JPS63225634A - Aniline/cation exchanger polymeric composite membrane and its production - Google Patents
Aniline/cation exchanger polymeric composite membrane and its productionInfo
- Publication number
- JPS63225634A JPS63225634A JP5871787A JP5871787A JPS63225634A JP S63225634 A JPS63225634 A JP S63225634A JP 5871787 A JP5871787 A JP 5871787A JP 5871787 A JP5871787 A JP 5871787A JP S63225634 A JPS63225634 A JP S63225634A
- Authority
- JP
- Japan
- Prior art keywords
- cation exchanger
- polymer
- polyaniline
- composite membrane
- aniline
- 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
- 150000001768 cations Chemical class 0.000 title claims abstract description 54
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000012528 membrane Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000767 polyaniline Polymers 0.000 claims abstract description 43
- 239000002019 doping agent Substances 0.000 claims abstract description 39
- 238000005341 cation exchange Methods 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 55
- 229920001940 conductive polymer Polymers 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 4
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000005349 anion exchange Methods 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006479 redox reaction Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 4
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- -1 and as a result Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は新規な導電性高分子に関するものであり、さら
に詳しくは高分子カチオン交換体のカチオン交換基を固
定ドーパントとするポリアニリンと高分子カチオン交換
体よりなる導電性高分子複合膜及びその製造法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel conductive polymer, and more particularly to a conductive polymer made of a polymer cation exchanger and polyaniline in which the cation exchange group of the polymer cation exchanger is a fixed dopant. This invention relates to a molecular composite membrane and its manufacturing method.
８Ｊ電電性弁子は、その新規な物理特性、電気化学特性
より、導体．半導体，電池，表示素子，光電変換素子，
センサー等の新しい機能材料として注目を集めている。8J electric valve is a conductor due to its novel physical and electrochemical properties. Semiconductors, batteries, display elements, photoelectric conversion elements,
It is attracting attention as a new functional material for sensors, etc.
［従来技術］
イオンドーピング法によりポリアセチレンの導電性が著
しく上昇することが見出されて以来、各種のイオンドー
パント型導電性高分子、例えばポリピロール、ポリアニ
リン、ポリチオフェン、ポリバラフェニレン等が提案さ
れている。[Prior Art] Since it was discovered that the conductivity of polyacetylene can be significantly increased by ion doping, various ion-doped conductive polymers, such as polypyrrole, polyaniline, polythiophene, and polyvaraphenylene, have been proposed. .
これらの導電性高分子は一般にアニオン、カチオン等の
ドーパントの出入り（導電性高分子の酸化、還元に対応
）により、化学ポテンシャルが変化するが、この現象を
利用して電池、センサー。Generally, the chemical potential of these conductive polymers changes due to the entry and exit of dopants such as anions and cations (corresponding to oxidation and reduction of the conductive polymer), and this phenomenon is used to develop batteries and sensors.
表示素子等の電気化学素子への応用が提案されている。Application to electrochemical devices such as display devices has been proposed.
電気化学反応は、電極と電解質の界面でイオンの移動と
電子の移動を変換、接合する反応であるが、上述したよ
うに一般的な導電性高分子は、酸化還元反応に対応して
ドーパントイオンを電解質から受取り又、電解質へ放出
する性質をもつ、いわゆる移動ドーパント型の導電性高
分子である。Electrochemical reactions are reactions that convert and combine the movement of ions and electrons at the interface between electrodes and electrolytes, but as mentioned above, general conductive polymers react with dopant ions in response to redox reactions. It is a so-called mobile dopant type conductive polymer that has the property of receiving and releasing ions from an electrolyte.
この様な移動ドーパント型の導電性高分子は、優れた導
電性を示す新規な機能材料として注目を集めているもの
であるが、導電性高分子の強度。Such mobile dopant-type conductive polymers are attracting attention as new functional materials that exhibit excellent conductivity, but the strength of conductive polymers is limited.
耐久性、安定性等の実用材料としての基本的な性質が問
題視されている。The basic properties of this material as a practical material, such as durability and stability, are being questioned.
