JPS60177197A - Electrochemical doping method of polymer having ferrocene nucleus - Google Patents
Electrochemical doping method of polymer having ferrocene nucleusInfo
- Publication number
- JPS60177197A JPS60177197A JP59032143A JP3214384A JPS60177197A JP S60177197 A JPS60177197 A JP S60177197A JP 59032143 A JP59032143 A JP 59032143A JP 3214384 A JP3214384 A JP 3214384A JP S60177197 A JPS60177197 A JP S60177197A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- ferrocene
- working electrode
- electrolyte
- doping
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 23
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 18
- -1 poly(vinyl ferrocene Chemical compound 0.000 abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- 238000003411 electrode reaction Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 2
- 229920002554 vinyl polymer Polymers 0.000 abstract 2
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 abstract 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VGBAECKRTWHKHC-UHFFFAOYSA-N cyclopenta-1,3-diene;1-ethenylcyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.[CH2-]C=C1C=CC=C1 VGBAECKRTWHKHC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はポリビニルフェロセン等のフェロセン核を有す
るポリマーの電気化学的ドーピングによる有機高分子導
電体の製造法に係わる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing organic polymeric conductors by electrochemical doping of polymers having ferrocene nuclei, such as polyvinylferrocene.
導電性ポリマーをつくるためには、ドーピングが重要で
ある。これまでにいくつかのドーピング方法が知られて
いる。即ち、（１）化学的方法、（２）電気化学的方法
、（３）イオンインプランテーション等である。化学的
ドーピングは、通常、■ガスにさらす方法あるいは■溶
液浸漬法によってなされている。従来、化学的ドーピン
グが多くなされたが、たとえば八ｓ Ｆ。Doping is important to create conductive polymers. Several doping methods are known so far. That is, (1) chemical method, (2) electrochemical method, (3) ion implantation, etc. Chemical doping is usually carried out by (1) gas exposure method or (2) solution immersion method. Conventionally, many chemical doping methods have been used, such as 8sF.
のような毒性の強い試剤の使用は実用上好ましくない。The use of highly toxic reagents such as these is practically undesirable.
電気化学的ドーピングの例としては、例えばポリアセチ
レン、フタロシアニネイトボリシロキサン、ポリ （Ｎ
−ビニルカルバゾール）等について報告されており、ま
た導電性ポリ（ピロール）の電気化学的形成もしられて
いる。Examples of electrochemical doping include, for example, polyacetylene, phthalocyaninate polysiloxane, poly(N
-vinylcarbazole), etc., and electrochemical formation of conductive poly(pyrrole) has also been reported.
一方、エレクトロクロミック表示素子における表示材料
および対極材料の作動機能は、電気化学的酸化あるいは
還元であり、これは見方を変えれば、電気化学的ドーピ
ングに相当する。On the other hand, the operating function of the display material and counter electrode material in an electrochromic display element is electrochemical oxidation or reduction, which corresponds to electrochemical doping from another perspective.
本発明者等はエレクトロクロミック表示素子用電極材料
ならびに対極材料としても利用し得ることを目的として
ポリビニルフェロセン等のフェロセン核を有するポリマ
ーの電気化学的ドーピングについて検討を行った結果、
電気化学的ドーピングの新しい簡単な技術により、電気
伝導性を有し、鮮明な着色を有する部分的に酸化された
フェロセン核を有するポリマーの膜を容易に製造し得る
ことを見いだし本発明に至ったものである。The present inventors have investigated electrochemical doping of a polymer having a ferrocene nucleus such as polyvinylferrocene with the aim of making it usable as an electrode material for electrochromic display elements and as a counter electrode material.
The inventors have discovered that a new and simple technique of electrochemical doping makes it possible to easily produce membranes of polymers with partially oxidized ferrocene nuclei that are electrically conductive and have a bright coloration. It is something.
即ち本発明は支持電解質を含むポリビニルフェロセン等
のフェロセン核を有するポリマーの有機溶剤溶液を定電
位陽極酸化することにより作用電極表面に導電性高分子
の膜を析出させることを特徴とする電気化学的ドーピン
グ法に係わる。That is, the present invention is an electrochemical method characterized by depositing a conductive polymer film on the surface of a working electrode by subjecting an organic solvent solution of a polymer having a ferrocene nucleus, such as polyvinylferrocene, containing a supporting electrolyte to constant potential anodic oxidation. Concerning doping laws.
本発明の電気化学的ドーピング法、即ち定電位陽極酸化
による電気化学的析出法をポリビニルフェロセンを用い
る場合について説明すると、中性のポリビニルフェロセ
ンポリマーを含む有機電解液から、ドープされたポリマ
ーが不溶化して析出することに基づいている。かかる電
気化学的ドーピングは適当な有機溶媒にポリマーを適当
な支持電解質と共に溶解して電解質溶液をつくり、この
電解液に作用電極のネサガラス板、或いはプラチナ板等
と対向電極（ネサガラス、白金板、ニッケル板など）を
挿入し、作用電極板が正極となる様に定電圧電極反応を
行って、作用電極板上に陽極酸化されたポリ （ビニル
フェロセン）が濃青色ポリマーの膜として析出すること
により行われる。この際電位がかけられる反応溶液は徐
々に青色に変化する。To explain the electrochemical doping method of the present invention, that is, the electrochemical deposition method by constant potential anodic oxidation, when polyvinylferrocene is used, the doped polymer is insolubilized from an organic electrolyte containing a neutral polyvinylferrocene polymer. It is based on the method of precipitation. Such electrochemical doping involves dissolving a polymer in an appropriate organic solvent together with an appropriate supporting electrolyte to create an electrolyte solution, and adding a working electrode such as a Nesa glass plate or a platinum plate and a counter electrode (Nesa glass, platinum plate, nickel plate, etc.) to this electrolyte solution. A constant voltage electrode reaction is performed with the working electrode plate serving as the positive electrode, and anodized poly(vinylferrocene) is deposited as a dark blue polymer film on the working electrode plate. be exposed. At this time, the reaction solution to which a potential is applied gradually turns blue.
適当な有機溶媒としてはジクロロメタンがあげられ、適
当な電解質としてはテトラ−ｎ−ブチルアンモニウムバ
ークロレイトがあげられる。A suitable organic solvent includes dichloromethane and a suitable electrolyte includes tetra-n-butylammonium verchlorate.
このようにして製造された導電性高分子は従来の化学的
ドーピングで製造されたものと比べて、導電性及び均一
性にすぐれ、またエレクトロクロミック表示素子用電極
材料あるいは対極材料としての利用に於いて、満足でき
るものであった。The conductive polymer produced in this way has superior conductivity and uniformity compared to those produced by conventional chemical doping, and is suitable for use as an electrode material or counter electrode material for electrochromic display elements. It was very satisfying.
以下本発明を実施例について説明するが、本発明はこの
実施例に限定されるものではない。The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.
実施例
ポリ （ビニルフェロセン）は７０℃におけるベンゼン
中のアゾビスイソブチロニトリル（ＡＩＢＮ）を開始剤
とするビニルフェロセンのフリーラジカル重合によって
作られ、メタノール中におけるＴＨＦによる再沈澱を繰
り返すことによって精製し、真空乾燥した。Ｍｎ ＝
２２００、Ｍｗ＝３７００ （ポリスチレンを標準とし
てＧＰＣによって決定される）。EXAMPLE Poly(vinylferrocene) was made by free radical polymerization of vinylferrocene initiated with azobisisobutyronitrile (AIBN) in benzene at 70°C and purified by repeated reprecipitation with THF in methanol. and vacuum dried. Mn =
2200, Mw=3700 (determined by GPC with polystyrene as standard).
電気化学的ドーピングは二車構造のセルを用い、支持電
解質としてテトラ−ｎ−ブチルアンモニウムバークロレ
イト（０，１ｍｏｌ ｄＩｌｌ−３）を含むポリ （ビ
ニルフェロセン） （１，ＯＸＩＯｍｏｌ ｄｎ＋ ）
のジクロロメタン溶液を定電位陽極酸化することによっ
てなされた。ネサガラス板（４，５Ｘ２．５ ｃＪ）ま
たはプラチナ板が作用電極として使われ、対向電極とし
てプラチナ板（２，ＯＸ２．Ｏｄ）が用いられた。参照
電極はアセトニトリル中のＡｇ／Δｇ” ０．０１ｍｏ
ｌ ｄｍ−’であった。定電位電極反応を適当な時間（
１８０分）行った後、電極の表面に析出した生成ポリマ
ーは精製されたジクロロメタンによって洗浄し、真空で
乾燥された。Electrochemical doping used a two-car cell with poly(vinylferrocene) (1,OXIOmol dn+) containing tetra-n-butylammonium verchlorate (0,1 mol dIll-3) as the supporting electrolyte.
was done by potentiostatic anodization of a dichloromethane solution. A Nesa glass plate (4,5X2.5 cJ) or a platinum plate was used as the working electrode, and a platinum plate (2,OX2.Od) was used as the counter electrode. The reference electrode was Ag/Δg” 0.01 mo in acetonitrile.
