＸ+イオン
を含有する溶液に−ＳＯ2ＮＸ’ＳＯ2Ｒf2基を有する含
フッ素スルホンイミドポリマーを浸漬することにより容
易に−ＳＯ2ＮＸＳＯ2−に変換できる。Unlike the conventional method of synthesizing a monomer having a sulfonimide group and polymerizing it with tetrafluoroethylene, in the present invention, a polymer having a -SO 2 F group is represented by the above (2). The monomer / tetrafluoroethylene copolymer is used as a raw material, and the compound represented by the formula (4) is allowed to act thereon, or the compound represented by the formula (3) is used in the presence of a base such as an amine or an alkali metal hydroxide. By acting the compound to be reacted,-in the copolymer
It is possible to convert the SO 2 F group directly -SO 2 NX'SO 2 R f2 groups. Here, X ′ is E in the formula (4) or a metal atom (eg, an alkali metal atom) that becomes a cation in the coexisting base. Therefore, -SO in equation (1)
A fluorine-containing sulfonimide polymer having a sulfonimide group represented by 2 NXSO 2- can be easily synthesized in a high purity state by a simple synthesis reaction in a high yield. When X and X ′ are different from each other, the fluorinated sulfonimide polymer having a —SO 2 NX′SO 2 R f2 group is immersed in a solution containing an X + ion to easily form —SO 2 NXSO 2 —. Can be converted.
【００１７】[0017]
【発明の実施の形態】以下、本発明の含フッ素スルホン
イミドポリマーの製造方法の好適な実施形態について詳
細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the method for producing a fluorine-containing sulfonimide polymer according to the present invention will be described below in detail.
【００１８】本発明の含フッ素スルホンイミドポリマー
の原料は、先に述べた式（２）で表されるモノマー／テ
トラフルオロエチレン共重合体と、式（３）又は（４）
で表されるパーフルオロスルホンアミド又はその誘導体
である。先ず、式（２）で表されるモノマー／テトラフ
ルオロエチレン共重合体につて説明する。この共重合体
は、式（２）で表されるモノマーとテトラフルオロエチ
レンとを共重合させることにより合成される。この共重
合体は高純度かつ高収率で再現性よく合成することがで
きる。この共重合体の合成方法は特に限定されず、バル
ク重合、溶液重合、乳化重合、懸濁重合等の公知の方法
を使用することができる。また、使用する式（２）で表
されるモノマー／テトラフルオロエチレン共重合体の形
態は特に限定されず、例えば、粉体状であってもよい、
膜状であってもよい、ペレット状であってもよい。The raw material of the fluorinated sulfonimide polymer of the present invention comprises the above-mentioned monomer / tetrafluoroethylene copolymer represented by the formula (2) and the formula (3) or (4)
Or a perfluorosulfonamide or a derivative thereof. First, the monomer / tetrafluoroethylene copolymer represented by the formula (2) will be described. This copolymer is synthesized by copolymerizing the monomer represented by the formula (2) with tetrafluoroethylene. This copolymer can be synthesized with high purity and high yield with good reproducibility. The method for synthesizing the copolymer is not particularly limited, and known methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used. Further, the form of the monomer / tetrafluoroethylene copolymer represented by the formula (2) to be used is not particularly limited, and may be, for example, a powder form.
It may be in the form of a film or a pellet.
【００１９】ここで、式（２）で表されるモノマーは、
下記式（５）で表されるモノマーであることが好まし
い。ただし、下記式（５）中、ｍは０〜３の整数、ｎは
１〜１２の整数、Ｙはフッ素原子又はトリフルオロメチ
ル基をそれぞれ示す。Here, the monomer represented by the formula (2) is
It is preferably a monomer represented by the following formula (5). However, in the following formula (5), m represents an integer of 0 to 3, n represents an integer of 1 to 12, and Y represents a fluorine atom or a trifluoromethyl group.
【化５】 Embedded image
【００２０】式（５）で表されるモノマーは、蒸留精製
が容易であり、高純度品を容易に入手することできる。
上記式（５）で表されるモノマーの好ましい例として
は、下記化学式（１１）〜（１３）で表されるモノマー
が挙げられる。ここで、下記化学式（１１）〜（１３）
中、ｑは１〜８の整数、ｒは１〜８の整数、ｓは２又は
３をそれぞれ示す。The monomer represented by the formula (5) can be easily purified by distillation, and a high-purity product can be easily obtained.
Preferred examples of the monomer represented by the above formula (5) include monomers represented by the following chemical formulas (11) to (13). Here, the following chemical formulas (11) to (13)
In the formula, q represents an integer of 1 to 8, r represents an integer of 1 to 8, and s represents 2 or 3, respectively.
【化６】 Embedded image
【００２１】更に、上記化学式（１１）〜（１３）で表
されるモノマーの中では、下記式（６）で表されるモノ
マーと、下記式（９）で表されるモノマーとが更に好ま
しい。Further, among the monomers represented by the chemical formulas (11) to (13), a monomer represented by the following formula (6) and a monomer represented by the following formula (9) are more preferable.
【化７】 Embedded image
【００２２】また、以上説明した式（２）で表されるモ
ノマーに関して、他の好ましい例としては、ＣＦ2＝Ｃ
ＦＣＦ2ＯＣＦ2ＣＦ2ＳＯ2Ｆが挙げられる。Another preferred example of the monomer represented by the above formula (2) is CF 2 ＣC
FCF 2 OCF 2 CF 2 SO 2 F is mentioned.
【００２３】更に、式（２）で表されるモノマー／テト
ラフルオロエチレン共重合体に含まれる−ＳＯ2Ｆ基の
含有量は、当該共重合体の構造安定性が保持可能であれ
ば特に限定されず、この共重合体から得られる含フッ素
スルホンイミドポリマーの用途に応じて適した−ＳＯ2
Ｆ基の含有量を有する共重合体を使用すればよい。例え
ば、含フッ素スルホンイミドポリマーを固体高分子型燃
料電池の電極構成材料又は電解質膜として使用する場合
には、これの原料となる式（２）で表されるモノマー／
テトラフルオロエチレン共重合体中の−ＳＯ2Ｆ基の含
有量は、−ＳＯ2Ｆ基を−ＳＯ3Ｈ基に変換した場合のイ
オン交換容量（以下、ＡRとする）として表現すると、
０．５〜２．０ミリ当量／ｇ乾燥樹脂（以下、ｍｅｑ．
／ｇとする）であることが好ましく、０．７〜１．５ｍ
ｅｑ．／ｇであることがより好ましい。Further, the content of the -SO 2 F group contained in the monomer / tetrafluoroethylene copolymer represented by the formula (2) is not particularly limited as long as the structural stability of the copolymer can be maintained. However, depending on the use of the fluorinated sulfonimide polymer obtained from this copolymer, -SO 2
A copolymer having an F group content may be used. For example, when a fluorine-containing sulfonimide polymer is used as an electrode constituent material or an electrolyte membrane of a polymer electrolyte fuel cell, the monomer / monomer represented by the formula (2),
The content of -SO 2 F groups in the tetrafluoroethylene copolymer, the ion exchange capacity in the case of converting -SO 2 F groups into -SO 3 H groups (hereinafter referred to as A R) is expressed as,
0.5 to 2.0 meq / g dry resin (hereinafter, meq.
/ G), preferably 0.7 to 1.5 m
eq. / G is more preferable.
【００２４】ＡRが０．５ｍｅｑ．／ｇ未満となると、
この共重合体から得られる含フッ素スルホンイミドポリ
マーのイオン伝導性が不十分となるので、例えば、固体
高分子型燃料電池の電極の構成材料として使用する場
合、十分な反応サイトを確保することが困難になり、電
極の分極特性が低下し易い。また、電解質膜として使用
する場合にも、電解質抵抗が大きくなり、十分な電池の
出力特性が得られないおそれがある。一方、ＡRが２．
０ｍｅｑ．／ｇを超えると、この共重合体から得られる
含フッ素スルホンイミドポリマー中のイオン交換基の密
度が増大するので、電極の構成材料として使用する場
合、電極におけるガス拡散性或いは排水性が低下し、水
が電極のガス拡散に有効な細孔を閉塞してしまうフラッ
ディングが発生し易くなる。また、電解質膜として使用
する場合には、膜としての強度が低下してしまい、これ
を用いて電池を構成することが困難となり易い。A R is 0.5 meq. / G is less than
Since the ionic conductivity of the fluorinated sulfonimide polymer obtained from this copolymer becomes insufficient, for example, when used as a constituent material of an electrode of a polymer electrolyte fuel cell, it is necessary to secure a sufficient reaction site. It becomes difficult, and the polarization characteristics of the electrode tend to deteriorate. Also, when used as an electrolyte membrane, the electrolyte resistance may increase and sufficient output characteristics of the battery may not be obtained. On the other hand, AR is 2.
0 meq. / G, the density of ion exchange groups in the fluorinated sulfonimide polymer obtained from this copolymer increases, so that when used as a constituent material of an electrode, the gas diffusion property or drainage property of the electrode decreases. In addition, flooding in which water blocks pores effective for gas diffusion of the electrode is likely to occur. In addition, when used as an electrolyte membrane, the strength of the membrane is reduced, and it is easy to configure a battery using the membrane.
【００２５】上記ポリマーは、式（３）で表されるパー
フルオロスルホンアミド又は式（４）で表されるパーフ
ルオロスルホンアミドの誘導体と反応することにより、
含フッ素スルホンアミドポリマーに変換される。上記反
応を起こす方法としては、式（３）で表される化合物
を、トリエチルアミン等の脂肪族アミン、ピリジン等の
複素環式アミン、アンモニア、水酸化アルカリ等の塩基
性化合物又はアルカリ金属水素化物と反応させた後、上
記ポリマーと反応させる方法、前記塩基性化合物又はア
ルカリ金属水素化物の存在下で式（３）で表される化合
物と上記ポリマーと反応させる方法を例示することがで
きる。何れの方法においても好ましくは、トリメチルア
ミン等の３級アミン、ピリジン等の複素環式アミンが用
いられる。また、式（４）で表される化合物と上記ポリ
マーを反応させる方法も好ましい。The above polymer is reacted with a perfluorosulfonamide represented by the formula (3) or a derivative of the perfluorosulfonamide represented by the formula (4) to obtain
It is converted to a fluorine-containing sulfonamide polymer. As a method for causing the above reaction, the compound represented by the formula (3) is combined with an aliphatic amine such as triethylamine, a heterocyclic amine such as pyridine, a basic compound such as ammonia and alkali hydroxide, or an alkali metal hydride. After the reaction, a method of reacting with the polymer, a method of reacting the compound represented by the formula (3) with the polymer in the presence of the basic compound or the alkali metal hydride can be exemplified. In any method, a tertiary amine such as trimethylamine and a heterocyclic amine such as pyridine are preferably used. Further, a method of reacting the compound represented by the formula (4) with the polymer is also preferable.
【００２６】また、式（４）で表される化合物は、特に
限定されず、−ＳｉＲ1Ｒ2Ｒ3が−Ｓｉ（ＣＨ3）3、Ｅ+
がＭ+である場合には、ＣＦ3ＳＯ2ＮＭＳｉ（Ｃ
Ｈ3）3、下記式（１０）で表される化合物等が挙げられ
る。なお、下記式（１０）中、ｔは２〜１２を示す。ま
た、このような化合物の構成元素Ｍとしては、Ｌｉ，Ｎ
ａ，Ｋなどが挙げられる。The compound represented by the formula (4) is not particularly limited, and -SiR 1 R 2 R 3 is represented by —Si (CH 3 ) 3 , E +
Is M + , CF 3 SO 2 NMSi (C
H 3 ) 3 and compounds represented by the following formula (10). In addition, in the following formula (10), t shows 2-12. Further, as the constituent element M of such a compound, Li, N
a, K and the like.
【化８】 Embedded image
【００２７】また、式（４）中のＥ+としては、アルカ
リ金属原子等の１価の金属原子の陽イオン、プロトン化
した３級アミンや複素環式アミンが挙げられ、後者で
は、下記式（１４）及び（１５）で表される陽イオンが
例示される。なお、下記式（１４）及び（１５）中、Ｒ
4、Ｒ5、Ｒ6、Ｒ7、及びＲ8はそれぞれ独立に水素原子
又は炭素数１〜５のアルキル基を示す。 （ＮＲ4Ｒ5Ｒ6Ｒ7）+…（１４）In addition, E + in the formula (4) includes a cation of a monovalent metal atom such as an alkali metal atom, a protonated tertiary amine or a heterocyclic amine. Cations represented by (14) and (15) are exemplified. In the following formulas (14) and (15), R
4, R 5, R 6, R 7, and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. (NR 4 R 5 R 6 R 7) + ... (14)
【化９】 Embedded image
【００２８】本発明の含フッ素スルホンイミドポリマー
は、式（２）で表されるモノマー／テトラフルオロエチ
レン共重合体と、式（４）で表される化合物とを以下に
示すスキームＣに従って化学反応させることにより高純
度がつ高収率で得ることができる。なお、下記のスキー
ムＣにおいては、式（２）で表されるモノマー／テトラ
フルオロエチレン共重合体の−ＳＯ2Ｆ基以外の分子構
造をＰとし、Ｐ−ＳＯ2Ｆとして示す。The fluorine-containing sulfonimide polymer of the present invention is obtained by chemically reacting a monomer / tetrafluoroethylene copolymer represented by the formula (2) with a compound represented by the formula (4) according to the following scheme C. By doing so, high purity and high yield can be obtained. In the Scheme C below, the molecular structure other than -SO 2 F groups of the monomers / tetrafluoroethylene copolymer of the formula (2) is P, shown as a P-SO 2 F.
【化１０】 Embedded image
【００２９】スキームＣに示すように、式（２）で表さ
れるモノマー／テトラフルオロエチレン共重合体は、式
（４）で表される化合物により、−ＳＯ2Ｆ基を−ＳＯ2
ＮＭＳＯ2Ｒf2で表される基に変換される。そして、こ
の共重合体中の−ＳＯ2ＮＭＳＯ2Ｒf2で表される基は、
溶媒や水で洗浄し、塩酸、硝酸又は硫酸などの酸水溶液
で処理することにより−ＳＯ2ＮＨＳＯ2Ｒf2で表される
基に変換される。As shown in Scheme C, the monomer / tetrafluoroethylene copolymer of the formula (2) is a compound represented by the formula (4), -SO 2 -SO 2 F groups
It is converted to a group represented by NMSO 2 R f2 . And, the group represented by -SO 2 NMSO 2 R f2 in this copolymer is
Washed with a solvent or water, hydrochloric acid, it is converted into the group represented by -SO 2 NHSO 2 R f2 by treatment with aqueous acid such as nitric acid or sulfuric acid.
【００３０】上記の反応を行なう場合の反応溶媒として
は、アセトニトリル、ジオキサン、スルホラン、テトラ
ヒドロフラン、ジメチルスルホキシド、ジエチルエーテ
ル、モノグライム、ジグライム、トリグライム、テトラ
グライム、ジメチルホルムアミド、ジメチルアセトアミ
ド、Ｎ−メチルピロリジノン等が挙げられる。そしてこ
れらの溶媒は、単独で用いてもよく少なくとも２種類を
混合させた混合溶媒として用いてもよい。また、原料の
式（２）で表されるモノマー／テトラフルオロエチレン
共重合体を上記の溶媒中において膨潤させるため、必要
に応じて、ハイドロフルオロカーボン類（ＨＦＣ）、ク
ロロフルオロカーボン類（ＣＦＣ）、ハイドロクロロフ
ルオロカーボン類（ＨＣＦＣ）、パーフルオロカーボン
類（ＨＣＦＣ）、ハイドロフルオロエーテル類（ＨＦ
Ｅ）等を溶媒中に更に添加してもよい。Examples of the reaction solvent for performing the above reaction include acetonitrile, dioxane, sulfolane, tetrahydrofuran, dimethyl sulfoxide, diethyl ether, monoglyme, diglyme, triglyme, tetraglyme, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone and the like. No. These solvents may be used alone or as a mixed solvent obtained by mixing at least two types. Further, since the monomer / tetrafluoroethylene copolymer represented by the formula (2) as a raw material is swollen in the above-mentioned solvent, hydrofluorocarbons (HFC), chlorofluorocarbons (CFC), Chlorofluorocarbons (HCFC), Perfluorocarbons (HCFC), Hydrofluoroethers (HF
E) and the like may be further added to the solvent.
【００３１】上記の反応を行なう場合の反応温度は０〜
２００℃であることが好ましく、５０〜１５０℃である
ことがより好ましい。生産効率の観点から反応時間は
０．１分〜１週間であることが好ましく、１分〜２４時
間であることがより好ましい。そのため、このような反
応時間で所望の含フッ素スルホンイミドポリマーが得ら
れるように、上記のような反応温度が設定される。The reaction temperature for performing the above reaction is 0 to
The temperature is preferably 200 ° C, more preferably 50 to 150 ° C. From the viewpoint of production efficiency, the reaction time is preferably from 0.1 minutes to 1 week, and more preferably from 1 minute to 24 hours. Therefore, the above-mentioned reaction temperature is set so that a desired fluorine-containing sulfonimide polymer can be obtained in such a reaction time.