又、電気化学素子としてａ能させようとすると、ドーパ
ントの出入りによりその導電性が著しく変化するため電
気抵抗が変化すること、ドーパントの出入りにより電気
化学素子内の電解液の組成が変化すること、電解重合時
のドーパントと電気化学素子内の電解液の組成達異なる
場合、素子の系を複雑にし、時には導電性高分子として
機能しなくなる等の点が指摘されている。これらの物理
的。In addition, when attempting to function as an electrochemical element, the conductivity changes significantly due to the inflow and outflow of dopants, resulting in changes in electrical resistance, and the composition of the electrolytic solution within the electrochemical element changes due to the inflow and outflow of dopants. It has been pointed out that if the composition of the dopant during electrolytic polymerization and the electrolyte in the electrochemical device are different, the device system becomes complicated and sometimes the device does not function as a conductive polymer. These physical.
電気化学的特性は、目的とする素子にとって必要な性質
である場合もあるが、逆に欠点となる場合もある。Although electrochemical properties may be necessary for the intended device, they may also be a drawback.
［発明の目的］
本発明の目的は、従来の移動ドーパント型の導電性高分
子に対し、固定ドーパント型の導電性高分子を提案する
ことであり、特に、高分子カチオン交換体のカチオン交
換基を固定ドーパントとするポリアニリンと高分子カチ
オン交換体よりなる新規な導電性高分子複合膜及びその
報造法を提案するものである。[Objective of the Invention] The object of the present invention is to propose a fixed dopant type conductive polymer, in contrast to the conventional mobile dopant type conductive polymer, and in particular, to propose a fixed dopant type conductive polymer. This paper proposes a novel conductive polymer composite membrane consisting of polyaniline and a polymer cation exchanger with 2 as a fixed dopant, and a method for fabricating the same.
［発明の詳細な説明］
本発明の高分子カチオン交換体のカチオン交換基を固定
ドーパントとするポリアニリンと高分子カチオン交換体
よりなる導電性高分子複合膜は、従来のポリアニリンと
は全く異なった新規な導電性高分子である。従来公知の
ポリアニリンは、アニオンをドーパントとする移動ドー
パント型の導電性高分子であり、電気化学的な酸化還元
反応に対応してこの７ニオンドーバントが出入りするが
、一方、本発明のポリアニリンと高分子カチオン交換体
との高分子複合膜においては、高分子カチオン交換体の
固定電荷（固定７ニオン基）であるカチオン交換基がド
ーパントとなり、このドーパントは導電性高分子の中に
固定されている。そのために、この様な固定ドーパント
型の導電性高分子に於ては、電気化学的な酸化還元反応
に対応して出入りするイオンはアニオンではなくカチオ
ンとなる。この関係をモデル的に図１に示す。図１のポ
リアニリン単独膜に於ては、電気化学的な酸化還元反応
に対応して、Ｃオーアニオンが出入りしているが、−力
木発明のポリアニリンと高分子カチオン交換体（図では
ＮａｆｉＯｎ）との高分子複合膜に於ては、Ｎａｆｉｏ
ｎのＳ０３がドーパントとして固定されその結果電気化
学的な酸化還元反応に対応してＮａ＋カチオンが出入り
するようになる。[Detailed Description of the Invention] The conductive polymer composite film made of polyaniline and a polymer cation exchanger in which the cation exchange group of the polymer cation exchanger of the present invention is a fixed dopant is a novel film completely different from conventional polyaniline. It is a conductive polymer. Conventionally known polyaniline is a mobile dopant type conductive polymer that uses an anion as a dopant, and this 7-ion dopant moves in and out in response to an electrochemical redox reaction.On the other hand, the polyaniline of the present invention In a polymer composite film with a polymer cation exchanger, the cation exchange group, which is a fixed charge (fixed 7 anion group) of the polymer cation exchanger, becomes a dopant, and this dopant is fixed in the conductive polymer. There is. Therefore, in such fixed dopant type conductive polymers, ions that enter and exit in response to electrochemical redox reactions are cations rather than anions. This relationship is shown in FIG. 1 as a model. In the polyaniline single film shown in Figure 1, C-o anions move in and out in response to electrochemical redox reactions; In the polymer composite membrane with Nafio
n S03 is fixed as a dopant, and as a result, Na + cations come in and out in response to an electrochemical redox reaction.
この様に本発明のポリアニリンと高分子カチオン交換体
との高分子複合膜は、従来の移動ドーパント型のポリア
ニリンと全く異なった性質を示す固定ドーパント型の新
規な導電性高分子であることがわかる。Thus, it can be seen that the polymer composite film of polyaniline and polymer cation exchanger of the present invention is a new fixed dopant type conductive polymer that exhibits properties completely different from conventional mobile dopant type polyaniline. .
本発明のポリアニリンと高分子カチオン交換体との高分
子複合膜に於て、高分子カチオン交換体とは、例えば、
スルフォン酸基やカルボン酸基等の固定アニオンを交換
基として持つペルフルオロカーボン骨格よりなるフッ素
系高分子カチオン交換体（Ｄｕｐｏｎｔ社のＮａｔｉｏ
ｎ等）やポリピニルサルフエイト、ポリスチレンスルフ
ォネイト等を例示することができる。In the polymer composite membrane of polyaniline and a polymer cation exchanger of the present invention, the polymer cation exchanger is, for example,
A fluorinated polymer cation exchanger consisting of a perfluorocarbon skeleton having fixed anions such as sulfonic acid groups and carboxylic acid groups as exchange groups (Natio
n, etc.), polypynylsulfate, polystyrene sulfonate, etc.
本発明のポリアニリンと高分子カチオン交換体との高分
子複合膜を製造するためには化学的合成法、ＬＢ腹膜法
電解重合法等を用いることができる。この中でも、電解
重合法は、得られる物質の均質性１反応制御の容易さ０
作業性、経済性等より好ましい製造法の一つである。電
解重合法とは、電気化学的に電極表面上でモノマーを電
解酸化あるいは還元して重合反応を行い高分子化合物を
合成する方法である。この合成法は、電解液中に挿入し
た電極に電位を与え、カチオンラジカルやアニオンラジ
カルのような反応活性種を生成し合成するものであるが
、電解重合とともにイオンドーピングを同時におこなう
ことが可能であり、得られる高分子は高いｓｍ性を有し
た高分子となる。In order to produce the polymer composite membrane of polyaniline and polymer cation exchanger of the present invention, chemical synthesis methods, LB peritoneal electrolytic polymerization methods, etc. can be used. Among these, the electrolytic polymerization method has the following advantages: 1) homogeneity of the obtained material, 1) ease of reaction control, 0)
This is one of the preferred manufacturing methods in terms of workability, economy, etc. The electrolytic polymerization method is a method of electrochemically oxidizing or reducing monomers on the surface of an electrode to perform a polymerization reaction and synthesize a polymer compound. In this synthesis method, a potential is applied to an electrode inserted into an electrolytic solution to generate and synthesize reactive species such as cation radicals and anion radicals, but it is possible to perform ion doping along with electrolytic polymerization at the same time. The resulting polymer has high SM properties.
本発明のポリアニリンと高分子カチオン交換体との高分
子複合膜を得るための電解゛重合法に於ては、電解液と
してアニリンのモノマーを含む電解液中で電解反応を行
うことにより、陽極表面に、高分子カチオン交換体のカ
チオン交換基を固定ドーパントとするポリアニリンと高
分子カチオン交換体よりなるｌ’ｉｌｉ性八分子複へ膜
を酸化重合する方法を用いることが望ましい。In the electrolytic polymerization method for obtaining a polymer composite membrane of polyaniline and a polymer cation exchanger of the present invention, the anode surface is In this case, it is desirable to use a method of oxidatively polymerizing a membrane into a l'ili octamolecular complex consisting of polyaniline and a polymer cation exchanger, in which the cation exchange group of the polymer cation exchanger is used as a fixed dopant.
本発明のポリアニリンと高分子カチオン交換体との高分
子複合膜を電解重合法で得るためには、例えば高分子イ
オン交換体のポリマー溶液とアニリンのモノマー溶液と
の混合溶液を用いて電解重合することも可能である。In order to obtain the polymer composite membrane of the present invention of polyaniline and a polymer cation exchanger by electrolytic polymerization, for example, electropolymerization is carried out using a mixed solution of a polymer solution of a polymer ion exchanger and a monomer solution of aniline. It is also possible.
電解重合法の好ましい実施態様の一つは高分子カチオン
交換体を被覆した導電性基体を陽極とし、電解液として
アニリンのモノマーを含む電解液中で電解反応を行うこ
とにより、該陽極表面に、高分子カチオン交換体のカチ
オン交換基を固定ドーパントとするポリアニリンと高分
子カチオン交換体よりなる導電性高分子複合膜を製造す
る方法である。One of the preferred embodiments of the electrolytic polymerization method is to use a conductive substrate coated with a polymeric cation exchanger as an anode, and conduct an electrolytic reaction in an electrolytic solution containing an aniline monomer, so that on the surface of the anode, This is a method for producing a conductive polymer composite membrane consisting of polyaniline and a polymer cation exchanger, in which the cation exchange group of the polymer cation exchanger is used as a fixed dopant.
上記導電性基体は、例えばＰｔ、Ａｕ等の金属や、表面
にＩＴＯ等の導電性物質を被覆した導電性硝子等の任意
の導電性基体の上にあらかじめ高分子カチオン交換体を
被覆したものをｍＡとして用いることができる。高分子
カチオン交換体を被覆する方法としては、特に限定され
ないが、例えば上記高分子カチオン交換体を含む溶液を
上記導電性を有する基体の上に塗布する方法が用いられ
る。The above-mentioned conductive substrate may be any conductive substrate, such as metal such as Pt or Au, or conductive glass whose surface is coated with a conductive substance such as ITO, on which a polymer cation exchanger is coated in advance. It can be used as mA. The method for coating the polymer cation exchanger is not particularly limited, but for example, a method of applying a solution containing the polymer cation exchanger onto the conductive substrate may be used.
カチオン交換体を被覆した導電性基体を得る好ましい実
施態様の一つは、高分子カチオン交換体として公知のＮ
ａｆｉｏｎの溶液を任意の導電性基体上に塗布し乾燥す
る方法である。このようにして、カチオン交換体を被覆
した導電性基体を陽極として用いて、アニリンのモノマ
ーを含む溶液を電解液として、陽極上に酸化重合するこ
とにより、本発明のポリアニリンと高分子カチオン交換
体との高分子複合膜を製造することができる。なお、こ
の場合、電解液としては導電性を持たせるために支持電
解質を含む有機溶媒や水溶液が用いられる。One of the preferred embodiments for obtaining a conductive substrate coated with a cation exchanger is N
This method involves applying a solution of afion onto any conductive substrate and drying it. In this way, by using the conductive substrate coated with the cation exchanger as an anode and oxidatively polymerizing the solution containing the aniline monomer as an electrolyte on the anode, the polyaniline and polymer cation exchanger of the present invention can be combined. It is possible to produce a polymer composite membrane with. In this case, as the electrolytic solution, an organic solvent or an aqueous solution containing a supporting electrolyte is used in order to impart conductivity.
電解液の例としては、例えば、過塩素酸塩や塩化ナトリ
ウム等を含む溶液に１０ １１０１／Ｊ〜１ｏ１ｍｏｌ
／ｊ！程アニリンを溶解した水溶液をあげることができ
る。陽極酸化重合の条件としては、必要とする導電性高
分子の性質により種々変化させることができるが、一般
に定電位電解法、７ｊ１位走査電解法、定電流電解法、
交流電解法、パルス電解法等を用いることができる。Examples of electrolytes include solutions containing perchlorate, sodium chloride, etc.
/j! An example is an aqueous solution in which aniline is dissolved. The conditions for anodic oxidation polymerization can be varied depending on the properties of the required conductive polymer, but generally include constant potential electrolysis, 7j1-position scanning electrolysis, constant current electrolysis,
AC electrolysis, pulse electrolysis, etc. can be used.
このような電解重合法により、カチオン交換体を被覆し
た陽極上にアニリンが酸化重合するが、単にアニリンが
電解重合するのではなく、カチオン交換体との高分子複
合膜を形成しながら重合反応が進行すると考えられる。In this electrolytic polymerization method, aniline is oxidatively polymerized on the anode coated with a cation exchanger, but aniline is not simply electropolymerized, but the polymerization reaction occurs while forming a polymer composite film with the cation exchanger. It is thought that it will progress.
このことは、得られる導電性高分子が、一般のポリアニ
リンのように酸化還元反応に於て、アニオンドーパント
の出入りを伴うものではなく、カチオンの出入りを伴い
、従って固定アニオンドーパント型となっていることに
より裏付けられる。This means that the resulting conductive polymer does not involve the inflow and outflow of anion dopants during the redox reaction as in general polyaniline, but rather the inflow and outflow of cations, and is therefore of a fixed anion dopant type. This is supported by this.
なお、本発明の説明に於ては、アニリンのモノマーを重
合する過程を説明したが、アニリンの誘導体、又はアニ
リンの２同体以上の多量体またはその誘導体より重合す
ることも可能である。In the description of the present invention, the process of polymerizing aniline monomers has been described, but it is also possible to polymerize aniline derivatives, aniline diisomers or more, or derivatives thereof.
［発明の効果］
本発明は、高分子カチオン交換体のカチオン交換基を固
定ドーパントとするポリアニリンと高分子カチオン交換
体よりなる導電性高分子複合膜及びその製造法を提案す
るものである。[Effects of the Invention] The present invention proposes a conductive polymer composite membrane made of polyaniline and a polymer cation exchanger in which the cation exchange group of the polymer cation exchanger is a fixed dopant, and a method for producing the same.
本発明のポリアニリンと高分子カチオン交換体との高分
子複合膜は、従来の移動ドーパント型のポリアニリンと
全く異なった性質を示す固定ドーパント型の新規な導電
性高分子であり、新規な電気化学素子を与えるものとし
て注目されるものである。The polymer composite film of polyaniline and a polymer cation exchanger of the present invention is a new fixed dopant type conductive polymer that exhibits properties completely different from conventional mobile dopant type polyaniline, and is a novel electrochemical device. It is attracting attention as it provides the following.
さらに、本発明のポリアニリンと高分子カチオン交換体
との高分子複合膜は、複合膜化されていることにより、
導電性高分子自体の強度、耐久性。Furthermore, the polymer composite membrane of polyaniline and polymer cation exchanger of the present invention has the following properties:
The strength and durability of the conductive polymer itself.
安定性等の向上が期待されるものである。This is expected to improve stability, etc.
［実施例］
以下、実施例を述べるが本発明はこれに限定されるもの
ではない。[Example] Examples will be described below, but the present invention is not limited thereto.
実施例１．比較例１
実施例１として、ＡＵ Ｐｌａｔｅ上にＮａｒｔｏｎ
１１７のアルコール溶液を塗布し乾燥したもの（有効′
Ｉ１１極面積１ａＩｌ）を陽極として用い、電解液とし
て、１ｓｏｌ／ｊのアニリンと２麿ｏｆ／オのＨＣオを
含む水溶液を用いて、０．２ｍＡ／ｄの定電流で１００
ｍＣ陽極酸化重合を実施し、ポリアニリンとＮａｆ ｉ
ｏｎとの導電性高分子複合膜を得た。Example 1. Comparative Example 1 As Example 1, Narton was placed on the AU Plate.
117 alcohol solution and dried (effective '
I11 electrode area 1aIl) was used as an anode, an aqueous solution containing 1 sol/j aniline and 2 sol/j HC2 was used as the electrolyte, and a constant current of 0.2 mA/d was applied at 100 mA/d.
Perform mC anodic oxidation polymerization to form polyaniline and Nafi
A conductive polymer composite film with on was obtained.
得られた試料の０．２ｓｏｌ／オ塩化ナトリウム水溶液
（ｐＨ＝ ７ ）の中でのサイクリックポルタモグラム
を測定した。The cyclic portamogram of the obtained sample in a 0.2 sol/sodium ochloride aqueous solution (pH=7) was measured.
その結果を図２のａ（実線）で示す。The results are shown in a (solid line) in FIG.
また、同様に０．２ｓｏｌ／Ｊのベンゼンスルフオン酸
ナトリウム水溶液（ｐＨ−７＞の中でのサイクリックポ
ルタモグラムも測定した。Similarly, a cyclic portamogram in a 0.2 sol/J sodium benzenesulfonate aqueous solution (pH-7>) was also measured.
その結果を図３のａ（実線）で示す。The results are shown in a (solid line) in FIG.
一方、比較例１としてＮａｆｉｏｎを被覆してない＾ｕ
Ｐｌａｔｅをそのまま陽極として用い、実施例１と同
一の電解液中、同一の電解条件で酸化重合を実施し、ポ
リアニリン被膜を得た。On the other hand, as Comparative Example 1, Nafion was not coated^u
Using the plate as it was as an anode, oxidative polymerization was carried out in the same electrolytic solution as in Example 1 under the same electrolytic conditions to obtain a polyaniline film.
得られた試料のサイクリックポルタモグラムを実施例１
と同様の条件下で測定した。The cyclic portamogram of the obtained sample is shown in Example 1.
Measured under the same conditions.
その結果を図２のｂ（破線）１図３のｂ（破線）で各々
示す。図２９図３より明らかな様に、本発明の実施例１
により得られたポリアニリンとＮａｆｉｏｎとの複合膜
は、アニオン種の違いに左右されることなく殆ど同一の
可逆的なポルタモグラムを示し反応応答性に優れた膜で
あることがわかるが、比較例１により得られたポリアニ
リン被膜は、非可逆的なポルタモグラムを示し、又塩化
ナトリウム溶液の場合は、比較的大きな電流値を与える
が、ベンゼンスルフオン酸ナトリウム溶液の様に電解質
アニオンのイオン半径が大きな場合は電流値が減少する
ことがわかる。The results are shown by b (broken line) in FIG. 2 and b (broken line) in FIG. 3, respectively. FIG. 29 As is clear from FIG. 3, Example 1 of the present invention
It can be seen that the composite membrane of polyaniline and Nafion obtained by the above method shows almost the same reversible portamogram regardless of the difference in anion species, and is a membrane with excellent reaction response. The obtained polyaniline film shows an irreversible portamogram, and in the case of a sodium chloride solution, it gives a relatively large current value, but in the case of a sodium benzenesulfonate solution where the ionic radius of the electrolyte anion is large, It can be seen that the current value decreases.
即ち、比較例１のポリアニリン被膜は、電気化学的酸化
還元反応に伴いアニオンが出入りする移動アニオンドー
パント型であるが、本発明の実施例１のポリアニリンと
ＨａｆｌＯｎとの導電性高分子複合膜は、酸化還元反応
に伴い出入りする移動極はアニオンではなくカチオンで
あり固定アニオンドーパント型（本実施例の場合は５ａ
ｒｔｏｎのスルフォン酸基をドーパントとして固定）の
新規な複合膜であることがわかる。That is, the polyaniline film of Comparative Example 1 is of a mobile anion dopant type in which anions enter and exit through an electrochemical redox reaction, but the conductive polymer composite film of polyaniline and HaflOn of Example 1 of the present invention The mobile electrode that enters and exits with the redox reaction is a cation rather than an anion, and is a fixed anion dopant type (in this example, 5a
It can be seen that this is a novel composite film in which the sulfonic acid group of rton is fixed as a dopant.
実施例２．比較例２
実施例２として、実施例１で得られたポリアニリン−Ｎ
ａｔｉｏｎ複合膜を０．２１ｏ１／Ｊ ＮａＣ１水溶
液（ｐＨ−４）の中で、数回電位走査により酸化還元さ
せた後に、＋０，４Ｖ ｖｓ ５ＣＥｔ’酸化させ
たもの、及び−０，６Ｖ ｖｓ ＳＣＥで還元させ
たものをＥＰＭＡで測定し、酸化体と還元体のＣオの差
を求めた。Example 2. Comparative Example 2 As Example 2, polyaniline-N obtained in Example 1
ation composite membrane was redoxed by potential scanning several times in a 0.21o1/J NaCl aqueous solution (pH-4), and then oxidized at +0.4V vs. 5CEt', and -0.6V vs. SCE. The reduced product was measured by EPMA to determine the difference in CO between the oxidized product and the reduced product.
その結果を図４に示す。The results are shown in FIG.
一方、比較例２として比較例１で得られたポリアニリン
被膜を実施例２と同様にＥＰＭＡで測定し、酸化体と還
元体のＣオの差を求めた。On the other hand, as Comparative Example 2, the polyaniline film obtained in Comparative Example 1 was measured by EPMA in the same manner as in Example 2, and the difference in CO between the oxidized form and the reduced form was determined.
その結果を図５に示す。図４，５より明らかな様に、実
施例２の被膜では酸化体、還元体ともＣＪ濃度の変化は
殆ど認められず、Ｈａｆ ｉｏｎのスルフォン酸基をド
ーパントとする固定アニオンドーパント型であることが
わかるが、一方比較例２の被膜では、酸化体のほうが還
元体より多くのＣオを含んでおり、一般のＣ１アニオン
ドーパント型であることがわかる。The results are shown in FIG. As is clear from FIGS. 4 and 5, in the film of Example 2, almost no change in CJ concentration was observed in both the oxidized and reduced forms, indicating that it was a fixed anion dopant type in which the sulfonic acid group of Hafion was used as the dopant. As can be seen, on the other hand, in the film of Comparative Example 2, the oxidized form contains more C than the reduced form, indicating that it is a general C1 anion dopant type.
図１は本発明のポリアニリンと高分子カチオン交換体と
の高分子複合膜と、従来のポリアニリン単独膜の電気化
学的酸化還元反応のモデルを示す図である。
図２は実施例１で得られたポリアニリンとＮａｆｉｏｎ
との高分子複合膜と、比較例１で得られたポリアニリン
被膜の、０．２■０１／ｉの塩化ナトリウム水溶液中で
のサイクリックポルタモグラムを示す図である。
図３は実施例１で得られたポリアニリンとＮａｆｉｏｎ
との高分子複合膜と、比較例１で得られたポリアニリン
被膜の０．２ｓｏｌ／ｊのベンゼンスルフオン酸ナトリ
ウム水溶液中でのサイクリックポルタモグラムを示す図
である。
尚、図２０図３中のａ（実線）は、実施例１で得られた
高分子複合膜のｂ（破線）は、比較例１で得られたポリ
アニリン被膜のサイクリックポルタモグラムを示す。
図４は実施例２におけるポリアニリンとＮａｔｉｏｎと
の高分子複合膜の、酸化体、還元体のＥ ＰＭＡ測定の
結果を示す図である。
図５は比較例２におけるポリアニリン単独膜の、酸化体
、還元体のＥＰＭＡ測定の結果を示す図である。
特許出願人 東洋曹達工業株式会社
酸化
膜へのアニオン流入
還元
膜からのアニオン流出
酸化還元機構モデル
還元
図２
Ｅ／ＶＶＳＳＣＥ
塩化ナトリウム溶液中
Ｅ／Ｖ ＶＳ、ＳＣＥ
ベンゼンスルフオン酸ナトリウム
溶液中FIG. 1 is a diagram showing a model of an electrochemical redox reaction between a polymer composite film of the present invention of polyaniline and a polymer cation exchanger and a conventional polyaniline single film. Figure 2 shows the polyaniline obtained in Example 1 and Nafion.
1 is a diagram showing cyclic portamograms of a polymer composite membrane of 100% and a polyaniline coating obtained in Comparative Example 1 in a 0.2×01/i sodium chloride aqueous solution. Figure 3 shows the polyaniline obtained in Example 1 and Nafion.
FIG. 2 is a diagram showing cyclic portamograms of a polymer composite film obtained in Comparative Example 1 and a polyaniline film obtained in Comparative Example 1 in a 0.2 sol/j sodium benzenesulfonate aqueous solution. Note that in FIGS. 20 and 3, a (solid line) shows the polymer composite film obtained in Example 1, and b (broken line) shows the cyclic portamogram of the polyaniline film obtained in Comparative Example 1. FIG. 4 is a diagram showing the results of EPMA measurement of oxidants and reductants of the polymer composite film of polyaniline and Nation in Example 2. FIG. 5 is a diagram showing the results of EPMA measurement of oxidized and reduced forms of the polyaniline single film in Comparative Example 2. Patent applicant Toyo Soda Kogyo Co., Ltd. Anion inflow into oxide film and anion outflow from reduction film Redox mechanism model reduction Figure 2 E/VVSSCE in sodium chloride solution E/V VS, SCE in sodium benzenesulfonate solution
Claims (1)
パントとするポリアニリンと高分子カチオン交換体より
なるアニリン／カチオン交換体高分子複合膜。 ２）電解液としてアニリンのモノマーを含む電解液中で
電解反応を行うことにより、陽極表面に、高分子カチオ
ン交換体のカチオン交換基を固定ドーパントとするポリ
アニリンと高分子カチオン交換体よりなる導電性複合膜
を酸化重合することを特徴とするアニリン／カチオン交
換体高分子複合膜の製造法。 ３）高分子カチオン交換体を被覆した導電性基体を陽極
とし、電解液としてアニリンのモノマーを含む電解液中
で電解反応を行うことにより、該陽極表面に、高分子カ
チオン交換体のカチオン交換基を固定ドーパントとする
ポリアニリンと高分子カチオン交換体よりなる導電性高
分子複合膜を酸化重合する特許請求の範囲第２項記載の
アニリン／カチオン交換体高分子複合膜の製造法。[Scope of Claims] 1) An aniline/cation exchanger polymer composite membrane comprising polyaniline and a polymer cation exchanger in which the cation exchange group of the polymer cation exchanger is a fixed dopant. 2) By carrying out an electrolytic reaction in an electrolytic solution containing an aniline monomer as an electrolyte, a conductive material made of polyaniline and a polymer cation exchanger with the cation exchange group of the polymer cation exchanger as a fixed dopant is formed on the anode surface. A method for producing an aniline/cation exchanger polymer composite membrane, which comprises subjecting the composite membrane to oxidative polymerization. 3) A conductive substrate coated with a polymeric cation exchanger is used as an anode, and an electrolytic reaction is performed in an electrolytic solution containing an aniline monomer to form a cation exchange group of the polymeric cation exchanger on the surface of the anode. 3. The method for producing an aniline/cation exchanger polymer composite membrane according to claim 2, wherein a conductive polymer composite membrane comprising polyaniline and a polymer cation exchanger is oxidatively polymerized, with the fixed dopant being polyaniline and a polymer cation exchanger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5871787A JPS63225634A (en) | 1987-03-16 | 1987-03-16 | Aniline/cation exchanger polymeric composite membrane and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5871787A JPS63225634A (en) | 1987-03-16 | 1987-03-16 | Aniline/cation exchanger polymeric composite membrane and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63225634A true JPS63225634A (en) | 1988-09-20 |
Family
ID=13092246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5871787A Pending JPS63225634A (en) | 1987-03-16 | 1987-03-16 | Aniline/cation exchanger polymeric composite membrane and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63225634A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01138237A (en) * | 1987-08-04 | 1989-05-31 | Kao Corp | Composite film of conjugated polymer and cation exchanger and its production |
| JPH01254588A (en) * | 1988-04-01 | 1989-10-11 | Ibiden Co Ltd | Tray case of semiconductor mounting board |
| JPH0269525A (en) * | 1988-09-05 | 1990-03-08 | Nitto Denko Corp | Thin film composite material of electroconductive organic polymer |
| JPH07105718A (en) * | 1992-03-19 | 1995-04-21 | Ind Technol Res Inst | Molecular complex consisting of conductive polymer and macromolecular electrolyte, and manufacture thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6339930A (en) * | 1986-08-04 | 1988-02-20 | Tokuyama Soda Co Ltd | Production of improved ion exchange membrane |
| JPS63118338A (en) * | 1986-11-06 | 1988-05-23 | Tokuyama Soda Co Ltd | Modified ion exchange membrane |
-
1987
- 1987-03-16 JP JP5871787A patent/JPS63225634A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6339930A (en) * | 1986-08-04 | 1988-02-20 | Tokuyama Soda Co Ltd | Production of improved ion exchange membrane |
| JPS63118338A (en) * | 1986-11-06 | 1988-05-23 | Tokuyama Soda Co Ltd | Modified ion exchange membrane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01138237A (en) * | 1987-08-04 | 1989-05-31 | Kao Corp | Composite film of conjugated polymer and cation exchanger and its production |
| JPH01254588A (en) * | 1988-04-01 | 1989-10-11 | Ibiden Co Ltd | Tray case of semiconductor mounting board |
| JPH0269525A (en) * | 1988-09-05 | 1990-03-08 | Nitto Denko Corp | Thin film composite material of electroconductive organic polymer |
| JPH07105718A (en) * | 1992-03-19 | 1995-04-21 | Ind Technol Res Inst | Molecular complex consisting of conductive polymer and macromolecular electrolyte, and manufacture thereof |
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