JPS6411209B2 - - Google Patents
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- Publication number
- JPS6411209B2 JPS6411209B2 JP6299986A JP6299986A JPS6411209B2 JP S6411209 B2 JPS6411209 B2 JP S6411209B2 JP 6299986 A JP6299986 A JP 6299986A JP 6299986 A JP6299986 A JP 6299986A JP S6411209 B2 JPS6411209 B2 JP S6411209B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymerization
- reference example
- doped
- electrical conductivity
- 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
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- 229920000642 polymer Polymers 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003115 supporting electrolyte Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000003577 thiophenes Chemical class 0.000 claims description 3
- -1 hexafluorophosphate ions Chemical class 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004020 conductor Substances 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WQYWXQCOYRZFAV-UHFFFAOYSA-N 3-octylthiophene Chemical compound CCCCCCCCC=1C=CSC=1 WQYWXQCOYRZFAV-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- RFKWIEFTBMACPZ-UHFFFAOYSA-N 3-dodecylthiophene Chemical compound CCCCCCCCCCCCC=1C=CSC=1 RFKWIEFTBMACPZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 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
- 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
- 239000000178 monomer Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 239000000615 nonconductor Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- 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
本発明は新規なチオフエン系重合体及びその製
造方法に関するものである。さらに詳しくいえ
ば、本発明の有機導電性材料の素材や各種用途の
高分子素材として有用な、溶剤に可溶で良好な成
形性を有する高重合度の新規なチオフエン系重合
体、及びこのものを電気化学的手法によつて容易
に製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel thiophene-based polymer and a method for producing the same. More specifically, a novel thiophene-based polymer with a high degree of polymerization that is soluble in solvents and has good moldability, which is useful as a material for the organic conductive material of the present invention and as a polymer material for various uses, and this polymer. The present invention relates to a method for easily manufacturing by an electrochemical method.
従来の技術
これまで、チオフエン系重合体としては、チオ
フエンや３―メチルチオフエンを電解重合させ、
次いで電解還元して得られたポリ―（２，５―チ
エニレン）やポリ―〔２，５―（メチルチエニレ
ン）〕が知られている。しかしながら、電気化学
的に製造された前記ポリ―（２，５―チエニレ
ン）やポリ―〔２，５―（３―メチルチエニレ
ン）〕は各種溶媒に不溶で、かつ不融であるため
成形が極めて困難であつて、高分子素材としての
実用的価値は少ない。Conventional technology Up until now, thiophene-based polymers have been produced by electrolytically polymerizing thiophene and 3-methylthiophene.
Poly-(2,5-thienylene) and poly-[2,5-(methylthienylene)] obtained by subsequent electrolytic reduction are known. However, the electrochemically produced poly-(2,5-thienylene) and poly-[2,5-(3-methylthienylene)] are insoluble and infusible in various solvents, so they cannot be molded. This is extremely difficult and has little practical value as a polymer material.
また、２，５―ジブロムチオフエンや３―メチ
ル―２，５―ジブロムチオフエンを脱臭素化重合
して得られるポリ―（２，５―チエニレン）やポ
リ―〔２，５―（３―メチルチエニレン）〕が知
られている〔「ブレテイン・ケミカル・ソサエテ
イ・オブ・ジヤパン（Bull.Chem.Soc.Jpn.）」第
56巻、第1497〜1502ページ、第1503〜1507ページ
（1983年）〕。しかしながら、これらのポリ―（２，
５―チエニレン）やポリ〔２，５―（３―メチル
チエニレン）〕は、ドーピングされた状態の電気
伝導度が1S／cm以下と低く、かつ重合体の可溶
性部分における重合度も30以下であつて、機械特
性に劣り、有機導電性材料の素材や、各種用途の
素材として実用的でない。 In addition, poly-(2,5-thienylene) and poly-[2,5-( 3-methylthienylene)] is known [Bulletin Chemical Society of Japan (Bull.Chem.Soc.Jpn.) No.
Volume 56, pages 1497-1502, pages 1503-1507 (1983)]. However, these poly(2,
5-thienylene) and poly[2,5-(3-methylthienylene)] have a low electrical conductivity of 1 S/cm or less in the doped state, and the degree of polymerization in the soluble part of the polymer is 30 or less. However, it has poor mechanical properties and is not practical as a material for organic conductive materials or for various uses.
ところで、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、すでに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
ることができることから、優れた特性を有する有
機導電性材料の開発が望まれている。 By the way, in recent years, with the remarkable technological development in the electrical and electronic industries, there has been a demand for new materials with excellent electrical functions.In the field of polymer chemistry, materials with various electrical properties have also been discovered and are already being developed. Although many materials have been put into practical use, 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, the development of organic conductive materials with excellent properties is desired. ing.
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、有
機導電性材料の素材や各種用途の高分子素材とし
て有用な、溶剤に可溶で良好な成形性を有し、か
つドーピングされたものが優れた電気伝導度を有
する新規な高重合度のチオフエン系重合体を提供
することにある。Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to provide a solvent-soluble material with good moldability that is useful as a raw material for organic conductive materials and as a polymeric material for various uses. The object of the present invention is to provide a novel thiophene-based polymer having a high degree of polymerization and having excellent electrical conductivity when doped.
問題点を解決するための手段
本発明者らは、前記のような望ましい特性を有
する新規な、有機導電性材料を開発するために鋭
意研究を重ねた結果、３位に炭素数６〜12の直鎖
アルキル基を有するチオフエン誘導体を電解重合
し、次いで電解還元して得られる重合体により、
その目的を達成しうることを見出し、この知見に
基づいて本発明を完成するに至つた。Means for Solving the Problems The present inventors have conducted intensive research to develop a novel organic conductive material having the above-mentioned desirable properties. A polymer obtained by electrolytically polymerizing a thiophene derivative having a straight-chain alkyl group and then electrolytically reducing it,
The inventors have discovered that the object can be achieved, and have completed the present invention based on this knowledge.
すなわち、本発明は、一般式
（式中のｎは５〜11の整数、ｍは80〜350の整数
である）
で示される３―ｎ―アルキルチオフエン重合体を
提供するものである。 That is, the present invention provides the general formula (In the formula, n is an integer of 5 to 11, and m is an integer of 80 to 350.)
この重合体は、例えば支持電解質を含有する溶
媒中において、一般式
（式中のｎは前記と同じ意味をもつ）
で示されるチオフエン誘導体を電解重合し、次い
で電解還元することによつて、好適に製造するこ
とができる。 This polymer, for example in a solvent containing a supporting electrolyte, has the general formula (n in the formula has the same meaning as above) It can be suitably produced by electrolytically polymerizing a thiophene derivative represented by the following and then electrolytically reducing it.
本発明の重合体は、文献未載の新規なものであ
つて、80〜350の重合度（分子量約10000〜50000）
を有し、かつ塩化メチレン、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などの
溶剤に可溶である。また、この重合体は電気的に
絶縁体であるが、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、トリフルオロメタ
ンスルホン酸イオンなどの陰イオンがドーピング
された状態では、実用化されるのに十分高い電気
伝導度を有する導電体となる。 The polymer of the present invention is novel and has not been described in any literature, and has a degree of polymerization of 80 to 350 (molecular weight of about 10,000 to 50,000).
and is soluble in solvents such as methylene chloride, chloroform, benzene, toluene, and tetrahydronaphthalene. Although this polymer is an electrical insulator, it also contains hexafluorophosphate ions,
When doped with anions such as hexafluoroarsenate ion, tetrafluoroborate ion, perchlorate ion, and trifluoromethanesulfonate ion, it becomes a conductor with high enough electrical conductivity to be put to practical use. .
本発明において、電解重合に用いる単量体は、
前記一般式（）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エン誘
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―ヘプチル基、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―ドデシル基が挙げられる。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
により大きいものは重合体の機械特性が劣り、ま
た所望の重合度が得られにくい。 In the present invention, the monomers used for electropolymerization are:
As shown in the general formula (), it is a thiophene derivative having a straight chain alkyl group having 6 to 12 carbon atoms at the 3-position, and specific examples of the alkyl group include n-
hexyl group, n-heptyl group, n-octyl group,
Examples include n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group. If the number of carbon atoms in the alkyl group is smaller than 6, the resulting polymer will be poorly soluble or insoluble in solvents, while if it is larger, the mechanical properties of the polymer will be poor and it will be difficult to obtain the desired degree of polymerization. .
本発明における支持電解質については、特に制
限はなく、通常の電解重合に慣用されているもの
を用いることができるが、陰イオンがドーピング
され、優れた電気伝導度を有する重合体を所望す
る場合は、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
ホン酸イオンなどを含む塩を用いることが好まし
い。 The supporting electrolyte in the present invention is not particularly limited, and those commonly used in ordinary electrolytic polymerization can be used. However, if a polymer doped with anions and having excellent electrical conductivity is desired, It is preferable to use a salt containing , hexafluorophosphate ion, hexafluoroarsenate ion, tetrafluoroborate ion, perchlorate ion, trifluoromethanesulfonate ion, or the like.
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ツケル、
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。 In the present invention, the electrodes used for electrolytic polymerization include noble metals such as gold and platinum, nickel,
Examples include those made of carbon, or glass electrodes with indium oxide, tin oxide, etc. deposited on the glass surface. In addition to these, aluminum or mercury may also be used as the cathode.
電解重合は、所望の支持電解質を例えばニトロ
ベンゼン、ベンゾニトリル、炭酸ブロピレンなど
の溶媒中に、0.01〜0.2モル／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に従つて
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に適宜選ばれ
る。 Electrolytic polymerization is carried out in an electrolytic solution prepared by dissolving a desired supporting electrolyte in a solvent such as nitrobenzene, benzonitrile, or propylene carbonate to a concentration of 0.01 to 0.2 mol/ml, preferably using nitrogen, argon, or the like. It is carried out under an inert atmosphere according to 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には、使用した
支持電解質中の陰イオンがドーピングされてお
り、したがつて、支持電解質として、前記陰イオ
ンを含む塩を用いることにより、優れた電気伝導
度を有する実用的価値の高い導電性重合体組成物
を得ることができる。このものはテトラヒドロナ
フタレンやトルエンなどの溶剤に可溶であつて、
成形性が良好である。 The polymer obtained in this way is doped with the anion in the supporting electrolyte used, and therefore, by using a salt containing the anion as the supporting electrolyte, it has excellent electrical conductivity. A conductive polymer composition having high practical value can be obtained. This substance is soluble in solvents such as tetrahydronaphthalene and toluene,
Good moldability.
本発明方法においては、このような電解重合を
行つたのち、さらに電解還元処理を行う。この電
解還元処理により、前記の陰イオンがドーピング
された重合体組成物から該陰イオンが脱離し、前
記一般式（）で示される重合体が得られる。 In the method of the present invention, after such electrolytic polymerization is performed, an electrolytic reduction treatment is further performed. Through this electrolytic reduction treatment, the anion is desorbed from the anion-doped polymer composition, and a polymer represented by the general formula () is obtained.
この重合体は塩化メチレン、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など
の溶媒に可溶であつて、容易に成形することがで
きる。このものは、赤外吸収スペクトルにおい
て、820cm-1の波長域に吸収が認められ、２，３，
５―トリ置換チオフエン環を有することが確認さ
れた。なお、重合度は蒸気圧式分子量測定装置に
よつて求めることができる。 This polymer is soluble in solvents such as methylene chloride, chloroform, benzene, toluene, and tetrahydronaphthalene, and can be easily molded. In the infrared absorption spectrum of this material, absorption is observed in the wavelength region of 820 cm -1 , and 2, 3,
It was confirmed that it had a 5-trisubstituted thiophene ring. The degree of polymerization can be determined using a vapor pressure molecular weight measuring device.
前記電解還元処理は、電解重合において用いた
電極の極性を反転して、電流を流すことにより、
容易に行うことができる。 The electrolytic reduction treatment is performed by reversing the polarity of the electrode used in electrolytic polymerization and passing a current.
It can be done easily.
発明の効果
本発明のチオフエン系重合体は、溶剤に可溶で
良好な成形性を有し、かつドーピングされたもの
が優れた電気伝導性を有する新規な高重合度のも
のであつて、有機導電性材料の素材や各種用途の
高分子素材として有用である。Effects of the Invention The thiophene-based polymer of the present invention is a novel high degree of polymerization that is soluble in solvents, has good moldability, and has excellent electrical conductivity when doped. It is useful as a material for conductive materials and as a polymer material for various uses.
実施例
次に実施例によつて本発明をさらに詳細に説明
する。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples.
参考例 １
３―ｎ―ヘキシルチオフエン0.673g（４ミリモ
ル）を20mlのニトロベンゼンに溶解し、これに支
持電解質としてヘキサフルオロリン酸テトラエチ
ルアンモニウム0.138g（0.5ミリモル）を加えた溶
液を調製した。Reference Example 1 A solution was prepared by dissolving 0.673 g (4 mmol) of 3-n-hexylthiophene in 20 ml of nitrobenzene and adding 0.138 g (0.5 mmol) of tetraethylammonium hexafluorophosphate as a supporting electrolyte.
次に、陽極としてITO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℃で電解重
合を行つた。電流密度2mA／cm2で10分間重合す
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。 Next, the above solution was placed in an electrolytic cell using an ITO glass electrode as an anode and a platinum plate as a cathode, and after argon gas was blown in for 15 minutes, electrolytic polymerization was performed at 5°C. When polymerized for 10 minutes at a current density of 2 mA/cm 2 , a black film-like polymer composition doped with hexafluorophosphate ions on the anode was obtained.
この膜状重合体組成物は厚みが7.0μmであり、
95S／cm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／Ｗ）溶解
した。 This film-like polymer composition has a thickness of 7.0 μm,
It showed an electrical conductivity of 95S/cm. It was also dissolved in toluene and tetrahydronaphthalene at a rate of about 60% (W/W).
参考例 ２
参考例１において、ニトロベンゼンの代りに炭
酸プロピレン20mlを用い、かつ電流密度10mA／
cm2で４分間電解重合する以外は、参考例１と同様
にして３―ｎ―ヘキシルチオフエンを電解重合し
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 2 In Reference Example 1, 20 ml of propylene carbonate was used instead of nitrobenzene, and the current density was 10 mA/
When 3-n-hexylthiophene was electrolytically polymerized in the same manner as in Reference Example 1 except that the electrolytic polymerization was carried out at cm 2 for 4 minutes, a black film-like polymer composition doped with hexafluorophosphate ions was obtained. Ta.
この重合体組成物は厚みが8.0μmであつて、
110S／cmの電導度を示した。 This polymer composition has a thickness of 8.0 μm,
It showed an electrical conductivity of 110S/cm.
参考例 ３
参考例１において、３―ｎ―ヘキシルチオフエ
ンの代りに３―ｎ―オクチルチオフエン0.786g
（４ミリモル）を用いる以外は、参考例１と全く
同様にして電解重合を行つたところ、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。Reference Example 3 In Reference Example 1, 0.786g of 3-n-octylthiophene was used instead of 3-n-hexylthiophene.
When electrolytic polymerization was carried out in exactly the same manner as in Reference Example 1 except that (4 mmol) was used, a black film-like polymer composition doped with hexafluorophosphate ions was obtained.
この重合体組成物は厚みが6.0μmであり、かつ
78S／cm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70％（Ｗ／Ｗ）溶解し
た。 This polymer composition has a thickness of 6.0 μm, and
It showed an electrical conductivity of 78S/cm. It was also dissolved in toluene and tetrahydronaphthalene at a rate of about 70% (W/W).
参考例 ４
参考例３において、ニトロベンゼンの代りに炭
酸プロピレン20mlを用い、かつ電流密度10mA／
cm2で４分間電解重合する以外は、参考例３と同様
にして３―ｎ―オクチルチオフエンを電解重合し
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 4 In Reference Example 3, 20 ml of propylene carbonate was used instead of nitrobenzene, and the current density was 10 mA/
When 3-n-octylthiophene was electrolytically polymerized in the same manner as in Reference Example 3, except that the electrolytic polymerization was carried out at cm 2 for 4 minutes, a black film-like polymer composition doped with hexafluorophosphate ions was obtained. Ta.
この膜状重合体組成物は厚みが6.8μmであり、
かつ52S／cmの電導度を示した。 This film-like polymer composition has a thickness of 6.8 μm,
It also showed an electrical conductivity of 52S/cm.
参考例 ５
参考例１において、３―ｎ―ヘキシルチオフエ
ンの代りに３―ｎ―ドデシル３―ｎ―ドデシルチ
オフエン1.008g（４ミリモル）を用い、かつ電流
密度2mA／cm2で５分間電解重合する以外は、参
考例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 5 In Reference Example 1, 1.008 g (4 mmol) of 3-n-dodecyl 3-n-dodecylthiophene was used instead of 3-n-hexylthiophene, and electrolysis was performed at a current density of 2 mA/cm 2 for 5 minutes. When electropolymerization was carried out in the same manner as in Reference Example 1 except for the polymerization, a black film-like polymer composition in which hexafluorophosphate ions were doped on the anode was obtained.
この膜状重合体は厚みが6.9μmであり、かつ
67S／cm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に約90
％（Ｗ／Ｗ）溶解した。 This film-like polymer has a thickness of 6.9 μm and
It showed an electrical conductivity of 67S/cm. Also, toluene has about
60% (W/W), about 90% to tetrahydronaphthalene
% (W/W) dissolved.
参考例 ６
参考例５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0.109g（0.5ミリモ
ル）を用いる以外は、参考例５と全く同様にし
て、３―ｎ―ドデシルチオフエンを電解重合した
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 6 In Reference Example 5, 3-n-dodecylthiophene was prepared in exactly the same manner as in Reference Example 5, except that 0.109 g (0.5 mmol) of tetraethylammonium tetrafluoroborate was used instead of tetraethylammonium hexafluorophosphate. As a result of electrolytic polymerization, a black film-like polymer composition doped with tetrafluoroborate ions was obtained.
この膜状重合体組成物は厚みが6.5μmであり、
かつ61S／cmの電導度を示した。 This film-like polymer composition has a thickness of 6.5 μm,
It also showed an electrical conductivity of 61S/cm.
実施例 １
参考例１と同様にして、３―ｎ―ヘキシルチオ
フエンを電流密度2mA／cm2で10分間電解重合し
たところ、陽極上にヘキサフルオロリン酸イオン
がドーピングされた黒色膜状重合体組成物が得ら
れた。Example 1 In the same manner as in Reference Example 1, 3-n-hexylthiophene was electrolytically polymerized at a current density of 2 mA/cm 2 for 10 minutes, resulting in a black film-like polymer doped with hexafluorophosphate ions on the anode. A composition was obtained.
次に、電極の極性を反転し、電流密度0.5mA／
cm2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。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。この重合体の赤外吸収ス
ペクトルを第１図に示す。 Next, reverse the polarity of the electrode and use a current density of 0.5 mA/
Electrolytic reduction was performed by flowing a current until the voltage difference between the two electrodes exceeded 5 V in cm 2 and reached a constant voltage, and hexafluorophosphate ions were removed from the composition. Next, this material was washed with methanol, dried, and
A red film-like polymer was obtained. The infrared absorption spectrum of this polymer is shown in FIG.
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／
Ｗ）以上溶解した。また、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であつた。 This polymer consists of methylene chloride, chloroform,
90% (W/
W) More dissolved. Further, the degree of polymerization determined by a vapor pressure molecular weight measuring device using chloroform was 230.
実施例 ２
参考例３と同様にして、３―ｎ―オクチルチオ
フエンを電流重合して黒色膜状重合体組成物が得
たのち、実施例１と同様にして電解還元を行つ
た。生成物をメタノールで洗浄したのち乾燥し
て、赤色膜状重合体を得た。Example 2 In the same manner as in Reference Example 3, 3-n-octylthiophene was subjected to electric current polymerization to obtain a black film-like polymer composition, and then electrolytic reduction was performed in the same manner as in Example 1. The product was washed with methanol and then dried to obtain a red filmy 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／
Ｗ）以上溶解した。またクロロホルムを用いた蒸
気圧式分子量測定装置にて求められた重合度は
140であつた。 This polymer is 90% (W/
W) More dissolved. In addition, the degree of polymerization determined by a vapor pressure molecular weight measuring device using chloroform is
It was 140.
実施例 ３
参考例５と同様にして、３―ｎ―ドデシルチオ
フエンを電解重合して黒色膜状重合体を得たの
ち、実施例１と同様にして電解還元を行つた。生
成物をメタノールで洗浄したのち、乾燥して赤色
膜状重合体を得た。この重合体の赤外吸収スペク
トルを第２図に示す。Example 3 In the same manner as in Reference Example 5, 3-n-dodecylthiophene was electrolytically polymerized to obtain a black film-like polymer, and then electrolytically reduced in the same manner as in Example 1. The product was washed with methanol and then dried to obtain a red filmy polymer. The infrared absorption spectrum of this polymer is shown in FIG.
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95％（Ｗ／
Ｗ）以上溶解した。またクロロホルムを用いた蒸
気圧式分子量測定装置にて求められた重合度は90
であつた。 This polymer is 95% (W/
W) More dissolved. In addition, the degree of polymerization determined by a vapor pressure molecular weight measuring device using chloroform was 90.
It was hot.
第１図及び第２図は、それぞれポリ―〔２，５
―３―ヘキシルチエニレン）〕及びポリ―〔２，
５―（３―ドデシルチエニレン）〕の赤外吸収ス
ペクトル図である。
Figures 1 and 2 are poly[2,5
-3-hexylthienylene)] and poly-[2,
5-(3-dodecylthienylene)] is an infrared absorption spectrum diagram.
Claims (1)
である） で示される３―ｎ―アルキルチオフエン重合体。 ２ 支持電解質を含有する溶媒中において、一般
式 （式中のｎは５〜11の整数である） で示されるチオフエン誘導体を電解重合し、次い
で電解還元することを特徴とする、一般式 （式中のｍは80〜350の整数であり、ｎは前記と
同じ意味をもつ） で示される３―ｎ―アルキルチオフエン重合体の
製造方法。[Claims] 1. General formula (In the formula, n is an integer of 5 to 11, and m is an integer of 80 to 350.) A 3-n-alkylthiophene polymer represented by the following. 2 In a solvent containing a supporting electrolyte, the general formula (n in the formula is an integer of 5 to 11) The general formula is characterized by electrolytically polymerizing a thiophene derivative and then electrolytically reducing it. (In the formula, m is an integer of 80 to 350, and n has the same meaning as above.) A method for producing a 3-n-alkylthiophene polymer represented by the following.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6299986A JPS62220518A (en) | 1986-03-20 | 1986-03-20 | Thiophene polymer 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 |
|---|---|---|---|
| JP6299986A JPS62220518A (en) | 1986-03-20 | 1986-03-20 | Thiophene polymer and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62220518A JPS62220518A (en) | 1987-09-28 |
| JPS6411209B2 true JPS6411209B2 (en) | 1989-02-23 |
Family
ID=13216583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6299986A Granted JPS62220518A (en) | 1986-03-20 | 1986-03-20 | Thiophene polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62220518A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2099041A1 (en) | 2008-03-04 | 2009-09-09 | Nec Tokin Corporation | Conductive polymer and solid electrolytic capacitor using the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2596566B1 (en) * | 1986-04-01 | 1989-03-10 | Solvay | CONDUCTIVE POLYMERS DERIVED FROM 3-ALKYLTHIOPHENES, PROCESS FOR THEIR MANUFACTURE AND ELECTRICALLY CONDUCTIVE DEVICES CONTAINING THEM |
| JPH03210326A (en) * | 1990-01-13 | 1991-09-13 | Dainippon Printing Co Ltd | Conductive polymer and its production |
| JP6308624B2 (en) * | 2012-07-31 | 2018-04-11 | 国立大学法人千葉大学 | Film having metallic luster, article formed therewith, and method for producing film having metallic luster |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5943060A (en) * | 1982-09-02 | 1984-03-09 | Matsushita Electric Ind Co Ltd | Five-membered heterocyclic compound polymer |
-
1986
- 1986-03-20 JP JP6299986A patent/JPS62220518A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2099041A1 (en) | 2008-03-04 | 2009-09-09 | Nec Tokin Corporation | Conductive polymer and solid electrolytic capacitor using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62220518A (en) | 1987-09-28 |
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