It was l dm-'. The constant potential electrode reaction is carried out for an appropriate time (
After 180 minutes), the resulting polymer deposited on the surface of the electrode was washed with purified dichloromethane and dried in vacuum.
電気伝導性は圧縮ペレットに金電極を蒸着し、端子ｄ、
ｃ、法によって測定された。Electrical conductivity is achieved by depositing gold electrodes on compressed pellets and connecting terminals d,
c, measured by the method.
上記の電気化学的ドーピングのための電気化学的析出法
は中性ポリマー溶液からのドープされたポリマーの不溶
解性に基づいている。電気化学的ドーピングは定電位陽
極酸化によって行われた。即ち、ジクロロメタン中に熔
解したポリ （ビニルフェロセン）は基準ｉ［ＩＡｇ／
Ａｇ”０．１ ｍｏｌ ｄｉ’に対して０．３００ Ｖ
で陽極酸化された（ジクロロメタン溶液に対する ｃｙ
ｃｌｉｃｖｏｌ ｔａｍｍｏｇｒａｍ により決定され
たポリ （ビニルフェロセン）のピークの酸化電位は参
照電極Ａｇ／Ａｇ＋０．０１ｍｏｌ ｄｍ−’に対し０
．１７９ Ｖ’） 、電位がかけられると反応溶液は徐
々に青色に変化する。反応が進むにつれ、濃青色ポリマ
ーが作用電極の表面に析出する。電流は約１ｍＡから１
８０分間の電気分解の間に徐々に約０．７ ｍＡに減少
する）。The electrochemical deposition method for electrochemical doping described above is based on the insolubility of the doped polymer from a neutral polymer solution. Electrochemical doping was performed by potentiostatic anodic oxidation. That is, poly(vinylferrocene) dissolved in dichloromethane has a standard i[IAg/
0.300 V for Ag”0.1 mol di’
anodized (cy against dichloromethane solution)
The peak oxidation potential of poly(vinylferrocene) determined by clicvol tammogram is 0 with respect to the reference electrode Ag/Ag+0.01 mol dm-'.
．． 179 V'), the reaction solution gradually turns blue when a potential is applied. As the reaction progresses, a dark blue polymer is deposited on the surface of the working electrode. The current is about 1mA to 1
(gradually decreases to approximately 0.7 mA during 80 minutes of electrolysis).
電極に析出したポリマーはフェロセンと対アニオンとし
てＣｔＯ、−をもつフェリセニウムイオンペンダント基
を含む部分的に酸化された混合原子価塩である。電気化
学的にドープされたポリ （ビニルフェロセン）の拡散
反射電子スペクトルは明らかに約４６０および６２５
ｎｍにピークをもつ吸収帯を示した。これらはそれぞれ
フェロセンとフエリセニウムイオンｃｈｒｏｍｏｐｈｏ
ｒｅｓに基づくものである。ドープされたポリマーの■
ＲスベクＩ・ルはＣｔＯＩ＋−による１１１０および１
０８０ＣＩ１１−１に強いハンドを示した。The polymer deposited on the electrode is a partially oxidized mixed valence salt containing ferrocene and a ferricenium ion pendant group with CtO, - as a counteranion. The diffuse reflection electron spectrum of electrochemically doped poly(vinylferrocene) is clearly about 460 and 625
It showed an absorption band with a peak at nm. These are ferrocene and ferricenium ion chromophores, respectively.
It is based on res. ■ of doped polymer
Rsubek I Le is 1110 and 1 by CtOI+-
He showed a strong hand with 080CI11-1.
このポリマーの構造は次の一般式で表されるものと推定
される。The structure of this polymer is presumed to be represented by the following general formula.
電気化学的にドープされたポリ （ビニルフェロセン）
はｌｘｌＯ５ｃｍの室温における高い伝導度を示し、伝
導度はドーピング量に依存する。結果を第１表に示す。Electrochemically doped poly(vinylferrocene)
shows a high conductivity at room temperature of lxlO5cm, and the conductivity depends on the doping amount. The results are shown in Table 1.
電気化学的にドープされたポリ （ビニルフェロセン）
の電気伝導度の値は化学的にドープされた ポリ （ビ
ニルフェロセン）、即ち２，３−ジクロロ−５，６−ジ
シアノ）−ｐ−ベンゾキノン（Ｄ Ｄ Ｑ）または３゜
４．５．６−チトラクロロー〇−ベンゾキノン（０−８
’−１″
−ＣＡ）［σｒｔ＝２ｘｌｏ Ｓｃｍ （対アニオンと
してＤＤＱ−をもつ６８％酸化）；σｒｔ−”ｘｌＱｓ
ｃｍ（対アニオンとして０−ＣＡ−をもつ６２％酸化）
コのような電子受容体によって部分的に酸化されたポリ
（ビニルフェロセン）に匹敵するか、或いはそれ以上
のものである。Electrochemically doped poly(vinylferrocene)
The electrical conductivity value of chemically doped poly(vinylferrocene), i.e. 2,3-dichloro-5,6-dicyano)-p-benzoquinone (DDQ) or 3°4.5.6- Citrachloro〇-benzoquinone (0-8
'-1''-CA) [σrt=2xlo Scm (68% oxidation with DDQ- as counter-anion); σrt-”xlQs
cm (62% oxidation with 0-CA- as counteranion)
It is comparable to, or better than, poly(vinylferrocene) partially oxidized by electron acceptors such as ferrocene.
電気化学的ドーピングはまた、電気的中性のポリビニル
フェロセン及びドープされたポリビニルフェロセンの両
者を溶解しないアセトニトリル中において作用電極上に
成膜されたポリマーの薄いフィルムに対しても行われた
。成膜はポリビニルフェロセンのＴ Ｉ−Ｉ Ｆ溶液（
２ｉｉ％）からキャスト法によってなされた。フィルム
ドーピングについて得られた結果も第１表に含まれてい
る。フィルムドーピングの方法に比較して本発明の電気
化学的析出法は、一般に、ドーピングが均一に行われる
こと、また、むしろ高い割合のドーピングが得られると
いう特徴がある。本発明の方法はドープされたポリマー
の析出が起こる高電導ポリ（ビロール）の電気化学的合
成方法に似ているが、後者が電解重合の過程を含むのに
対して、本発明の方法は出発物質としてポリマーを用い
る点において異なる。Electrochemical doping was also performed on thin films of the polymer deposited on the working electrode in acetonitrile, which does not dissolve both the electrically neutral polyvinylferrocene and the doped polyvinylferrocene. The film was formed using a T I-IF solution of polyvinylferrocene (
2ii%) by the casting method. The results obtained for film doping are also included in Table 1. Compared to the film doping method, the electrochemical deposition method according to the invention is generally characterized in that the doping is uniform and that a rather high percentage of doping is obtained. The method of the present invention is similar to the method of electrochemical synthesis of highly conductive poly(virol) in which the precipitation of doped polymers occurs, but whereas the latter involves a step of electropolymerization, the method of the present invention It differs in that a polymer is used as the substance.
本発明の方法は操作が簡単でフィルム形成能力の乏しい
ポリマーに対しても適用できる。この方法はその他のフ
ェロセン核を含むポリマー、電性ポリマーに変えるのに
適用できる。The method of the present invention is easy to operate and can be applied even to polymers with poor film-forming ability. This method can be applied to convert into other polymers containing ferrocene nuclei and electrically conductive polymers.
第１表
電気化学的ドーピングされたポリビニルフェロセンａ）
の電気伝導度及び活性化エネルギー（註）ａ）対アニオ
ン： Ｃ１Ｏ，−
ｂ）実験番号１−３については電気化学的析出法による
ドーピング、実験番号４は１８０分のフィルムドーピン
グ
Ｃ）炭素元素分析から推定
ｄ）電気伝導度は１５〜７０℃の温度範囲で測定
出願人代理人 古 谷 馨
手続補正書（自発）
１．事件の表示
特願昭５９−３２１４３号
２、発明の名称
フェロセン核を有するポリマーの電気
化学的ドーピング法
３、補正をする者
事件との関係 特許出願人
（２９０）ダイセル化学工業株式会社
４、 代 理 人
明細書の発明の詳細な説明の欄
（１） 同３頁１２行「ポリマー」を削除（１）同４頁
末行〜５頁１行「メタノール・・・・・・再沈歌を」を
ｒＴＨＦ溶液からメタノール中へ再沈澱した。この操作
を３回」と訂正
（１） 同５頁末行「端子ｄ、ｃ、Ｊを「直流二端子」
と訂正
（１）同６頁２行「中性ポリマー・溶液からの」を削除
（１） 同７頁下２行「伝導度」を「電導度」と訂正Table 1 Electrochemically doped polyvinylferrocene a)
Electrical conductivity and activation energy (Note) a) Paired with anion: C1O, - b) Doping by electrochemical deposition method for experiment numbers 1-3, 180 minutes film doping for experiment number 4C) Carbon elemental analysis d) Electrical conductivity is measured in the temperature range of 15 to 70℃ Applicant's agent Kaoru Furuya Procedural amendment (voluntary) 1. Display of the case Japanese Patent Application No. 59-32143 2, Name of the invention Electrochemical doping method for polymers having ferrocene nuclei 3, Person making the amendment Relationship to the case Patent applicant (290) Daicel Chemical Industries, Ltd. 4, representative Column for detailed explanation of the invention in the applicant's specification (1) Delete "polymer" on page 3, line 12 (1) From the end of page 4 to line 1 on page 5, "methanol...re-sinking"' was reprecipitated from rTHF solution into methanol. ``This operation is repeated 3 times.'' (1) At the end of page 5, ``terminals d, c, and J are ``two DC terminals.''
(1) Delete "neutral polymer/from solution" in the second line of page 6 (1) Correct "conductivity" in the bottom two lines of page 7 to read "electrical conductivity"
Claims (1)
剤溶液を定電位陽極酸化することにより作用電極表面に
導電性高分子の膜を析出させることを特徴とするフェロ
セン核を有するポリマーの電気化学的ドーピング法。An electrochemical doping method for a polymer having a ferrocene nucleus, which is characterized by depositing a conductive polymer film on the surface of a working electrode by electrostatically anodizing an organic solvent solution of a supporting electrolyte and a polymer having a ferrocene nucleus. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59032143A JPS60177197A (en) | 1984-02-22 | 1984-02-22 | Electrochemical doping method of polymer having ferrocene nucleus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59032143A JPS60177197A (en) | 1984-02-22 | 1984-02-22 | Electrochemical doping method of polymer having ferrocene nucleus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60177197A true JPS60177197A (en) | 1985-09-11 |
| JPH0352555B2 JPH0352555B2 (en) | 1991-08-12 |
Family
ID=12350669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59032143A Granted JPS60177197A (en) | 1984-02-22 | 1984-02-22 | Electrochemical doping method of polymer having ferrocene nucleus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60177197A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000058418A1 (en) * | 1999-03-29 | 2000-10-05 | Bayer Aktiengesellschaft | Flat electrochromic contrast system |
| JP2010243563A (en) * | 2009-04-01 | 2010-10-28 | Konica Minolta Holdings Inc | Modified electrode and electrochemical display element |
| US20140212753A1 (en) * | 2013-01-30 | 2014-07-31 | Battelle Memorial Institute | Organometallic - inorganic hybrid electrodes for lithium-ion batteries |
-
1984
- 1984-02-22 JP JP59032143A patent/JPS60177197A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000058418A1 (en) * | 1999-03-29 | 2000-10-05 | Bayer Aktiengesellschaft | Flat electrochromic contrast system |
| JP2010243563A (en) * | 2009-04-01 | 2010-10-28 | Konica Minolta Holdings Inc | Modified electrode and electrochemical display element |
| US20140212753A1 (en) * | 2013-01-30 | 2014-07-31 | Battelle Memorial Institute | Organometallic - inorganic hybrid electrodes for lithium-ion batteries |
| US9444096B2 (en) * | 2013-01-30 | 2016-09-13 | Battelle Memorial Institute | Organometallic-inorganic hybrid electrodes for lithium-ion batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0352555B2 (en) | 1991-08-12 |
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