【００３２】得られる含フッ素スルホンイミドポリマー
を固体高分子型燃料電池の電解質膜或いは電極構成材料
として使用する場合、要求されるイオン伝導性、撥水性
及び強度などの観点から出発物質である式（１）で表さ
れるモノマー／テトラフルオロエチレン共重合体の溶融
押し出し温度（以下、ＴQという）が５０〜４００℃で
あることが好ましく、１００〜３５０℃であることがよ
り好ましい。When the obtained fluorine-containing sulfonimide polymer is used as an electrolyte membrane or an electrode constituent material of a polymer electrolyte fuel cell, the starting material represented by the formula (1) is required from the viewpoints of required ion conductivity, water repellency and strength. 1) a melt extrusion temperature of the monomer / tetrafluoroethylene copolymer represented (hereinafter, it is preferred that T Q) is 50 to 400 ° C., and more preferably 100 to 350 ° C..
【００３３】なお、このＴQとは、長さ１ｍｍ、内径１
ｍｍのノズルを用い、３０ｋｇ／ｃｍ2の押出し圧力の
条件でポリマーの溶融押出しを行った際、押出し量が１
００ｍｍ3／秒となる温度を示す。ＴQは、樹脂の分子量
の目安となる数値であり、一般にＴQが高いほど分子量
は大きくなる。そして、得られる含フッ素スルホンイミ
ドポリマーは、分子量が小さいほど分子鎖の絡みが少な
く膨潤し易くなるので高い含水率を有することになり、
一方、分子量が大きいほど分子鎖の絡みが多く膨潤しに
くくなるので低い含水率を有することになる。The T Q is 1 mm in length and 1 in inner diameter.
When a polymer was melt-extruded using a nozzle of 30 mm under an extrusion pressure of 30 kg / cm 2 , the amount of extrusion was 1
Shows the temperature at which 00 mm 3 / sec. T Q is a numerical value that is a measure of the molecular weight of the resin. In general, the higher the T Q , the higher the molecular weight. And the obtained fluorine-containing sulfonimide polymer has a high water content because the molecular weight is small and the entanglement of the molecular chain is easy to swell.
On the other hand, the higher the molecular weight, the more entanglement of the molecular chains and the more difficult it is to swell, resulting in a low water content.
【００３４】また、本発明の製造方法により得られる含
フッ素スルホンイミドポリマーは食塩電解、燃料電池な
どの各種電気化学セルの電極構成材料及び電解質膜とし
て使用でき、他にも選択透過膜、除湿膜、固体酸触媒等
としても使用することができる。なかでも、固体高分子
型燃料電池の電極構成材料及び電解質膜として好適に使
用することができる。ここで、得られる含フッ素スルホ
ンイミドポリマーを固体高分子型燃料電池の電解質膜或
いは電極構成材料として使用する場合には、酸型（−Ｓ
Ｏ2ＮＨＳＯ2Ｒf2）で使用される。Further, the fluorine-containing sulfonimide polymer obtained by the production method of the present invention can be used as an electrode constituent material and an electrolyte membrane of various electrochemical cells such as a salt electrolysis and a fuel cell. And solid acid catalysts. Among them, it can be suitably used as an electrode constituent material and an electrolyte membrane of a polymer electrolyte fuel cell. Here, when the obtained fluorine-containing sulfonimide polymer is used as an electrolyte membrane or an electrode constituent material of a polymer electrolyte fuel cell, an acid type (-S
O 2 NHSO 2 R f2 ).
【００３５】[0035]
【実施例】以下、実施例を挙げて本発明の含フッ素スル
ホンイミドポリマーの製造方法ついて更に詳しく説明す
るが、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES Hereinafter, the method for producing the fluorine-containing sulfonimide polymer of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００３６】（実施例１）式（６）で表されるモノマー
／テトラフルオロエチレン共重合体（−ＳＯ2Ｆ基を−
ＳＯ3Ｈ基に変換した場合のＡR＝１．１ｍｅｑ．／ｇ、
ＴQ＝１８０℃）の粉体５ｇ、ＣＦ3ＳＯ2ＮＮａＳｉ
（ＣＨ3）3５ｇ、アセトニトリル２５ｍＬ、１，４−ジ
オキサン２５ｍＬを容積１００ｍＬのオートクレーブに
入れ、８０℃で２日間撹拌し反応させた。その後、内容
物を水洗後、濃塩酸に１６時間浸漬した。次に、イオン
交換水で洗浄し、更に真空乾燥することにより、−ＳＯ
2ＮＨＳＯ2ＣＦ3基を有する含フッ素スルホンイミドポ
リマーを得た。Example 1 A monomer / tetrafluoroethylene copolymer represented by the formula (6) (-SO 2 F
A R = 1.1 meq. When converted to SO 3 H group. / G,
T Q = powder 5g of 180 ℃), CF 3 SO 2 NNaSi
5 g of (CH 3 ) 3 , 25 mL of acetonitrile, and 25 mL of 1,4-dioxane were put in an autoclave having a volume of 100 mL, and reacted by stirring at 80 ° C. for 2 days. Thereafter, the contents were washed with water and immersed in concentrated hydrochloric acid for 16 hours. Next, the substrate is washed with ion-exchanged water and further dried under vacuum to obtain -SO
A fluorinated sulfonimide polymer having 2 NHSO 2 CF 3 groups was obtained.
【００３７】（実施例２）式（６）で表されるモノマー
／テトラフルオロエチレン共重合体（−ＳＯ2Ｆ基を−
ＳＯ3Ｈ基に変換した場合のＡR＝１．１ｍｅｑ．／ｇ、
ＴQ＝２２０℃）のフィルム（大きさ：２０×３０ｍ
ｍ、厚さ：５０μｍ）とＣＦ3ＳＯ2ＮＮａＳｉ（Ｃ
Ｈ3）3１０g、アセトニトリル１００ｍＬを容積２００
ｍＬのアンプルに入れ、２日間８０℃に保持した。その
後、内容物を水洗後、濃塩酸に１６時間浸漬した。次
に、イオン交換水で洗浄し、真空乾燥することにより、
−ＳＯ2ＮＨＳＯ2ＣＦ3基を有する含フッ素スルホンイ
ミドポリマーのフィルムを得た。Example 2 A monomer / tetrafluoroethylene copolymer of the formula (6) (-SO 2 F
A R = 1.1 meq. When converted to SO 3 H group. / G,
TQ = 220 ° C.) film (size: 20 × 30 m)
m, thickness: 50 μm) and CF 3 SO 2 NNaSi (C
H 3 ) 3 10 g, acetonitrile 100 mL with a volume of 200
Placed in mL ampoules and kept at 80 ° C. for 2 days. Thereafter, the contents were washed with water and immersed in concentrated hydrochloric acid for 16 hours. Next, by washing with ion exchanged water and vacuum drying,
To obtain a film of a fluorine-containing sulfonimide polymer having -SO 2 NHSO 2 CF 3 group.
【００３８】（実施例３）式（６）で表されるモノマー
／テトラフルオロエチレン共重合体（−ＳＯ2Ｆ基を−
ＳＯ3Ｈ基に変換した場合のＡR＝１．１ｍｅｑ．／ｇ、
ＴQ＝１８０℃）の粉体５ｇ、ＣＦ3ＳＯ2ＮＨ2５ｇ、ア
セトニトリル４５ｍＬ、トリエチルアミン５ｇを容積１
００ｍＬのオートクレーブに入れ、５０℃で２日間撹拌
し反応させた。その後、内容物を水洗後、濃塩酸に１６
時間浸漬した。次に、イオン交換水で洗浄し、更に真空
乾燥することにより、−ＳＯ2ＮＨＳＯ2ＣＦ3基を有す
る含フッ素スルホンイミドポリマーを得た。Example 3 A monomer / tetrafluoroethylene copolymer represented by the formula (6) (-SO 2 F
A R = 1.1 meq. When converted to SO 3 H group. / G,
(T Q = 180 ° C.), 5 g of CF 3 SO 2 NH 2 , 45 mL of acetonitrile, and 5 g of triethylamine in a volume of 1
The mixture was placed in a 00 mL autoclave and reacted by stirring at 50 ° C. for 2 days. After washing the contents with water, add
Soaked for hours. Then washed with deionized water, by further vacuum-dried to obtain a fluorine-containing sulfonimide polymer having -SO 2 NHSO 2 CF 3 group.
【００３９】（実施例４）式（６）で表されるモノマー
／テトラフルオロエチレン共重合体（−ＳＯ2Ｆ基を−
ＳＯ3Ｈ基に変換した場合のＡR＝１．１ｍｅｑ．／ｇ、
ＴQ＝２２０℃）のフィルム（大きさ：２０×３０ｍ
ｍ、厚さ：５０μｍ）とＣＦ3ＳＯ2ＮＨ2１０g、アセト
ニトリル９０ｍＬ、ピリジン１０ｇを容積２００ｍＬの
アンプルに入れ、２日間８０℃に保持した。その後、内
容物を水洗後、濃塩酸に１６時間浸漬した。次に、イオ
ン交換水で洗浄し、真空乾燥することにより、−ＳＯ2
ＮＨＳＯ2ＣＦ3基を有する含フッ素スルホンイミドポリ
マーのフィルムを得た。Example 4 A monomer / tetrafluoroethylene copolymer represented by the formula (6) (-SO 2 F
A R = 1.1 meq. When converted to SO 3 H group. / G,
TQ = 220 ° C.) film (size: 20 × 30 m)
m, thickness: 50 μm), 10 g of CF 3 SO 2 NH 2 , 90 mL of acetonitrile, and 10 g of pyridine were put in a 200 mL ampoule and kept at 80 ° C. for 2 days. Thereafter, the contents were washed with water and immersed in concentrated hydrochloric acid for 16 hours. Next, the substrate is washed with ion-exchanged water and dried under vacuum to obtain -SO 2
A film of a fluorinated sulfonimide polymer having NHSO 2 CF 3 groups was obtained.
【００４０】[0040]
【発明の効果】以上説明したように、本発明の製造方法
によれば、高純度の含フッ素スルホンイミドポリマーを
シンプルな合成反応の組み合わせにより容易にかつ高収
率で得ることができる。As described above, according to the production method of the present invention, a high-purity fluorine-containing sulfonimide polymer can be easily obtained in a high yield by a combination of simple synthesis reactions.
Claims (5)
ラフルオロエチレン共重合体である含フッ素スルホンイ
ミドポリマーの製造方法であって、 下記式（２）で表されるモノマー／テトラフルオロエチ
レン共重合体と下記式（３）で表される化合物とを化学
反応させる工程を経ることを特徴とする含フッ素スルホ
ンイミドポリマーの製造方法。 ＣＦ2＝ＣＦＲf1ＳＯ2ＮＸＳＯ2Ｒf2 …（１） ＣＦ2＝ＣＦＲf1ＳＯ2Ｆ …（２） Ｒf2ＳＯ2ＮＨ2 …（３） ［式（１）〜（３）中、Ｘは水素原子又はアルカリ金属
原子であり、 Ｒf1は単結合若しくは直鎖又は分岐構造を有するパーフ
ルオロアルキレン基であって、エーテル結合性の酸素原
子を含んでいてもよく、 Ｒf2は直鎖又は分岐構造を有するパーフルオロアルキル
基であって、エーテル結合性の酸素原子及び／又は−Ｓ
Ｏ2ＮＸＳＯ2−で表される基を含んでいてもよい。］1. A method for producing a fluorinated sulfonimide polymer which is a monomer / tetrafluoroethylene copolymer represented by the following formula (1), comprising: a monomer / tetrafluoroethylene represented by the following formula (2): A method for producing a fluorine-containing sulfonimide polymer, which comprises a step of chemically reacting a copolymer with a compound represented by the following formula (3). CF 2 = CFR f1 SO 2 NXSO 2 R f2 (1) CF 2 = CFR f1 SO 2 F (2) R f2 SO 2 NH 2 (3) [In the formulas (1) to (3), X represents is a hydrogen atom or an alkali metal atom, R f1 is a perfluoroalkylene group having a single bond or a linear or branched structure, may contain an etheric oxygen atom, R f2 is a linear or branched A perfluoroalkyl group having a structure, comprising an ether-bonding oxygen atom and / or -S
It may contain a group represented by O 2 NXSO 2 —. ]
ラフルオロエチレン共重合体である含フッ素スルホンイ
ミドポリマーの製造方法であって、 下記式（２）で表されるモノマー／テトラフルオロエチ
レン共重合体と下記式（４）で表される化合物とを化学
反応させる工程を経ることを特徴とする含フッ素スルホ
ンイミドポリマーの製造方法。 ＣＦ2＝ＣＦＲf1ＳＯ2ＮＸＳＯ2Ｒf2 …（１） ＣＦ2＝ＣＦＲf1ＳＯ2Ｆ …（２） （Ｒf2ＳＯ2ＮＳｉＲ1Ｒ2Ｒ3）-Ｅ+ …（４） ［式（１）、（２）及び（４）中、Ｘは水素原子又はア
ルカリ金属原子であり、 Ｒf1は単結合若しくは直鎖又は分岐構造を有するパーフ
ルオロアルキレン基であって、エーテル結合性の酸素原
子を含んでいてもよく、 Ｒf2は直鎖又は分岐構造を有するパーフルオロアルキル
基であって、エーテル結合性の酸素原子及び／又は−Ｓ
Ｏ2ＮＸＳＯ2−で表される基を含んでいてもよく、 Ｒ1、Ｒ2及びＲ3はアルキル基であって、それぞれ同一
であっても異なっていてもよく、 Ｅ+は１価の陽イオンである。］2. A method for producing a fluorine-containing sulfonimide polymer which is a monomer / tetrafluoroethylene copolymer represented by the following formula (1), wherein the monomer / tetrafluoroethylene represented by the following formula (2) is provided. A method for producing a fluorine-containing sulfonimide polymer, which comprises a step of chemically reacting a copolymer with a compound represented by the following formula (4). CF 2 = CFR f1 SO 2 NXSO 2 R f2 ... (1) CF 2 = CFR f1 SO 2 F ... (2) (R f2 SO 2 NSiR 1 R 2 R 3) - E + ... (4) [ Formula (1 ), (2) and (4), X is a hydrogen atom or an alkali metal atom, and R f1 is a single bond or a perfluoroalkylene group having a linear or branched structure, and has an ether bond oxygen atom. R f2 may be a perfluoroalkyl group having a linear or branched structure, and may have an ether bond oxygen atom and / or —S
O 2 NXSO 2 - may contain a group represented by, R 1, R 2 and R 3 is an alkyl group, each of which represents be the same, E + represents a monovalent It is a cation. ]
て、Ｅが１価の金属原子であることを特徴とする請求項
２に記載の含フッ素スルホンイミドポリマーの製造方
法。3. The method for producing a fluorine-containing sulfonimide polymer according to claim 2, wherein in the compound represented by the formula (4), E is a monovalent metal atom.
式（５）で表されるモノマーであることを特徴とする請
求項１〜３の何れかに記載の含フッ素スルホンイミドポ
リマーの製造方法。 【化１】 ［式（５）中、ｍは０〜３の整数、ｎは１〜１２の整
数、Ｙはフッ素原子又はトリフルオロメチル基をそれぞ
れ示す。］4. The fluorine-containing sulfonimide polymer according to claim 1, wherein the monomer represented by the formula (2) is a monomer represented by the following formula (5). Production method. Embedded image [In the formula (5), m represents an integer of 0 to 3, n represents an integer of 1 to 12, and Y represents a fluorine atom or a trifluoromethyl group. ]
式（６）で表されるモノマーであり、かつ、前記式
（４）で表される化合物が下記式（７）で表される化合
物であることを特徴とする請求項３に記載の含フッ素ス
ルホンイミドポリマーの製造方法。 【化２】 ［式（７）中、Ｚはアルカリ金属原子を示す。］5. The monomer represented by the formula (2) is a monomer represented by the following formula (6), and the compound represented by the formula (4) is represented by the following formula (7). The method for producing a fluorine-containing sulfonimide polymer according to claim 3, wherein the compound is a compound. Embedded image [In the formula (7), Z represents an alkali metal atom. ]
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| JP2006342342A (en) * | 2005-05-13 | 2006-12-21 | Toyota Central Res & Dev Lab Inc | Ion-conductive polymer and imide monomer |
| US7473748B2 (en) * | 2004-01-22 | 2009-01-06 | Asahi Kasei Kabushiki Kaisha | Vinyl monomer with superacid ester group and polymer of the same |
| JP2016507611A (en) * | 2012-12-21 | 2016-03-10 | トヨタ自動車株式会社 | Proton exchange material and method for producing the same |
| US9663600B2 (en) | 2012-12-21 | 2017-05-30 | Audi Ag | Method of fabricating an electrolyte material |
| WO2017170055A1 (en) * | 2016-03-29 | 2017-10-05 | 旭硝子株式会社 | Perfluoro block polymer, liquid composition, solid polymer electrolyte membrane and membrane electrode assembly for solid polymer fuel cells |
| US9923223B2 (en) | 2012-12-21 | 2018-03-20 | Audi Ag | Electrolyte membrane, dispersion and method therefor |
| US10505197B2 (en) | 2011-03-11 | 2019-12-10 | Audi Ag | Unitized electrode assembly with high equivalent weight ionomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7473748B2 (en) * | 2004-01-22 | 2009-01-06 | Asahi Kasei Kabushiki Kaisha | Vinyl monomer with superacid ester group and polymer of the same |
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