JPH0336050B2 - - Google Patents
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- Publication number
- JPH0336050B2 JPH0336050B2 JP60046816A JP4681685A JPH0336050B2 JP H0336050 B2 JPH0336050 B2 JP H0336050B2 JP 60046816 A JP60046816 A JP 60046816A JP 4681685 A JP4681685 A JP 4681685A JP H0336050 B2 JPH0336050 B2 JP H0336050B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer composition
- film
- carried out
- polymer
- doped
- 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
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電子デバイスまたは高分子素材とし
て有用な新規チオフエン系重合体より成る導電性
重合体組成物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a conductive polymer composition comprising a novel thiophene-based polymer useful as an electronic device or a polymer material.
従来の技術
チオフエン系重合体組成物としては、チオフエ
ンを電解重合して得られた重合体組成物〔「ジヤ
ーナル・オブ・ケミカル・ソサエテイ・ケミカ
ル・コミユニケイシヨン（J.C.S.Chem.
Commun.）」、382頁（1983年）〕や、３−メチル
チオフエンを電解重合して得られた重合体組成物
〔「シンセテイツク・メタル（Synth.Met.）」、第
６巻、317頁（1983年）〕が知られている。Prior Art As a thiophene-based polymer composition, a polymer composition obtained by electrolytic polymerization of thiophene [Journal of Chemical Society Chemical Industry Co., Ltd. (JCSChem.
Commun.), p. 382 (1983)] and a polymer composition obtained by electropolymerizing 3-methylthiophene ["Synth.Met.", Vol. 6, p. 317 ( 1983)] is known.
しかしながら、チオフエンや３−メチルチオフ
エンの重合体組成物は、導電道度が120S／cm以
下しかもたない。 However, polymer compositions of thiophene and 3-methylthiophene have a conductivity of only 120 S/cm or less.
発明が解決しようとする問題点
本発明は、陰イオンをドーピングされた重合体
の電導度が実用化されるに十分高い値をもつ新規
なチオフエン系重合体組成物の製造方法を提供す
ることを目的とする。Problems to be Solved by the Invention The present invention aims to provide a method for producing a novel thiophene-based polymer composition in which the electrical conductivity of the anion-doped polymer is high enough to be put to practical use. purpose.
問題点を解決しようとする手段
本発明者らは、このような従来の重合体組成物
のもつ欠点を克服すべく鋭意研究を行つた結果、
ある種の条件下で製造されたポリー〔２，５−
（３−エチルチエニレン）〕に陰イオンをドーピン
グさせて成る高導電性重合体組成物がその目的に
適合することを見出し、この知見に基づいて本発
明をなすに至つた。Means for Solving the Problems The present inventors have conducted extensive research to overcome the drawbacks of conventional polymer compositions, and have found that:
Poly[2,5-
(3-Ethylthienylene)] was found to be suitable for this purpose, and the present invention was completed based on this finding.
本発明のチオフエン系重合体組成物の製造方法
は、３−エチルチオフエンと支持電解質および溶
媒を含む反応系にて３−エチルチオフエンを電解
重合することを特徴とする。 The method for producing a thiophene-based polymer composition of the present invention is characterized by electrolytically polymerizing 3-ethylthiophene in a reaction system containing 3-ethylthiophene, a supporting electrolyte, and a solvent.
電解重合は、支持電解質としてのヘキサフルオ
ロリン酸イオン、ヘキサフルオロヒ素酸イオン、
テトラフルオロホウ酸イオン、過塩素酸イオン、
トリフルオロメタンスルホン酸イオン等を含む塩
の存在のもとに、炭酸プロピレン中でおこなわれ
る。 Electropolymerization uses hexafluorophosphate ions, hexafluoroarsenate ions, as supporting electrolytes,
Tetrafluoroborate ion, perchlorate ion,
It is carried out in propylene carbonate in the presence of a salt containing trifluoromethanesulfonate ion, etc.
電極材料には、金、白金などの貴金属、ニツケ
ル、炭素のほかに酸化第二インジウム、酸化第二
スズなどをガラス表面に蒸着したガラス電極も用
いられる。また、陰極としては、アルミニウムや
水銀も用いられる。 In addition to precious metals such as gold and platinum, nickel, and carbon, glass electrodes in which indium oxide, stannic oxide, and the like are deposited on the glass surface are also used as electrode materials. Furthermore, aluminum and mercury are also used as the cathode.
電解重合は、定電流電解、定電圧電解、定電位
電解のいずれの方法に従つてもよい。また、電解
重合は、窒素、アルゴンなどの不活性雰囲気下で
行なうのが有利である。重合膜は、通電時間によ
り膜厚を調整することができる。 Electrolytic polymerization may be carried out by any one of constant current electrolysis, constant voltage electrolysis, and constant potential electrolysis. Furthermore, electrolytic polymerization is advantageously carried out under an inert atmosphere such as nitrogen or argon. The thickness of the polymer film can be adjusted by adjusting the current application time.
本発明によつて製造された重合体組成物は、ヘ
キサフルオロリン酸イオン、ヘキサフルオロヒ素
酸イオン、テトラルオロホウ酸イオン、過塩素酸
イオン、トリフルオロメタンスルホン酸イオンの
ような陰イオンを、モノマーユニツトあたり0.15
〜0.50個の範囲でドーピングされた状態で得ら
れ、その電導度は150〜270S／cmであつた。ま
た、脱ドープされたポリー［２，５−（３−エチ
ルチエニレン）］の重合度は、赤外分光より求め
られ90〜250であつた。 The polymer compositions prepared according to the present invention contain anions such as hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, perchlorate, and trifluoromethanesulfonate per monomer unit. 0.15
It was obtained in a doped state in the range of ~0.50 atoms, and its conductivity was 150-270 S/cm. Further, the degree of polymerization of the dedoped poly[2,5-(3-ethylthienylene)] was determined from infrared spectroscopy and was 90 to 250.
実施例
以下、実施例により本発明を更に詳細に説明す
る。Examples Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
３−エチルチオフエン0.224ｇ（２ミリモル）
を10mlの炭酸プロピレンに溶解し、支持電解質と
してヘキサフルオロリン酸テトラエチルアンモニ
ウムを0.083ｇ（0.3ミリモル）を加えた溶液を作
成した。電極として、陽極には、ITOガラス電極
を用い、陰極には白金板を用いた。アルゴンを15
分間吹込んだ後、５℃で電解重合を行つた。電流
密度10ｍＡ／cm2で４分間重合させると、陽極上に
ヘキサフルオロリン酸イオンがドーピングされた
黒色膜状重合体組成物が得られた。この膜状重合
体組成物は、厚みが6.3μｍであり、240S／cmの電
導度を示した。Example 1 3-ethylthiophene 0.224g (2 mmol)
was dissolved in 10 ml of propylene carbonate, and 0.083 g (0.3 mmol) of tetraethylammonium hexafluorophosphate was added as a supporting electrolyte to prepare a solution. As electrodes, an ITO glass electrode was used for the anode, and a platinum plate was used for the cathode. 15 argon
After blowing for a minute, electrolytic polymerization was carried out at 5°C. When polymerized for 4 minutes at a current density of 10 mA/cm 2 , a black film-like polymer composition doped with hexafluorophosphate ions on the anode was obtained. This film-like polymer composition had a thickness of 6.3 μm and exhibited an electrical conductivity of 240 S/cm.
実施例 ２
実施例１において、行つたと同様に電解重合を
電流密度10ｍＡ／cm3で80秒間重合させたところ、
ヘキサフルオロリン酸イオンがドーピングされた
黒色膜状重合体組成物が得られた。この膜状重合
体組成物は、厚みが2.0μｍであり、270S／cmの電
導度を示した。Example 2 Electrolytic polymerization was carried out for 80 seconds at a current density of 10 mA/cm 3 in the same manner as in Example 1.
A black film-like polymer composition doped with hexafluorophosphate ions was obtained. This film-like polymer composition had a thickness of 2.0 μm and exhibited an electrical conductivity of 270 S/cm.
実施例 ３
実施例１において、ヘキサフルオロリン酸テト
ラエチルアンモニウムの代わりに、テトラフルオ
ロホウ酸テトラエチルアンモニウム0.065ｇ（0.3
ミリモル）を用いて、同様に電解重合を電流密度
10ｍＡ／cm2で３分間重合させると、陽極上にテト
ラフルオロホウ酸イオンがドーピングされた黒色
膜状重合体組成物が得られた。この膜状重合体組
成物が得られた。この膜状重合体組成物は厚みが
5.3μｍであり、190S／cmの電導度を示した。Example 3 In Example 1, 0.065 g (0.3
Electropolymerization is similarly carried out using a current density of
When polymerized for 3 minutes at 10 mA/cm 2 , a black film-like polymer composition doped with tetrafluoroborate ions on the anode was obtained. This film-like polymer composition was obtained. This film-like polymer composition has a thickness
It was 5.3 μm and showed an electrical conductivity of 190 S/cm.
実施例 ４
実施例１において，ヘキサフルオロリン酸テト
ラエチルアンモニウムの代わりにヘキサフルオロ
ヒ素酸ナトリウム0.064ｇ（0.3ミリモル）をま
た、陰極にアルミニウムを用いて、同様に電解重
合を電流密度５ｍＡ／cm2で８分間重合させたとこ
ろ、ヘキサフルオロヒ素酸イオンがドーピングさ
れた黒色膜状重合体組成物が得られた。この膜状
重合体組成物は、厚みが7.1μｍであり、270S／cm
の電導度を示した。Example 4 In Example 1, 0.064 g (0.3 mmol) of sodium hexafluoroarsenate was used instead of tetraethylammonium hexafluorophosphate, and aluminum was used as the cathode, and electrolytic polymerization was carried out in the same manner at a current density of 5 mA/cm 2 . When polymerized for 8 minutes, a black film-like polymer composition doped with hexafluoroarsenate ions was obtained. This film-like polymer composition has a thickness of 7.1 μm and a thickness of 270 S/cm.
It showed a conductivity of .
発明の効果
以上のように本発明は、電子材料等の分野に利
用されるすぐれた特性を有する導電性重合体組成
物を提供するものである。Effects of the Invention As described above, the present invention provides a conductive polymer composition having excellent properties that can be used in fields such as electronic materials.
Claims (1)
解質を含む媒質中で３−エチルチオフエンを電解
重合させることを特徴とするポリー［２，５−
（３−エチルチエニレン）］に陰イオンをドーピン
グさせてなる導電性重合体組成物の製造方法。1 Poly[2,5-
(3-Ethylthienylene)] is doped with an anion.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4681685A JPS61209223A (en) | 1985-03-09 | 1985-03-09 | Electrically conductive polymer composition and production thereof |
| US06/831,494 US4691005A (en) | 1985-03-09 | 1986-02-21 | Thiophene derivative polymer, polymer composition, and methods for manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4681685A JPS61209223A (en) | 1985-03-09 | 1985-03-09 | Electrically conductive polymer composition and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61209223A JPS61209223A (en) | 1986-09-17 |
| JPH0336050B2 true JPH0336050B2 (en) | 1991-05-30 |
Family
ID=12757859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4681685A Granted JPS61209223A (en) | 1985-03-09 | 1985-03-09 | Electrically conductive polymer composition and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61209223A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5130054A (en) * | 1984-04-02 | 1992-07-14 | Polaroid Corporation | Processable conductive polymers |
-
1985
- 1985-03-09 JP JP4681685A patent/JPS61209223A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61209223A (en) | 1986-09-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |