JPS6411208B2 - - Google Patents
Info
- Publication number
- JPS6411208B2 JPS6411208B2 JP4681785A JP4681785A JPS6411208B2 JP S6411208 B2 JPS6411208 B2 JP S6411208B2 JP 4681785 A JP4681785 A JP 4681785A JP 4681785 A JP4681785 A JP 4681785A JP S6411208 B2 JPS6411208 B2 JP S6411208B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer composition
- ion
- thiophene
- methylthiophene
- hexafluorophosphate
- 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
Links
Landscapes
- 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
て有用なチオフエン系重合体より成る高導電性重
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 highly conductive polymer composition comprising a thiophene 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 electrolytic polymerization of 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、電導度が120S／cm以下
しかもたない。 However, polymer compositions of thiophene and 3-methylthiophene have electrical conductivities 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 An object of the present invention is to provide a method for producing a thiophene-based polymer composition in which the electrical conductivity of the anion-doped polymer is high enough to be put to practical use. do.
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、
ある種の条件下でチオフエン及び３―メチルチオ
フエンの電解重合によつて得られる重合体組成物
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:
It was discovered that a polymer composition obtained by electrolytic polymerization of thiophene and 3-methylthiophene under certain conditions is suitable for the purpose, and based on this finding, the present invention was accomplished.
本発明は、炭酸プロピレン中、チオフエンまた
は３―メチルチオフエンと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、過塩素酸イオンまたはトリ
フルオロメタンスルホン酸イオンを含む支持電解
質を溶解させた反応系にて、チオフエンまたは３
―メ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―（２，５―チエニレン）またはポリ
―〔２，５―（３―メチルチエニレン）〕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
物の製造方法を提供するものである。これらの重
合体組成物は、170〜520S／cmの高い電導度を有
する。 The present invention involves dissolving a supporting electrolyte containing thiophene or 3-methylthiophene and hexafluorophosphate ion, hexafluoroarsenate ion, tetrafluoroborate ion, perchlorate ion or trifluoromethanesulfonate ion in propylene carbonate. In the reaction system, thiophene or 3
-Highly conductive polymer made by doping poly-(2,5-thienylene) or poly-[2,5-(3-methylthienylene)] with anions, characterized by electrolytically polymerizing methylthiophene. A method for producing a composition is provided. These polymer compositions have high electrical conductivities of 170-520 S/cm.
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
行うのが有利である。 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.
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―メチルチオフエン0.196g（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。この膜状重合組成
物は、厚みが6.8μmであり、520S／cmの電導度を
示した。Example 1 0.196g (2 mmol) of 3-methylthiophene
A solution was prepared by dissolving it in 10 ml of propylene carbonate and adding 0.083 g (0.3 mmol) of tetraethylammonium hexafluorophosphate as a supporting electrolyte. As electrodes, an ITO glass electrode was used for the anode, and a platinum plate was used for the cathode. After bubbling argon for 15 minutes, electrolytic polymerization was carried out at 5°C. Current density
When polymerized for 4 minutes at 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 6.8 μm and exhibited an electrical conductivity of 520 S/cm.
実施例 ２
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10mA／cm2で４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
重合組成物は、厚みが6.8μmであり、500S／cmの
電導度を示した。Example 2 In Example 1, 0.064 g (0.3 mmol) of sodium hexafluoroarsenate was used instead of tetraethylammonium hexafluorophosphate, aluminum was used as the cathode, and electropolymerization was carried out in the same manner at a current density of 10 mA/cm 2 When the mixture was polymerized for 4 minutes, a black film-like polymer composition doped with hexafluoroarsenate ions was obtained. This film-like polymer composition had a thickness of 6.8 μm and exhibited an electrical conductivity of 500 S/cm.
実施例 ３
実施例２において、ヘキサフルオロヒ素酸ナト
リウムの代わりにヘキサフルオロリン酸ナトリウ
ム0.050g（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４分間重合させたとこ
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
重合組成物は、厚みが6.5μmであり、480S／cmの
電導度を示した。Example 3 In Example 2, 0.050 g (0.3 mmol) of sodium hexafluorophosphate was used instead of sodium hexafluoroarsenate, and electrolytic polymerization was performed in the same manner at a current density of 10 mA/cm 2 for 4 minutes. A black film-like polymer composition doped with hexafluorophosphate ions was obtained. This film-like polymer composition had a thickness of 6.5 μm and exhibited an electrical conductivity of 480 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４分間重合させたところ、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。この膜状重合組成物
は、厚みが6.9μmであり、450S／cmの電導度を示
した。Example 4 In Example 1, 0.065 g (0.3 mmol) of tetraethylammonium tetrafluoroborate was used instead of tetraethylammonium hexafluorophosphate, and electrolytic polymerization was carried out in the same manner as the current density.
When polymerized for 4 minutes at 10 mA/cm 2 , a black film-like polymer composition doped with tetrafluoroborate ions was obtained. This film-like polymer composition had a thickness of 6.9 μm and exhibited an electrical conductivity of 450 S/cm.
実施例 ５
実施例１において、陽極のITOガラス電極の代
わりに白金電極を用いて、同様に電解重合を電流
密度10mA／cm2で４分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
膜重合体組成物が得られた。この膜状重合組成物
は、厚みが6.6μmであり、490S／cmの電導度を示
した。Example 5 In Example 1, a platinum electrode was used in place of the ITO glass electrode of the anode, and electrolytic polymerization was performed for 4 minutes at a current density of 10 mA/cm 2 , and hexafluorophosphate ions were doped. A black film polymer composition was obtained. This film-like polymer composition had a thickness of 6.6 μm and exhibited an electrical conductivity of 490 S/cm.
実施例 ６
チオフエン0.168g（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。この膜状重合組成物は、厚
みが8.3μmであり、190S／cmの電導度を示した。Example 6 0.168 g (2 mmol) of thiophene was dissolved in 10 ml of propylene carbonate, and 0.083 g of tetraethylammonium hexafluorophosphate was added as a supporting electrolyte.
(0.3 mmol) was added to the solution. As electrodes, an ITO glass electrode was used for the anode, and a platinum plate was used for the cathode. After bubbling argon for 15 minutes, electrolytic polymerization was carried out at 5°C. Current density 10mA/
After polymerization at cm 2 for 4 minutes, a black film-like polymer composition doped with hexafluorophosphate ions on the anode was obtained. This film-like polymer composition had a thickness of 8.3 μm and exhibited an electrical conductivity of 190 S/cm.
実施例 ７
実施例６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
組成物は、厚みが5.4μmであり、170S／cmの電導
度を示した。Example 7 In Example 6, 0.064 g (0.3 mmol) of sodium hexafluoroarsenate was also used instead of tetraethylammonium hexafluorophosphate.
When electrolytic polymerization was similarly carried out at a current density of 5 mA/cm 2 for 8 minutes using aluminum as the cathode,
A black film-like polymer composition doped with hexafluoroarsenate ions was obtained. This film-like polymer composition had a thickness of 5.4 μm and exhibited an electrical conductivity of 170 S/cm.
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高導電性重合体組
成物の製造方法を提供するものである。Effects of the Invention As described above, the present invention provides a method for producing a highly conductive polymer composition having excellent properties that can be used in fields such as electronic materials.
Claims (1)
チルチオフエンと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、過塩素酸イオンまたはトリフルオロ
メタンスルホン酸イオンを含む支持電解質を溶解
させた反応系にて、チオフエンまたは３―メチル
チオフエンを電解重合させることを特徴とするポ
リ―（２，５―チエニレン）またはポリ―〔２，
５―（３―メチルチエニレン）〕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の製造
方法。[Claims] 1. Thiophene or 3-methylthiophene and hexafluorophosphate ion in propylene carbonate,
It is characterized by electrolytically polymerizing thiophene or 3-methylthiophene in a reaction system in which a supporting electrolyte containing hexafluoroarsenate ion, tetrafluoroborate ion, perchlorate ion or trifluoromethanesulfonate ion is dissolved. Poly-(2,5-thienylene) or poly-[2,
A method for producing a highly conductive polymer composition comprising doping 5-(3-methylthienylene) with an anion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4681785A JPS61207427A (en) | 1985-03-09 | 1985-03-09 | Production of highly electroconductive polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4681785A JPS61207427A (en) | 1985-03-09 | 1985-03-09 | Production of highly electroconductive polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61207427A JPS61207427A (en) | 1986-09-13 |
| JPS6411208B2 true JPS6411208B2 (en) | 1989-02-23 |
Family
ID=12757889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4681785A Granted JPS61207427A (en) | 1985-03-09 | 1985-03-09 | Production of highly electroconductive polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61207427A (en) |
-
1985
- 1985-03-09 JP JP4681785A patent/JPS61207427A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61207427A (en) | 1986-09-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |