JP2001233974A - Ion-exchange membrane and method for producing it - Google Patents
Ion-exchange membrane and method for producing itInfo
- Publication number
- JP2001233974A JP2001233974A JP2000046079A JP2000046079A JP2001233974A JP 2001233974 A JP2001233974 A JP 2001233974A JP 2000046079 A JP2000046079 A JP 2000046079A JP 2000046079 A JP2000046079 A JP 2000046079A JP 2001233974 A JP2001233974 A JP 2001233974A
- Authority
- JP
- Japan
- Prior art keywords
- exchange membrane
- ion
- film
- ion exchange
- membrane
- 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.)
- Pending
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
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イオン交換膜とそ
の製造方法に関し、さらに詳しくは、薄膜で、機械的強
度に優れ、リチウムイオン電池の隔膜や燃料電池の高分
子電解質膜として必要なイオン伝導性を有し、湿潤後の
耐久性、耐熱性に優れ、イオン交換基の場所によるバラ
ツキが小さく、大面積の量産にも適したイオン交換膜、
並びにその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion-exchange membrane and a method for producing the same, and more particularly, to an ion-exchange membrane which is thin and has excellent mechanical strength and is required as a membrane for a lithium ion battery or a polymer electrolyte membrane for a fuel cell. It has conductivity, excellent durability after wetting, heat resistance, small variation due to the location of the ion exchange group, suitable for mass production of large area,
And its manufacturing method.
【０００２】[0002]
【従来の技術】従来より、イオン交換膜は、電気分解、
電気透析、拡散透析、圧透析、ドナン透析、逆浸透、浸
透気化などの隔膜；リチウムイオン電池や燃料電池など
の隔膜や高分子固体電解質膜；などの広範な用途に使用
されている。汎用のイオン交換膜は、材質から分類する
と、炭化水素系イオン交換膜とパーフルオロカーボン系
イオン交換膜に分けられる。2. Description of the Related Art Conventionally, ion exchange membranes have been used for electrolysis,
It is used in a wide range of applications such as diaphragms for electrodialysis, diffusion dialysis, pressure dialysis, donnan dialysis, reverse osmosis, and pervaporation; diaphragms for lithium ion batteries and fuel cells, and solid polymer electrolyte membranes. General-purpose ion-exchange membranes are classified into hydrocarbon-based ion-exchange membranes and perfluorocarbon-based ion-exchange membranes according to their materials.
【０００３】炭化水素系イオン交換膜の殆どは、スチレ
ンージビニルベンゼン共重合体に陽イオン交換基または
陰イオン交換基を導入したものである。イオン交換基と
しては、スルホン酸基やカルボン酸基などの陽イオン交
換基、あるいは四級アンモニウム塩基などの陰イオン交
換基が使用されている。また、スチレンービニルピリジ
ンージビニルベンゼン共重合体膜をスルホン化、四級化
することにより、陽イオン交換基と陰イオン交換基とを
有する両性イオン交換膜を作ることができる。[0003] Most of the hydrocarbon ion exchange membranes are obtained by introducing a cation exchange group or an anion exchange group into a styrene divinyl benzene copolymer. As the ion exchange group, a cation exchange group such as a sulfonic acid group or a carboxylic acid group, or an anion exchange group such as a quaternary ammonium base is used. Further, an amphoteric ion exchange membrane having a cation exchange group and an anion exchange group can be produced by sulfonating and quaternizing the styrene-vinylpyridine divinylbenzene copolymer membrane.
【０００４】燃料電池の高分子固体電解質膜として開発
されたパーフルオロカーボン系イオン交換膜は、耐酸化
性、耐アルカリ性に優れているため、食塩電解のための
隔膜をはじめとして、広範な技術分野で使用されるに至
っている。イオン交換基としてスルホン酸基やカルボン
酸基を用いたパーフルオロカーボン系陽イオン交換膜
は、ナフィオン（デユポン）、フレミオン（旭硝子）、
アシプレックス（旭化成）、ネオセプタ（徳山曹達）な
どの商品名（登録商標名）で市販されている。デユポン
社製のナフィオン（Ｎａｆｉｏｎ）は、テトラフルオロ
エチレンとパーフルオロスルホニルエトキシビニルエー
テルとの共重合体を加水分解したものである。A perfluorocarbon ion exchange membrane developed as a polymer solid electrolyte membrane for a fuel cell has excellent oxidation resistance and alkali resistance. Therefore, it has been used in a wide range of technical fields, including a diaphragm for salt electrolysis. Has been used. Perfluorocarbon cation exchange membranes using sulfonic acid groups or carboxylic acid groups as ion exchange groups are available from Nafion (DuPont), Flemion (Asahi Glass),
It is marketed under the trade name (registered trademark) such as Aciplex (Asahi Kasei) and Neosepta (Tokuyama Soda). Nafion manufactured by DuPont is obtained by hydrolyzing a copolymer of tetrafluoroethylene and perfluorosulfonylethoxyvinyl ether.
【０００５】このように、パーフルオロカーボン系イオ
ン交換ポリマーは、パーフルオロアルキレン基を主鎖骨
格とし、一部にパーフルオロビニルエーテル側鎖の末端
にイオン交換基を有する構造を持っている。これらのイ
オン交換膜は、例えば、容易にイオン交換基にできる−
ＳＯ2Ｆまたはカルボン酸エステルを有するパーフルオ
ロカーボンスルホン酸膜のスルホン酸基を化学反応によ
って陰イオン交換基に変換すれば、パーフルオロカーボ
ン系陰イオン交換膜を得ることができる。[0005] As described above, the perfluorocarbon ion exchange polymer has a structure in which a perfluoroalkylene group is used as a main chain skeleton and an ion exchange group is partially provided at a terminal of a perfluorovinyl ether side chain. These ion exchange membranes, for example, can be easily converted into ion exchange groups.
A perfluorocarbon-based anion exchange membrane can be obtained by converting a sulfonic acid group of a perfluorocarbon sulfonic acid membrane having SO 2 F or a carboxylic acid ester into an anion exchange group by a chemical reaction.
【０００６】[0006]
【発明が解決しようとする課題】以上に述べた従来のイ
オン交換膜には、次のような問題がある。すなわち、炭
化水素系イオン交換膜は、電気化学的性質に優れている
ものの、耐薬品性及び耐酸化性が十分ではなく、特に、
高温や強い酸化雰囲気中などの過酷な条件下で使用する
と、耐久性が著しく低下する。たとえば、炭化水素系イ
オン交換膜を電解用隔膜や電池用隔膜として使用する
と、化学変化を受けて、イオン交換性能が低下する。パ
ーフルオロカーボン系イオン交換膜は、前記の通り、耐
酸化性、耐アルカリ性に優れているが、高温雰囲気、具
体的には、１００℃以上の温度で使用しようとすると、
膜が軟化し、使用に耐えられない。特開平９―７３９０
８号公報には、イオン交換膜の耐熱性を上げるために、
ポリベンズイミダゾールをスルホン化したイオン交換膜
が提案されているが、材料の合成、スルホン化などの工
程が難しく、コストが高いという問題点がある。The conventional ion exchange membrane described above has the following problems. That is, although the hydrocarbon-based ion-exchange membrane is excellent in electrochemical properties, its chemical resistance and oxidation resistance are not sufficient.
When used under severe conditions such as high temperature and strong oxidizing atmosphere, the durability is significantly reduced. For example, when a hydrocarbon-based ion exchange membrane is used as a membrane for electrolysis or a membrane for a battery, the ion exchange performance is reduced due to a chemical change. As described above, the perfluorocarbon ion exchange membrane has excellent oxidation resistance and alkali resistance, but when used in a high-temperature atmosphere, specifically, at a temperature of 100 ° C. or higher,
The film softens and cannot be used. JP-A-9-7390
In order to improve the heat resistance of the ion exchange membrane,
Although ion exchange membranes in which polybenzimidazole is sulfonated have been proposed, there is a problem that steps such as material synthesis and sulfonation are difficult, and the cost is high.
【０００７】[0007]
【課題を解決するための手段】本発明は、パーフルオロ
カーボン系イオン交換膜と同等の耐化学安定性を持ち、
１００℃以上の高温雰囲気でも使用可能な耐熱性を持
ち、容易に低コストで作製できるイオン交換膜とその製
造方法を提供することを目的とするもので、イミド結合
を有する耐熱性高分子を薄膜にした後、スルホン化剤に
浸漬し、スルホン化することを特徴とするものである。The present invention has the same chemical stability as a perfluorocarbon ion exchange membrane,
An object of the present invention is to provide an ion-exchange membrane having heat resistance that can be used even in a high-temperature atmosphere of 100 ° C. or more and can be easily manufactured at low cost, and a method for manufacturing the same. And then immersing in a sulfonating agent for sulfonation.
【０００８】[0008]
【発明の実施の形態】本発明でいうイミド結合を有する
耐熱性高分子とは、分子構造中にイミド結合を有し、芳
香族環、シアヌル環等の環状構造を主成分とする高分子
である。たとえば、ポリイミド、ポリアミドイミド、ポ
リエーテルイミド、ポリエステルイミドなどが挙げられ
る。ポリイミド、ポリアミドイミドとして、更に具体的
には、次のような高分子が挙げられる。ピロメリット酸
とジアミノジフェニルエーテルより合成されるポリイミ
ド、ビフェニルテトラカルボン酸とフェニレンジアミン
より合成されるポリイミド、トリメリット酸又はその無
水物と、芳香族ジアミン又はジイソシアネートより合成
されるポリアミドイミド、トリメリット酸又はその無水
物と、ジアミノジフェニルエーテル又はジアミノジフェ
ニルメタン又はジフェニルメタンジイソシアネートより
合成されるポリアミドイミド。BEST MODE FOR CARRYING OUT THE INVENTION The term "heat-resistant polymer having an imide bond" as used in the present invention refers to a polymer having an imide bond in the molecular structure and having a cyclic structure such as an aromatic ring or a cyanuric ring as a main component. is there. For example, polyimide, polyamide imide, polyether imide, polyester imide and the like can be mentioned. More specifically, examples of the polyimide and the polyamideimide include the following polymers. Polyimide synthesized from pyromellitic acid and diaminodiphenyl ether, polyimide synthesized from biphenyltetracarboxylic acid and phenylenediamine, trimellitic acid or its anhydride, and polyamideimide synthesized from aromatic diamine or diisocyanate, trimellitic acid or A polyamideimide synthesized from the anhydride and diaminodiphenyl ether or diaminodiphenylmethane or diphenylmethane diisocyanate.
【０００９】前記のような、分子構造中にイミド結合を
有し、芳香族環、シアヌル環等の環状構造を主成分とす
る高分子は、薄膜化した後、スルホン化剤に浸漬したと
きに、主鎖の切断等の高分子の劣化が生じ難く、スルホ
ン化がスムーズに進行するという特徴がある。中でも、
ビフェニルテトラカルボン酸とフェニレンジアミンより
合成されるポリイミド、及び、トリメリット酸又はその
無水物と、ジアミノジフェニルエーテル又はジアミノジ
フェニルメタン又はジフェニルメタンジイソシアネート
より合成されるポリアミドイミドは、上記の特徴が顕著
であり、好ましい。The above-mentioned polymer having an imide bond in the molecular structure and having a cyclic structure such as an aromatic ring or a cyanuric ring as a main component is formed into a thin film and then immersed in a sulfonating agent. In addition, there is a feature that deterioration of the polymer such as breakage of the main chain hardly occurs and sulfonation proceeds smoothly. Among them,
Polyimide synthesized from biphenyltetracarboxylic acid and phenylenediamine, and polyamideimide synthesized from trimellitic acid or its anhydride, and diaminodiphenyl ether, diaminodiphenylmethane, or diphenylmethane diisocyanate are preferable because of the remarkable characteristics described above.
【００１０】スルホン化剤としては、濃硫酸、発煙硫
酸、クロルスルホン酸等、通常使用されるスルホン化剤
が使用できる。このスルホン化剤をそのまま又は溶剤に
希釈して、その中に、前記の耐熱性高分子をフィルム化
したものを、所定の温度で、所定の時間、浸漬すること
によりスルホン化を実施することができる。As the sulfonating agent, commonly used sulfonating agents such as concentrated sulfuric acid, fuming sulfuric acid and chlorosulfonic acid can be used. This sulfonating agent can be used as it is or by diluting it in a solvent, in which a film of the heat-resistant polymer is immersed at a predetermined temperature for a predetermined time to perform sulfonation. it can.
【００１１】スルホン化ポリイミドや、スルホン化ポリ
アミドイミドは、特開昭６３―２８３７０４号公報、特
開昭６３―２８３７０５号公報、特開平９―１０５６７
号公報等に開示されているが、これらはいずれも、フィ
ルム化する前にスルホン化していて、フィルム化が難し
く、イオン交換膜に適した物性のフィルムを得るのが難
しい。スルホン化に使用する耐熱性高分子のフィルムの
厚さとしては、スルホン化したものをイオン交換膜とし
て使用する上から、０．００５ｍｍ〜０．１００ｍｍが
好ましい。また、スルホン化剤中への浸漬の条件として
は、スルホン化剤として濃硫酸を使用したときは、溶剤
で希釈せず、室温〜６０℃程度で、数分〜数時間といっ
た条件で浸漬することが推奨でき、スルホン化剤にクロ
ルスルホン酸を使用する場合は、クロロホルム、ジクロ
ルメタン、トリクロルエチレン等の溶剤を使用して数％
〜１５％に希釈し、室温〜１００℃で、数分〜数時間と
いった条件で浸漬することが推奨できる。Sulfonated polyimides and sulfonated polyamideimides are disclosed in JP-A-63-283704, JP-A-63-283705, and JP-A-9-10567.
However, these are all sulfonated before forming into a film, making it difficult to form a film, and making it difficult to obtain a film having physical properties suitable for an ion exchange membrane. The thickness of the heat-resistant polymer film used for sulfonation is preferably 0.005 mm to 0.100 mm from the viewpoint of using the sulfonated film as an ion exchange membrane. When using concentrated sulfuric acid as the sulfonating agent, do not dilute with a solvent, but immerse it at room temperature to about 60 ° C for several minutes to several hours. If chlorosulfonic acid is used as the sulfonating agent, use a solvent such as chloroform, dichloromethane, trichloroethylene, etc.
It is recommended to dilute to １５15% and immerse at room temperature to 100 ° C. for several minutes to several hours.
【００１２】[0012]
【実施例】以下に、本発明について、実施例、及び比較
例を挙げて、具体的に説明する。なお、実施例、比較例
のイオン交換膜についての、物性の測定には、次の方法
を使用した。 （１）膜厚：ダイアルゲージを用いた測定。 （２）膜強度：ＪＩＳ Ｋ−７１１３に準拠したインス
トロン引張試験機を用いた測定。（抗張力、伸び） （３）膜の電気抵抗：複素インピーダンス法による測
定。（ 直径１ｃｍのステンレス円板電極使用 ）The present invention will be specifically described below with reference to examples and comparative examples. The following methods were used to measure the physical properties of the ion exchange membranes of Examples and Comparative Examples. (1) Film thickness: Measurement using a dial gauge. (2) Membrane strength: Measured using an Instron tensile tester based on JIS K-7113. (Tensile strength, elongation) (3) Electric resistance of membrane: Measured by complex impedance method. (Uses stainless steel electrode with a diameter of 1cm)
【００１３】（実施例１）ビフェニルテトラカルボン酸
無水物とフェニレンジアミンより合成したポリイミドを
用いて作製した膜厚５０μｍのフィルムを、濃硫酸（濃
度９６％以上）に、４０℃で、１時間浸漬した。その
後、フィルムを水洗し、蒸留水中で１日放置した。こう
して得られたポリイミドのスルホン化フィルムの特性
は、表１に示した通りで、イオン交換膜として必要な低
い電気抵抗性を持ち、耐熱性にも優れていることが判っ
た。Example 1 A 50 μm-thick film made from a polyimide synthesized from biphenyltetracarboxylic anhydride and phenylenediamine was immersed in concentrated sulfuric acid (concentration of 96% or more) at 40 ° C. for 1 hour. did. Thereafter, the film was washed with water and left in distilled water for one day. The characteristics of the polyimide sulfonated film thus obtained were as shown in Table 1, and it was found that the film had a low electric resistance required for an ion exchange membrane and was excellent in heat resistance.
【００１４】（実施例２〜３）濃硫酸中への浸漬温度を
２５℃（ 実施例２）、６０℃（ 実施例３）とした以外
は実施例１と同様にして、ポリイミドのスルホン化フィ
ルムを得た。得られたポリイミドのスルホン化フィルム
の特性は、表１に示した通りで、イオン交換膜として必
要な低い電気抵抗性を持ち、耐熱性にも優れていること
が判った。(Examples 2 and 3) Sulfonated polyimide film in the same manner as in Example 1 except that the immersion temperature in concentrated sulfuric acid was 25 ° C. (Example 2) and 60 ° C. (Example 3). I got The properties of the obtained polyimide sulfonated film were as shown in Table 1, and it was found that the polyimide had a low electric resistance required for an ion exchange membrane and was excellent in heat resistance.
【００１５】（実施例４）トリメリット酸無水物とジフ
ェニルメタンジイソシアネートより合成したポリアミド
イミドのワニス（ ＨＩ−４００：日立化成社製）を用
いて、２５０℃で塗布・焼付けして、膜厚５０μｍのフ
ィルムを作製した。得られたポリアミドイミドフィルム
を実施例１と同様に処理して、ポリアミドイミドのスル
ホン化フィルムを得た。得られたポリアミドイミドのス
ルホン化フィルムの特性は、表１に示した通りで、イオ
ン交換膜として必要な低い電気抵抗性を持ち、耐熱性に
も優れていることが判った。Example 4 A polyamideimide varnish synthesized from trimellitic anhydride and diphenylmethane diisocyanate (HI-400: manufactured by Hitachi Chemical Co., Ltd.) was applied and baked at 250 ° C. to give a film having a thickness of 50 μm. A film was prepared. The obtained polyamideimide film was treated in the same manner as in Example 1 to obtain a polyamideimide sulfonated film. The properties of the obtained polyamideimide sulfonated film were as shown in Table 1, and it was found that the film had a low electric resistance necessary for an ion exchange membrane and was excellent in heat resistance.
【００１６】（実施例５）濃硫酸の代わりにクロルスル
ホン酸をトリクロルエタンに容量比で５％に混合したス
ルホン化剤を使用した以外は実施例１と同様にして、ポ
リイミドのスルホン化フィルムを得た。得られたポリイ
ミドのスルホン化フィルムの特性は、表１に示した通り
で、イオン交換膜として必要な低い電気抵抗性を持ち、
耐熱性にも優れていることが判った。Example 5 A sulfonated polyimide film was prepared in the same manner as in Example 1 except that a sulfonating agent obtained by mixing chlorosulfonic acid with trichloroethane at a volume ratio of 5% was used instead of concentrated sulfuric acid. Obtained. The properties of the obtained sulfonated polyimide film are as shown in Table 1, and have a low electrical resistance required as an ion exchange membrane.
It turned out that it was also excellent in heat resistance.
【００１７】（比較例１）パーフルオロ系イオン交換膜
（ ナフィオン膜厚５０μｍ：デユポン社製）を使用
し、特性を評価した結果は、表１に示した通りで、１２
０℃では、膜が軟化してしまって、電気抵抗の測定もで
きなかった。(Comparative Example 1) Using a perfluoro-based ion-exchange membrane (Nafion film thickness 50 μm: manufactured by DuPont), the characteristics were evaluated.
At 0 ° C., the film softened, and the electrical resistance could not be measured.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】以上に述べた通り、イミド結合を有する
耐熱性高分子を薄膜にした後、スルホン化剤に浸漬し、
スルホン化することにより、パーフルオロカーボン系イ
オン交換膜と同等の耐化学安定性を持ち、１００℃以上
の高温雰囲気でも使用可能な耐熱性を持ったイオン交換
膜が容易に低コストで得ることができ、その工業的価値
は高い。As described above, after a heat-resistant polymer having an imide bond is formed into a thin film, it is immersed in a sulfonating agent,
By sulfonating, an ion-exchange membrane having the same chemical resistance as a perfluorocarbon-based ion-exchange membrane and having heat resistance that can be used even in a high-temperature atmosphere of 100 ° C. or higher can be easily obtained at low cost. , Its industrial value is high.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｂ Ｃ０８Ｌ 79:08 Ｃ０８Ｌ 79:08 (72)発明者 山内 雅晃 大阪市此花区島屋一丁目１番３号 住友電 気工業株式会社大阪製作所内 Ｆターム(参考） 4F071 AA60 AA60C AB23 AG01 AH15 FA05 FB01 FC01 4J043 PA01 QB15 QB26 QB31 QB32 RA05 RA35 SA06 SB01 SB02 TA13 TA14 TA21 TB01 UA121 UA131 UA132 UB011 UB121 YB05 YB13 ZA06 ZA11 ZB14 ZB47 5H026 AA06 BB03 CX05 EE18 5H029 AJ01 AJ06 AJ14 AM16 CJ13 EJ12 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // H01M 10/40 H01M 10/40 B C08L 79:08 C08L 79:08 (72) Inventor Masaaki Yamauchi Osaka 1-3-3 Shimaya, Konohana-ku, Ichigo Sumitomo Electric Industries, Ltd. Osaka Works F-term (reference) 4F071 AA60 AA60C AB23 AG01 AH15 FA05 FB01 FC01 4J043 PA01 QB15 QB26 QB31 QB32 RA05 RA35 SA06 SB01 SB02 TA13 TA14 TA21 TB131 UA121 UA132 UB011 UB121 YB05 YB13 ZA06 ZA11 ZB14 ZB47 5H026 AA06 BB03 CX05 EE18 5H029 AJ01 AJ06 AJ14 AM16 CJ13 EJ12
Claims (6)
ルム化した後に、これをスルホン化剤に浸漬し、スルホ
ン化したことを特徴とするイオン交換膜。1. An ion-exchange membrane obtained by forming a heat-resistant polymer having an imide bond into a film and then immersing the film in a sulfonating agent to sulfonate the film.
イミドであることを特徴とする請求項１に記載のイオン
交換膜。2. The ion exchange membrane according to claim 1, wherein the heat-resistant polymer having an imide bond is polyimide.
ェニルテトラカルボン酸とフェニレンジアミンより合成
されるポリイミドであることを特徴とする請求項１に記
載のイオン交換膜。3. The ion exchange membrane according to claim 1, wherein the heat-resistant polymer having an imide bond is a polyimide synthesized from biphenyltetracarboxylic acid and phenylenediamine.
アミドイミドであることを特徴とする請求項１に記載の
イオン交換膜。4. The ion exchange membrane according to claim 1, wherein the heat-resistant polymer having an imide bond is a polyamide imide.
メリット酸又はその無水物と、ジアミノジフェニルエー
テル又はジアミノジフェニルメタン又はジフェニルメタ
ンジイソシアネートより合成されるポリアミドイミドで
あることを特徴とする請求項１に記載のイオン交換膜。5. The heat-resistant polymer having an imide bond is a polyamideimide synthesized from trimellitic acid or its anhydride and diaminodiphenyl ether, diaminodiphenylmethane or diphenylmethane diisocyanate. Ion exchange membrane.
ルム化した後に、これをスルホン化剤に浸漬し、スルホ
ン化することを特徴とするイオン交換膜の製造方法。6. A method for producing an ion exchange membrane, comprising forming a film of a heat-resistant polymer having an imide bond, and immersing the film in a sulfonating agent to sulfonate the film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000046079A JP2001233974A (en) | 2000-02-23 | 2000-02-23 | Ion-exchange membrane and method for producing it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000046079A JP2001233974A (en) | 2000-02-23 | 2000-02-23 | Ion-exchange membrane and method for producing it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001233974A true JP2001233974A (en) | 2001-08-28 |
Family
ID=18568561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000046079A Pending JP2001233974A (en) | 2000-02-23 | 2000-02-23 | Ion-exchange membrane and method for producing it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001233974A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003035609A1 (en) * | 2001-10-25 | 2003-05-01 | 3M Innovative Properties Company | Zwitterionic imides |
| WO2006001083A1 (en) * | 2004-06-29 | 2006-01-05 | Samsung Yokohama Research Institute | Solid polymer electrolyte, electrode for fuel cell, and fuel cell |
| JP2008117663A (en) * | 2006-11-06 | 2008-05-22 | Cheil Industries Inc | Polymer electrolyte membrane for fuel cell, membrane-electrode assembly, and fuel cell |
| US20090087748A1 (en) * | 2007-10-02 | 2009-04-02 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same |
| US8022165B2 (en) | 2006-02-16 | 2011-09-20 | Basf Se | Catalytic process for the phosphonylation of high-temperature polymers |
| JP2014046264A (en) * | 2012-08-31 | 2014-03-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Ion exchanger having high thermostability and high durability, and collection method of useful metal and toxic metal using the same |
-
2000
- 2000-02-23 JP JP2000046079A patent/JP2001233974A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003035609A1 (en) * | 2001-10-25 | 2003-05-01 | 3M Innovative Properties Company | Zwitterionic imides |
| WO2006001083A1 (en) * | 2004-06-29 | 2006-01-05 | Samsung Yokohama Research Institute | Solid polymer electrolyte, electrode for fuel cell, and fuel cell |
| US8022165B2 (en) | 2006-02-16 | 2011-09-20 | Basf Se | Catalytic process for the phosphonylation of high-temperature polymers |
| JP2008117663A (en) * | 2006-11-06 | 2008-05-22 | Cheil Industries Inc | Polymer electrolyte membrane for fuel cell, membrane-electrode assembly, and fuel cell |
| US20090087748A1 (en) * | 2007-10-02 | 2009-04-02 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same |
| US8529801B2 (en) * | 2007-10-02 | 2013-09-10 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same |
| JP2014046264A (en) * | 2012-08-31 | 2014-03-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Ion exchanger having high thermostability and high durability, and collection method of useful metal and toxic metal using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6248469B1 (en) | Composite solid polymer electrolyte membranes | |
| Smitha et al. | Solid polymer electrolyte membranes for fuel cell applications—a review | |
| CA2300934C (en) | Composite solid polymer electrolyte membranes | |
| US7550216B2 (en) | Composite solid polymer electrolyte membranes | |
| US20220352534A1 (en) | Bipolar ionomer membrane | |
| Xu et al. | Novel ether-free sulfonated poly (biphenyl) tethered with tertiary amine groups as highly stable amphoteric ionic exchange membranes for vanadium redox flow battery | |
| EP1690314B1 (en) | Polymer electrolyte with aromatic sulfone crosslinking | |
| Ren et al. | Preparation and investigation of reinforced PVP blend membranes for high temperature polymer electrolyte membranes | |
| JP2002324559A (en) | Multifunctional electrolyte, electrochemical device using the same and production method of the multifunctional electrolyte | |
| JP5008272B2 (en) | Composite proton exchange membrane | |
| JP4102299B2 (en) | Ionomer used in fuel cell and method for producing the same | |
| JP4065424B2 (en) | Cross-linked sulfonated polyimide film | |
| JP5627198B2 (en) | Proton conducting polymer electrolyte membrane, membrane-electrode assembly and polymer electrolyte fuel cell using the same | |
| JP2004131532A (en) | Polybenzimidazole compound having phosphonic acid group and resin composition comprising the same and method for producing the same | |
| JP2001233974A (en) | Ion-exchange membrane and method for producing it | |
| JP2004131533A (en) | Polybenzimidazole compound having sulfonic acid group and/or phosphonic acid group and resin composition comprising the same and method for producing the same | |
| Sha’rani et al. | Evaluation of Perfluorinated Sulfonic Acid Membranes for Vanadium Redox | |
| JP2000090945A (en) | Solid polymer electrolyte film, manufacture thereof and solid polymer electrolyte fuel cell | |
| JP4913397B2 (en) | Proton conducting solid polymer electrolyte and fuel cell | |
| Peckham et al. | Proton exchange membranes | |
| KR20110090051A (en) | Branched and sulfonated copolymer containing perfluorocyclobutane rings, preparation method thereof and electrolyte membrane using the same | |
| JP2008138104A (en) | Aromatic hydrocarbon-based ion exchange membrane and method for producing the same | |
| Lancheros et al. | Development and characterization of poly (oxy-1, 4-phenylenesulfonyl-1, 4-phenylene) for proton exchange membranes | |
| CN116769201A (en) | Poly (chlorotrifluoroethylene) film, preparation method and application thereof | |
| US20150010847A1 (en) | Method for the production of a proton exchange membrane for a fuel cell by means of solvent-casting |