JPS62220517A - Electrically conductive polymer composition and production thereof - Google Patents
Electrically conductive polymer composition and production thereofInfo
- Publication number
- JPS62220517A JPS62220517A JP6299886A JP6299886A JPS62220517A JP S62220517 A JPS62220517 A JP S62220517A JP 6299886 A JP6299886 A JP 6299886A JP 6299886 A JP6299886 A JP 6299886A JP S62220517 A JPS62220517 A JP S62220517A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- dopant
- formula
- polymer composition
- polymer
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229920001940 conductive polymer Polymers 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 239000002019 doping agent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 7
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 7
- -1 hexafluorophosphate ion Chemical class 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 4
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- NJPMFDNZCLKTHE-UHFFFAOYSA-N 2-dodecylthiophene Chemical compound CCCCCCCCCCCCC1=CC=CS1 NJPMFDNZCLKTHE-UHFFFAOYSA-N 0.000 description 1
- GIFWAJGKWIDXMY-UHFFFAOYSA-N 2-octylthiophene Chemical compound CCCCCCCCC1=CC=CS1 GIFWAJGKWIDXMY-UHFFFAOYSA-N 0.000 description 1
- WQYWXQCOYRZFAV-UHFFFAOYSA-N 3-octylthiophene Chemical compound CCCCCCCCC=1C=CSC=1 WQYWXQCOYRZFAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規な導電性重合体組成物及びその製造方法に
関するものである。さらに詳しくいえば、本発明は、各
種電子部品、電極、センサー、光電変換素子などに有用
な、新規なチオフェン系重合体を主体とする導電性重合
体組成物、及びこのものを電解重合により容易に製造す
る方法（二関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel conductive polymer composition and a method for producing the same. More specifically, the present invention provides a conductive polymer composition mainly composed of a novel thiophene polymer, which is useful for various electronic parts, electrodes, sensors, photoelectric conversion elements, etc., and which can be easily produced by electrolytic polymerization. (2) method of manufacturing
従来の技術
近年、電気、電子産業における著しい技術発展に伴い、
新しい優れた電気的機能を有する材料が求められており
、高分子化学の分野においても各種の電気特性を有する
材料が見出され、すて（−多くのものが実用化されてい
るが、より一層優れた電気特性を有する材料の探索が盛
んに行われている。特に電気伝導性を有する有機導電性
材料は、例えば各種電子部品、電極、センサー、光電変
換素子などの素材として幅広く利用することができるの
で、優れた特性を有する有機導電性材料の開発研究が積
極的になされている。Conventional technology In recent years, with the remarkable technological development in the electrical and electronic industries,
There is a need for new materials with excellent electrical functions, and materials with various electrical properties have been discovered in the field of polymer chemistry. The search for materials with even better electrical properties is actively underway.In particular, organic conductive materials with electrical conductivity can be widely used as materials for various electronic components, electrodes, sensors, photoelectric conversion elements, etc. Therefore, research and development are actively being conducted to develop organic conductive materials with excellent properties.
これまで、有機導電性材料としては、ポリアセチレン、
ポリ（ｐ−フェニレン）、ポリフェニレンスルフィド、
ポリピロールなどにドーピング剤を添加させたものや、
有機金属ポリマーなどが知られている。しかしながら、
゛これらの有機導電性材料は、導電性、成形性あるいは
経済性などの点で必ずしも満足しうるものではない。Until now, organic conductive materials such as polyacetylene,
poly(p-phenylene), polyphenylene sulfide,
Doping agents added to polypyrrole, etc.
Organometallic polymers are known. however,
``These organic conductive materials are not necessarily satisfactory in terms of conductivity, moldability, economic efficiency, etc.
他方、チオフェン系重合体組成物としては、チオフェン
を電解重合して得られた重合体組成物〔「ジャーナル°
オブ°ケミカル°ソサエティ。On the other hand, as a thiophene-based polymer composition, a polymer composition obtained by electrolytic polymerization of thiophene [Journal °
Of°Chemical Society.
ケミカル°コミユニケイジョン（Ｊ、 Ｃ６Ｓ、Ｏｈｅ
ｍ。Chemical ° Comic Union (J, C6S, Ohe
m.
Ｃｏｍｍｕｎ、） Ｊ第３８２ページ（１９８３年）」
や、３−メチルチオフェンを電解重合して得られる重合
体組成物〔「シンセティック°メタル（５ｙｎｔｈ。Common,) J page 382 (1983)”
A polymer composition obtained by electrolytically polymerizing 3-methylthiophene and 3-methylthiophene ["Synthetic ° Metal (5ynth.
Ｍｅｔ、）Ｊ第６巻、第３１７ページ（１９８５年）〕
が知られている。Met,) J Volume 6, Page 317 (1985)]
It has been known.
しかしながら、これらの重合体組成物は適当な支持電解
質を選ぶことにより、良好な電気伝導度を有するものに
なφが、各種溶媒に不溶で、かつ不融であるため、成形
が極めて困難であって、導電性重合体組成物としての実
用的価値は少ない。However, these polymer compositions can be made to have good electrical conductivity by selecting an appropriate supporting electrolyte, and are extremely difficult to mold because φ is insoluble and infusible in various solvents. Therefore, it has little practical value as a conductive polymer composition.
発明が解決しようとする問題点
本発明の目的は、このような事情のもとで、優れた電気
伝導度を有し、かつ成形性が良好である上に経済的（二
製造しうるなど、実用的価値の高い新規な導電性重合体
組成物を提供することにある。Problems to be Solved by the Invention Under these circumstances, the object of the present invention is to provide a material that has excellent electrical conductivity, good moldability, and is economical (such as easy to manufacture). The object of the present invention is to provide a novel conductive polymer composition with high practical value.
問題点を解決するための手段
本発明者らは、前記目的を達成するために、チオフェン
類の電解重合について鋭意研究を重ねた結果、チオフェ
ン類として３位に炭素数６〜１２の直鎖アルキル基を有
するものを、支持電解質としてドーパントを供与しうる
ものを用いて、該チオフェン類を電解重合することによ
り、新規な導電性重合体組成物が容易に得られ、このも
のは優れた電気伝導度を有し、かつ各種溶剤に可溶で容
易に成形することができ、実用的価値が高いことを見出
し、この知見に基づいて本発明を完成するに至った。Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive research on the electrolytic polymerization of thiophenes, and have found that as a thiophene, a linear alkyl having 6 to 12 carbon atoms is added to the 3-position. A new conductive polymer composition can be easily obtained by electrolytically polymerizing the thiophenes using a dopant-containing polymer as a supporting electrolyte, which has excellent electrical conductivity. The inventors have discovered that the material has a high practical value because it has a high degree of strength, is soluble in various solvents, and can be easily molded. Based on this knowledge, the present invention has been completed.
すなわち、本発明は、一般式
（式中のｎは５ん１１の整数である）
で示される単量体単位から成る°重合体に対しドーパン
トを単量体単位に基づき０．０１〜０．５七ルチの量で
ドーピングさせて成る導電性重合体組成物を提供するも
のであり、このものは、ドーパントを供与しつる支持電
解質を含有する媒質中において、一般式
（式中のｎは前記と同じ意味をもつ）
で示されるチオフェン誘導体を電解重合することによっ
て製造することができる。That is, the present invention provides a polymer comprising monomer units represented by the general formula (n in the formula is an integer between 5 and 11), in which the dopant is added in an amount of 0.01 to 0.0, based on the monomer units. The present invention provides conductive polymer compositions doped in an amount of It can be produced by electrolytically polymerizing a thiophene derivative represented by (having the same meaning as ).
本発明において、電解重合に用いる単量体は、前記一般
式ω）で示されるように、３位に炭素数６〜１２の直鎖
アルキル基を有するチオフェン誘導体であり、アルキル
基の具体例としては、ｎ−ヘキシル基、ｎ−へブチル基
、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−
ウンデシル基及びｎ−ドデンル基が挙げられる。このア
ルキル基の炭素数が６より小さいものは、得られる重合
体が溶剤に対して難溶性又は不溶性となり、一方１２よ
り大きいものは重合体の機械特性が劣り、また重合度も
低くて好ましくない。In the present invention, the monomer used for electrolytic polymerization is a thiophene derivative having a straight chain alkyl group having 6 to 12 carbon atoms at the 3-position, as shown by the general formula ω), and specific examples of the alkyl group include is n-hexyl group, n-hebutyl group, n-octyl group, n-nonyl group, n-decyl group, n-
Examples include undecyl group and n-dodenyl group. If the number of carbon atoms in the alkyl group is less than 6, the resulting polymer will be poorly soluble or insoluble in solvents, while if it is more than 12, the mechanical properties of the polymer will be poor and the degree of polymerization will be low, which is not preferred. .
本発明における支持電解質はドーパントを供与しうるも
のであり、このドーパントとしては、例えばヘキサフル
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、。The supporting electrolyte in the present invention can provide a dopant, and examples of the dopant include hexafluorophosphate ion, hexafluoroarsenate ion, and tetrafluoroborate ion.
過塩素酸イオン、トリフルオロメタンスルホン酸イオン
、各種ハロゲンイオン、硫酸イオンなどの陰イオンが挙
げられるが、これらの中で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、過塩素酸イオン及びトリフルオロメタンスルホ
ン酸イオンは、得られる重合体に実用化するのに十分高
い電気伝導度（６０〜１１０８／ｃ１１１）を付与しう
るので好適である。該支持電解質としては、前記陰イオ
ンを含む塩が用いられる。Examples include anions such as perchlorate ion, trifluoromethanesulfonate ion, various halogen ions, and sulfate ion; among these, hexafluorophosphate ion, hexafluoroarsenate ion, tetrafluoroborate ion, and perchlorate ion. Acid ions and trifluoromethanesulfonate ions are suitable because they can impart sufficiently high electrical conductivity (60 to 1108/c111) to the resulting polymer for practical use. As the supporting electrolyte, a salt containing the anion is used.
本発明において電解重合に用いられる電極としては、例
えば金、白金などの貴金属やニッケル、炭素から成るも
の、あるいは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などが挙げられ、また
、陰極にはこれらの外にアルミニウムや水銀から成″る
ものも用いることができる。Examples of the electrode used in electrolytic polymerization in the present invention include those made of noble metals such as gold and platinum, nickel, and carbon, or glass electrodes with indium oxide, stannic oxide, etc. deposited on the glass surface. Furthermore, in addition to these, materials made of aluminum or mercury can also be used for the cathode.
電解重合は、前記支持電解質を例えばニトロベンゼン、
ベンゾニトリル、炭酸プロピレンなどの溶媒中に、 ０
．０１〜０．２モル／２の濃度になるように溶解して成
る電解液中において、好ましくは窒素やアルゴンなどの
不活性雰囲気下、定電流電解、定電位電解、定電圧電解
などの方法（二従って行われる。通電時間は、陽極上に
形成される重合体の膜厚が所望の厚みになるよう（−適
宜選ばれる。In electrolytic polymerization, the supporting electrolyte is, for example, nitrobenzene,
0 in a solvent such as benzonitrile or propylene carbonate.
．． 01 to 0.2 mol/2, preferably under an inert atmosphere such as nitrogen or argon, by methods such as constant current electrolysis, constant potential electrolysis, and constant voltage electrolysis ( The current application time is appropriately selected so that the polymer film formed on the anode has a desired thickness.
このようにして、得られた重合体組成物は、一般式
（式中のｎは前記と同じ意味をもつ）
で示される単量体単位°から成る重合体に対し、前記ド
ーパントが単量体単位に基づき０．０１〜０．５モルチ
の範囲でドーピングされたものである。ドーパントの量
が単量体単位１：基づき０．０１ モル係未満では電気
伝導度が低くて、実用的な導電性が得られず、また単量
体単位に基づき０．５モルチを超えると量の割には電気
伝導度は高くならず、むしろ機械特性が低下して好まし
くない。この重合体組成物は、トルエンやテトラヒドロ
ナフタレンなどの溶媒Ｃ：可溶である。In this way, the obtained polymer composition is a polymer composed of monomer units represented by the general formula (n in the formula has the same meaning as above), in which the dopant is a monomer. It is doped in a range of 0.01 to 0.5 mole based on the unit. If the amount of the dopant is less than 0.01 molar ratio based on 1 monomer unit, the electrical conductivity is low and practical conductivity cannot be obtained, and if the amount exceeds 0.5 molar ratio based on the monomer unit. However, the electrical conductivity is not high, and the mechanical properties are rather deteriorated, which is not preferable. This polymer composition is soluble in solvent C such as toluene and tetrahydronaphthalene.
本発明の重合体組成物は、文献未載の新規なものであり
、電解還元することにより、陰イオンのドーパントが脱
離して、前記一般式（１）で示される単量体単位から成
る重合体となる。このものは塩化メチレン、クロロホル
ム、ベンゼン、トルエン、テトラヒドロナフタレンのよ
うな溶媒に可溶で、成形が容易であるので、新規な高分
子素材としての利用が可能である。また、該重合体は、
赤外吸収スペクトルＬ：おいて、８２０ｃｌｌ−１の波
長域に吸収が認められ、 ２，３．５− ） ９置換チ
オフエン環を有することが確認された。The polymer composition of the present invention is novel and has not been published in any literature, and by electrolytic reduction, the anionic dopant is eliminated and the polymer composition is composed of a monomer unit represented by the general formula (1). It becomes a combination. This material is soluble in solvents such as methylene chloride, chloroform, benzene, toluene, and tetrahydronaphthalene, and is easily molded, so it can be used as a new polymeric material. Moreover, the polymer is
In the infrared absorption spectrum L:, absorption was observed in the wavelength range of 820 cll-1, and it was confirmed that the product had a 2,3.5-)9-substituted thiophene ring.
本発明の重合体組成物における前記重合体は、重合度が
８０〜３５０、分子量が１０，０００〜ｓｏ 、ｏｏｏ
の範囲にあるものが、機械特性や成形性の点で好ましい
。なお、該重゛合度は蒸気圧式分子量測定装置にて求め
ることができる。The polymer in the polymer composition of the present invention has a degree of polymerization of 80 to 350 and a molecular weight of 10,000 to so, ooo.
Those within this range are preferable in terms of mechanical properties and moldability. The degree of polymerization can be determined using a vapor pressure molecular weight measuring device.
発明の効果
本発明の導電性重合体組成物は、優れた電気伝導度を有
し、かつ成形性が良好である上１″−経済的（＝製造し
うるなど、実用的価値が高く、例えば各種電子部品、電
極、センサー、光電変換素子などに利用が可能である。Effects of the Invention The conductive polymer composition of the present invention has excellent electrical conductivity, good moldability, and has high practical value, such as being economical (= being able to be manufactured), such as It can be used in various electronic components, electrodes, sensors, photoelectric conversion elements, etc.
実施例 次に実施例（：よって本発明をさらに詳細に説明する。Example EXAMPLES Next, the present invention will be described in further detail in Examples.
実施例１
３−ｎ−ヘキシルｆオフエｙ ０．６７３ｇ （４ミリ
モル） ヲ２０ ｍｌのニトロベンゼン（二溶解し、こ
れに支持電解質としてヘキサフルオロリン酸テトジエテ
ルアンモニウム°０，１３８ ｇ（０，５ミリモル）を
加えた溶液を作成した。Example 1 0.673 g (4 mmol) of 3-n-hexyl foffay was dissolved in 20 ml of nitrobenzene, and 0.138 g (0.5 A solution was prepared by adding 1 mmol).
次に、陽極としてＩＴ○ガラス電極を、陰極として白金
板を用いた電解槽に、前記溶液を入れ、アルゴンガスを
１５分間吹込んだのち、５℃で電解チドーピングされた
黒色膜状重合体組成物が得ら；□・・れた。Next, the above solution was put into an electrolytic cell using an IT○ glass electrode as an anode and a platinum plate as a cathode, and after blowing argon gas for 15 minutes, the black film-like polymer electrolytically doped at 5°C was heated. A composition was obtained; □.
この膜状重合体組成物は厚みが７．０μｍであり、９５
Ｓ ／ ３の電導度を示した。また、トルエン、テト
ラヒドロナフタレンに約６０％（Ｗ、、Ｖ） 溶解し
た。This film-like polymer composition has a thickness of 7.0 μm and a thickness of 95 μm.
It showed a conductivity of S/3. It was also dissolved in toluene and tetrahydronaphthalene at a concentration of about 60% (W, V).
参考例
実施例１と同様にして、３−ｎ−へキシルチオフェンを
電流密度２ ｍＡ ／ａｘ２で１０分間電解重合したと
ころ、陽極上（二へ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。Reference Example When 3-n-hexylthiophene was electrolytically polymerized for 10 minutes at a current density of 2 mA/ax2 in the same manner as in Example 1, a black film-like polymer doped with dihexafluorophosphate ions was formed on the anode. A combined composition was obtained.
次に、電極の極性を反転し、電流密度０．５７７ＬＡ／
（”Ｊ１２で両極の電圧差が５ｖを越え、かつ一定電圧
になるまで電流を流して電解還元を行い、該組成物から
ヘキサフルオロリン酸イオンを除去した。Next, the polarity of the electrodes is reversed, and the current density is 0.577 LA/
(At J12, a current was applied until the voltage difference between the two electrodes exceeded 5 V and the voltage became constant to perform electrolytic reduction, and hexafluorophosphate ions were removed from the composition.
次いで、このものをメタノール洗浄後、乾燥して、赤色
膜状重合体を得た。Next, this product was washed with methanol and dried to obtain a red film-like polymer.
この重合体は、塩化メチレン、クロロホルム、ベンゼン
、テトラヒドロナフタレンに９０％（／Ｗ）以上溶解し
た。まだ、クロロホルムを用いた蒸気圧式分子量測定装
置に、より求められた重合度は２３０であった。This polymer dissolved at least 90% (/W) in methylene chloride, chloroform, benzene, and tetrahydronaphthalene. However, the degree of polymerization determined by a vapor pressure molecular weight measuring device using chloroform was 230.
実施例２
実施例１において、ニトロベンゼンの代りに炭酸プロピ
レン２０．／を用い、かつ電流密度１０ｍＡ／ｃＩ１１
２で４分間電解重合する以外は、実施例１と同様にして
３−ｎ−へキシルチオフェンを電解重合体に対し、単量
体単位に基づきｇモルチ ド＋４ピングされた黒色膜状
重合体組成物が得られた。Example 2 In Example 1, 20% of propylene carbonate was used instead of nitrobenzene. / and a current density of 10 mA/cI11
A black film-like polymer composition in which 3-n-hexylthiophene was added to the electrolytic polymer in the same manner as in Example 1, except that it was electrolytically polymerized for 4 minutes at No. 2 for 4 minutes, based on the monomer unit. I got something.
この重合体組成物は厚みが８．Ｏｌｔｍであって、１１
０Ｓ／ｃ！Ｍの電導度を示した。This polymer composition has a thickness of 8. Oltm, 11
0S/c! It showed the conductivity of M.
実施例３
実施例１（二おいて、３−ｎ−へキシルチオフェンの代
りに５−ｎ−オクチルチオフェン０．７８６＃（４ミリ
モル）を用いる以外は、実施例１と全く同様にして電解
重合を行ったところ、ヘキサフルオロリン酸イオンが重
合体に対し、単量体単位に０．２６
基づき＃＃モルチドーピングされた黒色膜状重合体組成
物が得られた。Example 3 Electropolymerization was carried out in exactly the same manner as in Example 1, except that 0.786# (4 mmol) of 5-n-octylthiophene was used instead of 3-n-hexylthiophene. As a result, a black film-like polymer composition was obtained in which the polymer was doped with hexafluorophosphate ions in an amount of ##molti based on 0.26 monomer units.
この重合体組成物は厚みが６．０μｍであり、かつ７８
８／ａの電導度を示した。また、トルエン、テトラヒド
ロナフタレン（二約７０％（／Ｖ）溶解した。This polymer composition has a thickness of 6.0 μm and a thickness of 78 μm.
It showed an electrical conductivity of 8/a. In addition, toluene and tetrahydronaphthalene (about 70% (/V)) were dissolved.
実施例４
実施例３において、ニトロベンゼンの代すに炭酸プロピ
レン２０１１７を用い、かつ電流密度１Ｑ ｍＡ／α２
で４分間電解重合する以外は、実施例６と同様（＝シて
３−オクチルチオフェンを電解重合したところ、ヘキサ
フルオロリン酸イオンが重合体に対し、単量体単位に基
づき０６２０モルチ ドーピングされた黒色膜状重合体
組成物が得られた。Example 4 In Example 3, propylene carbonate 20117 was used instead of nitrobenzene, and the current density was 1Q mA/α2.
Same as Example 6 except that 3-octylthiophene was electrolytically polymerized for 4 minutes at A black filmy polymer composition was obtained.
この膜状重合体組成物は厚みが６．８μｍであり、かっ
５２Ｂ／ＣＩＩＫの電導度を示した。This film-like polymer composition had a thickness of 6.8 μm and exhibited an electrical conductivity of 52B/CIIK.
実施例５
実施例１において、３−ｎ−へキシルチオフェンの代り
（二３−ｎ−ドデシノＬ′チオフェン１，００８Ｊ（４
ミリモル）を用い、かつ電流密度２ ｍＡ ／ａｔｒ２
で５分間電解重合する以外は、実施例１と同様にして電
解重合したところ、陽極上にヘキサフルオロリン酸イオ
ンが重合体に対し、単量体単位に基、 ０．２Ｚ１
つき＝＝＝モルチ ドーピングされた黒色膜状重合体組
成物が得られた。Example 5 In Example 1, instead of 3-n-hexylthiophene (23-n-dodecino L'thiophene 1,008J (4
mmol) and a current density of 2 mA/atr2
Electrolytic polymerization was carried out in the same manner as in Example 1, except that electrolytic polymerization was carried out for 5 minutes at A doped black filmy polymer composition was obtained.
この膜状重合体は厚みが６．９Ｐであり、かつ６７Ｓ／
ｃ！ＩＩの電導度を示した。また、トルエンに約６０
（ｗ／Ｗ） ％テトラヒドロナフタレン約９０チ（ｗ／
Ｗ ）溶解した。This film-like polymer has a thickness of 6.9P and 67S/
c! It showed a conductivity of II. Also, toluene has about 60
(w/w)% Tetrahydronaphthalene approx. 90% (w/w)
W) Dissolved.
実施例６
実施例５において、ヘキサフルオロリン酸テトラエテル
アンモニウムの代りにテトラフルオロホウ酸テトラエチ
ルアンモニウム０．１０９１ｉ （０，５ミリモル）を
用いる以外は、実施例５と全く同様にして、３−ｎ−ド
デシルチオフェンを電解重合したところ、テトラフルオ
ロホウ酸イオンがＮ合体に対し、単量体単位に基づき０
．３０モルチドーピングされた黒色膜状重合体組成物が
得られた。Example 6 In Example 5, 3-n - When dodecylthiophene was electrolytically polymerized, tetrafluoroborate ions were found to be 0 based on the monomer unit relative to the N-combined
．． A black film-like polymer composition doped with 30 moles was obtained.
この膜状重合体組成物は厚みが６．５μｍであ°す、か
つ６１Ｓ／ｃＩＩの電導度を示した。This film-like polymer composition had a thickness of 6.5 μm and exhibited an electrical conductivity of 61 S/cII.
Claims (1)
を単量体単位に基づき０．０１〜０．５モル％の量でド
ーピングさせて成る導電性重合体組成物。 ２ ドーパントが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、
過塩素酸イオン及びトリフルオロメタンスルホン酸イオ
ンの中から選ばれた陰イオンである特許請求の範囲第１
項記載の組成物。 ３ ドーパントを供与しうる支持電解質を含有する媒質
中において、一般式 ▲数式、化学式、表等があります▼ （式中のｎは５〜１１の整数である） で示されるチオフェン誘導体を電解重合することを特徴
とする、一般式 ▲数式、化学式、表等があります▼ （式中のｎは前記と同じ意味をもつ） で示される単量体単位から成る重合体に対しドーパント
を単量体単位に基づき０．０１〜０．５モル％の量でド
ーピングさせて成る導電性重合体組成物の製造方法。 ４ ドーパントが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、
過塩素酸イオン及びトリフルオロメタンスルホン酸イオ
ンの中から選ばれた陰イオンである特許請求の範囲第３
項記載の製造方法。[Claims] 1 A dopant is monomerized into a polymer consisting of monomer units represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (n in the formula is an integer from 5 to 11) An electrically conductive polymer composition doped in an amount of 0.01 to 0.5 mole % based on body units. 2 The dopant is a hexafluorophosphate ion, a hexafluoroarsenate ion, a tetrafluoroborate ion,
Claim 1, which is an anion selected from perchlorate ion and trifluoromethanesulfonate ion.
Compositions as described in Section. 3 In a medium containing a supporting electrolyte capable of donating a dopant, electrolytically polymerize a thiophene derivative represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (n in the formula is an integer from 5 to 11) There are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (n in the formula has the same meaning as above), which is characterized by A method for producing a conductive polymer composition comprising doping in an amount of 0.01 to 0.5 mol% based on 4 The dopant is a hexafluorophosphate ion, a hexafluoroarsenate ion, a tetrafluoroborate ion,
Claim 3, which is an anion selected from perchlorate ion and trifluoromethanesulfonate ion
Manufacturing method described in section.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6299886A JPS62220517A (en) | 1986-03-20 | 1986-03-20 | Electrically conductive polymer composition and production thereof |
| US07/028,620 US4737557A (en) | 1986-03-20 | 1987-03-20 | 3-N-higher alkylthiophene polymer and composition thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6299886A JPS62220517A (en) | 1986-03-20 | 1986-03-20 | Electrically conductive polymer composition and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62220517A true JPS62220517A (en) | 1987-09-28 |
| JPH0138805B2 JPH0138805B2 (en) | 1989-08-16 |
Family
ID=13216552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6299886A Granted JPS62220517A (en) | 1986-03-20 | 1986-03-20 | Electrically conductive polymer composition and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62220517A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62253617A (en) * | 1986-04-01 | 1987-11-05 | ソルベイ（ソシエテ アノニム） | Conductive polymer and its production |
| WO1990008792A1 (en) * | 1989-01-31 | 1990-08-09 | Nippon Oil And Fats Co., Ltd. | Fluoroalkylated heteroaromatic polymer |
| JPH02292872A (en) * | 1989-05-02 | 1990-12-04 | Agency Of Ind Science & Technol | Manufacture of stabilized semiconductor electrode |
| JPH03210326A (en) * | 1990-01-13 | 1991-09-13 | Dainippon Printing Co Ltd | Conductive polymer and its production |
-
1986
- 1986-03-20 JP JP6299886A patent/JPS62220517A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62253617A (en) * | 1986-04-01 | 1987-11-05 | ソルベイ（ソシエテ アノニム） | Conductive polymer and its production |
| WO1990008792A1 (en) * | 1989-01-31 | 1990-08-09 | Nippon Oil And Fats Co., Ltd. | Fluoroalkylated heteroaromatic polymer |
| JPH02292872A (en) * | 1989-05-02 | 1990-12-04 | Agency Of Ind Science & Technol | Manufacture of stabilized semiconductor electrode |
| JPH03210326A (en) * | 1990-01-13 | 1991-09-13 | Dainippon Printing Co Ltd | Conductive polymer and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0138805B2 (en) | 1989-08-16 |
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