JP4815672B2 - Method for producing fluorine-containing sulfonimide polymer - Google Patents
Method for producing fluorine-containing sulfonimide polymer Download PDFInfo
- Publication number
- JP4815672B2 JP4815672B2 JP2001013464A JP2001013464A JP4815672B2 JP 4815672 B2 JP4815672 B2 JP 4815672B2 JP 2001013464 A JP2001013464 A JP 2001013464A JP 2001013464 A JP2001013464 A JP 2001013464A JP 4815672 B2 JP4815672 B2 JP 4815672B2
- 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.)
- Expired - Lifetime
Links
Classifications
-
- 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
Description
【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。
【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。
【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）
【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, Proceedings, 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、−ＳＯ2ＮＨＳＯ2−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。
【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。
【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。
【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（ＣＦ2）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。
【化３】
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、−ＳＯ2Ｆ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。
【化４】
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)。
【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。
【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。
【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、粉体状、膜状、又はペレット状の下記式（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を提供する。
ＣＦ2＝ＣＦＲf1ＳＯ2ＮＸＳＯ2Ｒf2 …（１）
ＣＦ2＝ＣＦＲf1ＳＯ2Ｆ …（２）
Ｒf2ＳＯ2ＮＨ2 …（３）
また、本発明は、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、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を提供する。
（Ｒf2ＳＯ2ＮＳｉＲ1Ｒ2Ｒ3）-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、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−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。
【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。
【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−ＳＯ2ＮＸＳＯ2−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。
【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。
【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。
【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。
【化５】
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。
【化６】
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。
【化７】
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＝ＣＦＣＦ2ＯＣＦ2ＣＦ2ＳＯ2Ｆが挙げられる。
【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−ＳＯ2Ｆ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、０．７〜１．５ｍｅｑ．／ｇであることがより好ましい。
【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。
【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。
【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（ＣＨ3）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，Ｎａ，Ｋなどが挙げられる。
【化８】
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、Ｒ4、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）
【化９】
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。
【化１０】
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−ＳＯ2ＮＭＳＯ2Ｒf2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。
【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（ＨＦＥ）等を溶媒中に更に添加してもよい。
【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。
【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。
【００３３】
なお、このＴQとは、長さ１ｍｍ、内径１ｍｍ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１００ｍｍ3／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。
【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（−ＳＯ2ＮＨＳＯ2Ｒf2）で使用される。
【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。
【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、−ＳＯ2ＮＨＳＯ2ＣＦ3基を有する含フッ素スルホンイミドポリマーを得た。
【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：２０×３０ｍｍ、厚さ：５０μｍ）とＣＦ3ＳＯ2ＮＮａＳｉ（ＣＨ3）3１０g、アセトニトリル１００ｍＬ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、−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。
【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１００ｍＬ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。
【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：２０×３０ｍｍ、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、−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。
【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。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a fluorine-containing sulfonimide polymer having a sulfonimide structure.
[0002]
[Prior art]
Conventionally, a fluorine-containing polymer having a sulfonic acid group has been used by using an electrolyte membrane or an electrode of an electrochemical cell such as a fuel cell as a constituent material. In this polymer, the usable temperature range is limited to about 150 ° C. or less from the viewpoint of heat resistance, and accordingly, the operating temperature of an electrochemical cell such as a fuel cell using this as a constituent material of an electrolyte membrane or an electrode is also described above. Limited to range. Therefore, development of a polymer having higher heat resistance than conventional fluorine-containing polymers having a sulfonic acid group is expected, and various studies have been made.
[0003]
For example, as a polymer useful for electrochemical cells such as fuel cells, US Pat. No. 5,463,005 proposes a fluorine-containing polymer having a group represented by the following formula (8) in the side chain. However, in the following formulas (8), J represents any one selected from hydrogen, alkali metals and alkaline earth metals, R f3 is a perfluoroalkyl group, -SO 2 NJSO 2 - represented by It may contain a group.
-SO 2 NJSO 2 -R f3 ... ( 8)
[0004]
Furthermore, an example in which this fluorine-containing sulfonimide polymer is applied to a fuel cell has been recently reported (The 3rd International Fuel Cell Conference, Nagoya, Proceedings, p129-p132, (1999)).
[0005]
In this specification, as described in Formula (1) of the above formula (8) in and later, -SO 2 NHSO 2 - group represented by and said -SO 2 NHSO 2 - with A group in which the hydrogen atom of the represented group is substituted with a monovalent cation is referred to as a “sulfonimide group”.
[0006]
This fluorine-containing polymer having a sulfonimide group (hereinafter referred to as a fluorine-containing sulfonimide polymer) has a feature of higher heat resistance than a conventional fluorine-containing polymer having a sulfonic acid group. By using it as a constituent material for the electrolyte membrane and electrode of an electrochemical cell, it is possible to improve the durability of these electrochemical cells as compared to conventional ones, and to increase the operating temperature compared to conventional ones and to include the electrochemical cells. It can be expected that the energy conversion efficiency of the entire system can be increased. And conventionally, said fluorine-containing sulfonimide polymer is synthesize | combined by superposition | polymerization with the monomer which has a sulfonimide group in a side chain, and tetrafluoroethylene.
[0007]
[Problems to be solved by the invention]
However, in order to obtain a high-molecular-weight fluorine-containing sulfonimide polymer with high yield and good reproducibility, it is necessary to carry out a polymerization reaction using a high-purity monomer. Since a monomer having a —SO 2 F group is synthesized as a starting material, a combination of multistage synthesis reactions is required. For this reason, there are problems that the manufacturing process is complicated and time-consuming, and that it is difficult to obtain high purity and high yield. In addition, a monomer having a sulfonimide group has a high boiling point, which is disadvantageous for purification by distillation. Also in this respect, it is difficult to obtain a monomer having a sulfonimide group with high purity and high yield with good reproducibility.
[0008]
For example, when synthesizing CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 2 NHSO 2 CF 3 as a monomer having a sulfonimide group, CF 2 ═CFOCF 2 CF (CF 3 ) O Using (CF 2 ) 2 SO 2 F as a starting material, a multistage synthesis reaction as shown in Scheme A below was required.
[Chemical 3]
In addition, 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, but this method requires a multistage polymer reaction, and the sulfonimide group has a high purity. It is difficult to introduce. In the following scheme B, a molecular structure other than the —SO 2 F group of a polymer having a —SO 2 F group is represented by P, and is represented as P—SO 2 F.
[Formula 4]
Furthermore, since a monomer having a sulfonimide group has a non-polar portion 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]
The present invention has been made in view of the above-described problems of the prior art, and provides a production method capable of easily obtaining a high-purity fluorine-containing sulfonimide polymer by a simple synthesis reaction in a high yield. With the goal.
[0012]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned object, the present inventors have used a polymer having —SO 2 F group as a raw material and allowed to act on a specific sulfonamide or a derivative thereof in the copolymer. The present inventors have found that the —SO 2 F group can be easily converted into a sulfonimide group at a high yield.
[0013]
That is, the present invention is a method for producing a fluorine-containing sulfonimide polymer that is a monomer / tetrafluoroethylene copolymer represented by the following formula (1), and is in the form of powder, film, or pellet: Provided is a method for producing a fluorine-containing sulfonimide polymer, comprising a step of chemically reacting the monomer / tetrafluoroethylene copolymer represented by (2) 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)
The present invention also provides a method for producing a fluorine-containing sulfonimide polymer that is a monomer / tetrafluoroethylene copolymer represented by the formula (1), the monomer / tetrafluoroethylene copolymer represented by the formula (2): Provided is a method for producing a fluorine-containing sulfonimide polymer, which comprises a step of chemically reacting a polymer and a compound represented by the following formula (4).
(R f2 SO 2 NSiR 1 R 2 R 3 ) − E + (4)
[0014]
Here, in the formulas (1) to (4), X is a hydrogen atom or an alkali metal atom, R f1 is a perfluoroalkylene group having a single bond, a straight chain or a branched structure, and is an ether-bonded oxygen R f2 may be a perfluoroalkyl group having a straight chain or branched structure, and may include an ether-bonded oxygen atom and / or a group represented by —SO 2 NXSO 2 —. R 1 , R 2 and R 3 are alkyl groups which may be the same or different, and E + is a monovalent cation.
[0015]
In this specification, the A / B copolymer refers to a copolymer composed of a repeating unit based on the monomer A and a repeating unit based on the monomer B.
[0016]
Unlike the conventional case of synthesizing a monomer having a sulfonimide group and polymerizing it with tetrafluoroethylene, in the present invention, the monomer represented by the above (2) which is a polymer having a —SO 2 F group / A compound represented by the formula (3) in which a tetrafluoroethylene copolymer is used as a raw material and the compound represented by the formula (4) is allowed to act on this or in the presence of a base such as an amine or an alkali metal hydroxide By acting, the —SO 2 F group in the copolymer can be directly converted to the —SO 2 NX′SO 2 R f2 group. Here, X ′ is E in the formula (4) or a metal atom (alkali metal atom or the like) that becomes a cation in the coexisting base. Therefore, a fluorine-containing sulfonimide polymer having a sulfonimide group represented by —SO 2 NXSO 2 — in the formula (1) is easily synthesized in a high purity state by a simple synthesis reaction with a high yield. be able to. In addition, when X and X ′ are different from each other, it is easily converted into —SO 2 NXSO 2 — by immersing the fluorine-containing sulfonimide polymer having —SO 2 NX′SO 2 R f2 group in a solution containing X + ions. Can be converted.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the method for producing a fluorine-containing sulfonimide polymer of the present invention will be described in detail.
[0018]
The raw materials for the fluorine-containing sulfonimide polymer of the present invention are the monomer / tetrafluoroethylene copolymer represented by the formula (2) described above and the perfluorosulfonamide represented by the formula (3) or (4). Or a derivative thereof. First, the monomer / tetrafluoroethylene copolymer represented by the formula (2) will be described. This copolymer is synthesized by copolymerizing a monomer represented by the formula (2) and tetrafluoroethylene. This copolymer can be synthesized with high purity and high yield with good reproducibility. The method for synthesizing this copolymer is not particularly limited, and known methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like can be used. Further, the form of the monomer / tetrafluoroethylene copolymer represented by the formula (2) to be used is not particularly limited. For example, the form may be a powder form, a film form, or a pellet form. There may be.
[0019]
Here, the monomer represented by the formula (2) is preferably a monomer represented by the following formula (5). However, in following formula (5), m is an integer of 0-3, n is an integer of 1-12, Y shows a fluorine atom or a trifluoromethyl group, respectively.
[Chemical formula 5]
The monomer represented by the formula (5) is easily purified by distillation, and a high-purity product can be easily obtained. Preferable examples of the monomer represented by the above formula (5) include monomers represented by the following chemical formulas (11) to (13). Here, in the following chemical formulas (11) to (13), q is an integer of 1 to 8, r is an integer of 1 to 8, and s is 2 or 3.
[Chemical 6]
Furthermore, among the monomers represented by the chemical formulas (11) to (13), the monomer represented by the following formula (6) and the monomer represented by the following formula (9) are more preferable.
[Chemical 7]
Further, regarding the monomer represented by the formula (2) described above, another preferred example is CF 2 ═CFCF 2 OCF 2 CF 2 SO 2 F.
[0023]
Furthermore, the content of —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. it may be used a copolymer having a content of -SO 2 F groups suitable in accordance with the copolymerization of fluorinated sulfonimide polymer obtained from body applications. For example, when a fluorine-containing sulfonimide polymer is used as an electrode constituent material or an electrolyte membrane of a solid polymer fuel cell, in the monomer / tetrafluoroethylene copolymer represented by the formula (2) as a raw material thereof content of -SO 2 F groups, 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 millimeters Equivalent / g dry resin (hereinafter referred to as meq./g) is preferable, and 0.7 to 1.5 meq. / G is more preferable.
[0024]
A R is 0.5 meq. When it is less than / g, the ionic conductivity of the fluorine-containing 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, a sufficient reaction is achieved. It becomes difficult to secure the site, and the polarization characteristics of the electrode are likely to deteriorate. Also, when used as an electrolyte membrane, the electrolyte resistance increases, and there is a possibility that sufficient battery output characteristics cannot be obtained. On the other hand, A R is 2.0 meq. When exceeding / g, the density of ion-exchange groups in the fluorine-containing sulfonimide polymer obtained from this copolymer increases, so when used as a constituent material of the electrode, the gas diffusibility or drainage in the electrode decreases. Flooding is likely to occur in which water clogs the pores effective for gas diffusion of the electrode. Further, when used as an electrolyte membrane, the strength as a membrane is lowered, and it is difficult to construct a battery using this.
[0025]
The polymer is converted to a fluorine-containing sulfonamide polymer by reacting with the perfluorosulfonamide represented by the formula (3) or the perfluorosulfonamide derivative represented by the formula (4). As a method for causing the above reaction, a compound represented by the formula (3) is converted into an aliphatic amine such as triethylamine, a heterocyclic amine such as pyridine, a basic compound such as ammonia or alkali hydroxide, or an alkali metal hydride. Examples thereof include a method of reacting with the polymer after the reaction, and 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. In any method, a tertiary amine such as trimethylamine or a heterocyclic amine such as pyridine is preferably used. A method of reacting the compound represented by formula (4) with the polymer is also preferred.
[0026]
The compound represented by formula (4) is not particularly limited, -SiR 1 R 2 R 3 is -Si (CH 3) 3, if E + is and M +, CF 3 SO 2 NMSi (CH 3) 3, include compounds represented by the following formula (10). In addition, in following formula (10), t shows 2-12. Examples of the constituent element M of such a compound include Li, Na, and K.
[Chemical 8]
Examples of E + in the formula (4) include a cation of a monovalent metal atom such as an alkali metal atom, a protonated tertiary amine or a heterocyclic amine. In the latter, the following formula (14) And the cation represented by (15). 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)
[Chemical 9]
The fluorine-containing sulfonimide polymer of the present invention is obtained by chemically reacting the monomer / tetrafluoroethylene copolymer represented by the formula (2) and the compound represented by the formula (4) according to the following scheme C. High purity and high yield can be obtained. In the following scheme C, the molecular structure other than the —SO 2 F group of the monomer / tetrafluoroethylene copolymer represented by the formula (2) is denoted by P and denoted as P—SO 2 F.
[Chemical Formula 10]
As shown in Scheme C, the monomer / tetrafluoroethylene copolymer represented by the formula (2) has a —SO 2 F group represented by —SO 2 NMSO 2 R f2 by the compound represented by the formula (4). Converted to the group represented. The group represented by —SO 2 NMSO 2 R f2 in this copolymer is washed with a solvent or water, and treated with an aqueous acid solution such as hydrochloric acid, nitric acid or sulfuric acid, to obtain —SO 2 NHSO 2 R f2. Is converted to the group represented by
[0030]
Examples of the reaction solvent for carrying out the above reaction include acetonitrile, dioxane, sulfolane, tetrahydrofuran, dimethyl sulfoxide, diethyl ether, monoglyme, diglyme, triglyme, tetraglyme, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone and the like. These solvents may be used alone or as a mixed solvent in which at least two kinds are mixed. Moreover, in order to swell the monomer / tetrafluoroethylene copolymer represented by the formula (2) of the raw material in the above solvent, hydrofluorocarbons (HFC), chlorofluorocarbons (CFC), hydro Chlorofluorocarbons (HCFC), perfluorocarbons (HCFC), hydrofluoroethers (HFE) and the like may be further added to the solvent.
[0031]
The reaction temperature when performing the above reaction is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. From the viewpoint of production efficiency, the reaction time is preferably 0.1 minute to 1 week, and more preferably 1 minute to 24 hours. Therefore, the reaction temperature as described above is set so that a desired fluorine-containing sulfonimide polymer can be obtained in such a reaction time.
[0032]
When the obtained fluorine-containing sulfonimide polymer is used as an electrolyte membrane or electrode constituent material of a polymer electrolyte fuel cell, it is represented by the formula (1) which is a starting material from the viewpoint of required ion conductivity, water repellency and strength. represented by the monomer / tetrafluoroethylene copolymer melt extrusion temperature (hereinafter, referred to as T Q) is preferably is 50 to 400 ° C., and more preferably 100 to 350 ° C..
[0033]
Note that the T Q, shows the length 1 mm, using a nozzle having an inner diameter of 1 mm, when subjected to melt extrusion of the polymer under the conditions of the extrusion pressure of 30kg / cm 2, the temperature at which the extrusion amount becomes 100 mm 3 / sec . T Q is a numerical value that serves as a standard for the molecular weight of the resin. In general, the higher the T Q , the higher the molecular weight. The resulting fluorine-containing sulfonimide polymer has a high water content because the smaller the molecular weight, the less entangled molecular chains and the easier it swells, while the larger the molecular weight, the more entangled molecular chains are less likely to swell. Therefore, it has a low water content.
[0034]
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 for various electrochemical cells such as salt electrolysis and a fuel cell. In addition, a permselective membrane, a dehumidifying membrane, a solid acid It can also be used as a catalyst or the like. Especially, it can use suitably as an electrode constituent material and electrolyte membrane of a polymer electrolyte fuel cell. Here, when the obtained fluorine-containing sulfonimide polymer is used as an electrolyte membrane or electrode constituent material of a solid polymer fuel cell, it is used in an acid form (—SO 2 NHSO 2 R f2 ).
[0035]
【Example】
EXAMPLES Hereinafter, although an Example is given and the manufacturing method of the fluorine-containing sulfonimide polymer of this invention is demonstrated in detail, this invention is not limited to these Examples.
[0036]
Example 1
Of the monomer / tetrafluoroethylene copolymer represented by formula (6) (A R = 1.1 meq./g, T Q = 180 ° C. when -SO 2 F group is converted to -SO 3 H group) 5 g of powder, 5 g of CF 3 SO 2 NNaSi (CH 3 ) 3 , 25 mL of acetonitrile, and 25 mL of 1,4-dioxane were placed in an autoclave having a volume of 100 mL and stirred at 80 ° C. for 2 days for reaction. Thereafter, the contents were washed with water and then immersed in concentrated hydrochloric acid for 16 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.
[0037]
(Example 2)
Of monomer / tetrafluoroethylene copolymer represented by formula (6) (A R = 1.1 meq./g, T Q = 220 ° C. when -SO 2 F group is converted to -SO 3 H group) A film (size: 20 × 30 mm, thickness: 50 μm), 10 g of CF 3 SO 2 NNaSi (CH 3 ) 3 and 100 mL of acetonitrile were placed in a 200 mL volume ampoule and kept at 80 ° C. for 2 days. Thereafter, the contents were washed with water and then immersed in concentrated hydrochloric acid for 16 hours. Next, it was washed with ion-exchanged water and vacuum-dried to obtain a fluorine-containing sulfonimide polymer film having —SO 2 NHSO 2 CF 3 groups.
[0038]
(Example 3)
Of the monomer / tetrafluoroethylene copolymer represented by formula (6) (A R = 1.1 meq./g, T Q = 180 ° C. when -SO 2 F group is converted to -SO 3 H group) 5 g of powder, 5 g of CF 3 SO 2 NH 2 , 45 mL of acetonitrile, and 5 g of triethylamine were placed in an autoclave having a volume of 100 mL and stirred at 50 ° C. for 2 days for reaction. Thereafter, the contents were washed with water and then immersed in concentrated hydrochloric acid for 16 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]
Example 4
Of monomer / tetrafluoroethylene copolymer represented by formula (6) (A R = 1.1 meq./g, T Q = 220 ° C. when -SO 2 F group is converted to -SO 3 H group) A film (size: 20 × 30 mm, thickness: 50 μm), CF 3 SO 2 NH 2 10 g, acetonitrile 90 mL, and pyridine 10 g were placed in a 200 mL capacity ampoule and kept at 80 ° C. for 2 days. Thereafter, the contents were washed with water and then immersed in concentrated hydrochloric acid for 16 hours. Next, it was washed with ion-exchanged water and vacuum-dried to obtain a fluorine-containing sulfonimide polymer film having —SO 2 NHSO 2 CF 3 groups.
[0040]
【Effect of the invention】
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)
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−ＳＯ2ＮＸＳＯ2−で表される基を含んでいてもよい。］A method for producing a fluorine-containing sulfonimide polymer that is a monomer / tetrafluoroethylene copolymer represented by the following formula (1), which is represented by the following formula (2) in the form of powder, film, or pellet A method for producing a fluorine-containing sulfonimide polymer, comprising a step of chemically reacting a monomer / tetrafluoroethylene copolymer and 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 is a hydrogen atom or an alkali metal atom, R f1 is a perfluoroalkylene group having a single bond, a straight chain or a branched structure, and an ether-bonded oxygen atom. R f2 may be a perfluoroalkyl group having a linear or branched structure, and may include an ether-bonded oxygen atom and / or a group represented by —SO 2 NXSO 2 —. . ]
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−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。］A method for producing a fluorine-containing sulfonimide polymer that is a monomer / tetrafluoroethylene copolymer represented by the following formula (1):
A method for producing a fluorine-containing sulfonimide polymer, comprising a step of chemically reacting a monomer / tetrafluoroethylene copolymer represented by the following formula (2) and 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)
[In the formulas (1), (2) and (4), X is a hydrogen atom or an alkali metal atom,
R f1 is a perfluoroalkylene group having a single bond, a straight chain or a branched structure, and may contain an etheric oxygen atom,
R f2 is a perfluoroalkyl group having a linear or branched structure, and may contain an etheric oxygen atom and / or a group represented by —SO 2 NXSO 2 —,
R 1 , R 2 and R 3 are alkyl groups, which may be the same or different,
E + is a monovalent cation. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001013464A JP4815672B2 (en) | 2001-01-22 | 2001-01-22 | Method for producing fluorine-containing sulfonimide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001013464A JP4815672B2 (en) | 2001-01-22 | 2001-01-22 | Method for producing fluorine-containing sulfonimide polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002212234A JP2002212234A (en) | 2002-07-31 |
| JP4815672B2 true JP4815672B2 (en) | 2011-11-16 |
Family
ID=18880313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001013464A Expired - Lifetime JP4815672B2 (en) | 2001-01-22 | 2001-01-22 | Method for producing fluorine-containing sulfonimide polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4815672B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7473748B2 (en) * | 2004-01-22 | 2009-01-06 | Asahi Kasei Kabushiki Kaisha | Vinyl monomer with superacid ester group and polymer of the same |
| JP4930690B2 (en) * | 2005-05-13 | 2012-05-16 | 株式会社豊田中央研究所 | Ion conductive polymers and imide monomers |
| US10505197B2 (en) | 2011-03-11 | 2019-12-10 | Audi Ag | Unitized electrode assembly with high equivalent weight ionomer |
| US9663600B2 (en) | 2012-12-21 | 2017-05-30 | Audi Ag | Method of fabricating an electrolyte material |
| EP2948997B1 (en) | 2012-12-21 | 2017-12-20 | Audi AG | Electrolyte membrane, dispersion and method therefor |
| KR102018941B1 (en) * | 2012-12-21 | 2019-09-05 | 도요타지도샤가부시키가이샤 | Proton exchange material and method therefor |
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1034197A (en) * | 1963-09-13 | 1966-06-29 | Du Pont | Sulphonic acid derivatives of fluorocarbon vinyl ethers, and polymers thereof |
| US5463005A (en) * | 1992-01-03 | 1995-10-31 | Gas Research Institute | Copolymers of tetrafluoroethylene and perfluorinated sulfonyl monomers and membranes made therefrom |
| JPH09188795A (en) * | 1995-12-29 | 1997-07-22 | Asahi Glass Co Ltd | Liquid composition of perfluorocarbon polymer containing fluorosulfonyl group |
| MXPA01012994A (en) * | 1999-06-16 | 2002-09-02 | Du Pont | Fluorinated ionic polymers. |
| WO2001027167A1 (en) * | 1999-10-12 | 2001-04-19 | Millipore Corporation | Fluorocarbon polymeric compositions having hydrophilic functional groups and process |
-
2001
- 2001-01-22 JP JP2001013464A patent/JP4815672B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002212234A (en) | 2002-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4774988B2 (en) | Solid polymer electrolyte material, production method, and membrane electrode assembly for solid polymer fuel cell | |
| EP1734603B1 (en) | Electrolyte material for polymer electrolyte fuel cells, electrolyte membrane and membrane- electrode assembly | |
| JP4788267B2 (en) | Polymer having fluorosulfonyl group and 1,3-dioxolane structure and use thereof | |
| CN101228117A (en) | Fluorosulfonyl group-containing compound, method for its production and polymer thereof | |
| JP6593346B2 (en) | Electrolyte material, liquid composition, and membrane electrode assembly for polymer electrolyte fuel cell | |
| JP2020534402A (en) | Fluoropolymer dispersions, methods for producing fluoropolymer dispersions, catalytic inks and polymer electrolyte membranes | |
| JPH1021943A (en) | Polymer electrolytic substance for fuel cell, and fuel cell | |
| JP2007009223A (en) | Fluorocarbon polymeric composition having hydrophilic functional group and method for producing the same | |
| JP4815672B2 (en) | Method for producing fluorine-containing sulfonimide polymer | |
| EP2882705B1 (en) | Allyl-bearing fluorinated ionomers | |
| JP5187999B2 (en) | Fluorinated ionomer | |
| JP2007537306A (en) | Stable trifluorostyrene-containing compounds and their use in polymer electrolyte membranes | |
| US7414102B2 (en) | Polymer electrolyte of high durability and a production process thereof | |
| US10022716B2 (en) | Method for producing ionic polymer membrane | |
| JP2002212246A (en) | Block polymer, production method for polymer, and liquid composition containing block polymer | |
| JPWO2020116647A1 (en) | Acid-type sulfonic acid group-containing polymer, liquid composition, solid polymer electrolyte membrane, membrane electrode assembly, polymer electrolyte fuel cell and ion exchange membrane for water electrolysis | |
| JP4334375B2 (en) | Vinyl monomer containing N-alkylbissulfonylimide group | |
| JP6007647B2 (en) | Ionic polymer and method for producing the same | |
| US7456314B2 (en) | Partially fluorinated ionic compounds | |
| EP2752431B1 (en) | Method for producing organic compound having sulfo group, method for producing liquid composition, and method for hydrolyzing organic compound having fluorosulfonyl group | |
| JP4176392B2 (en) | Method for producing sulfonamide group-containing monomer | |
| US8415070B2 (en) | Partially fluorinated cyclic ionic polymers and membranes | |
| CA3213611A1 (en) | Polymer electrolyte membrane, block copolymer, polymer electrolyte material, polymer electrolyte molded body, electrolyte membrane with catalyst layer, membrane electrode composite, solid polymer fuel cell, and water electrolytic hydrogen generator | |
| CN115403691A (en) | Perfluorinated anion resin, preparation method thereof and alkaline anion exchange membrane | |
| CN115572339A (en) | Ion-modified perfluorinated anion resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20050603 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20050610 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071207 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100915 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100928 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101122 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20101124 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110802 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110815 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140909 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4815672 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140909 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |