JPS6320326A - Polyanthracene and its production - Google Patents
Polyanthracene and its productionInfo
- Publication number
- JPS6320326A JPS6320326A JP16338786A JP16338786A JPS6320326A JP S6320326 A JPS6320326 A JP S6320326A JP 16338786 A JP16338786 A JP 16338786A JP 16338786 A JP16338786 A JP 16338786A JP S6320326 A JPS6320326 A JP S6320326A
- Authority
- JP
- Japan
- Prior art keywords
- polyanthracene
- anthracene
- film
- anodic oxidation
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 tetrabutylammonium tetrafluoroborate Chemical compound 0.000 claims abstract description 22
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 16
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 14
- 229960003280 cupric chloride Drugs 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 125000005577 anthracene group Chemical group 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000007710 freezing Methods 0.000 abstract description 2
- 230000008014 freezing Effects 0.000 abstract description 2
- 150000008040 ionic compounds Chemical class 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 abstract 1
- 239000010408 film Substances 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GYMFBYTZOGMSQJ-UHFFFAOYSA-N 2-methylanthracene Chemical compound C1=CC=CC2=CC3=CC(C)=CC=C3C=C21 GYMFBYTZOGMSQJ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920000265 Polyparaphenylene Polymers 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001454 anthracenes Chemical group 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film 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
- 238000005406 washing Methods 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、半導体材料として有用な新規高分子化合物ポ
リアントラセン及びその製造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 polymer compound polyanthracene useful as a semiconductor material and a method for producing the same.
科学技術の進歩と共に新しい機能を有する電気・電子材
料、特に半導体の開発が求められており、高分子の分野
においても研究が活発に行われている。その結果、ポリ
アセチレン、ポリフェニレン等の共役系高分子、或いは
これに電子供与性化合物、電子吸引性化合物を添加した
有機半導体がこれまでに開発された。例えば、本発明者
らによる「ジャーナル・オブ・ジ・ケミカル・ソサエテ
ィ」誌、１９８５年、１６２９頁にはベンゼンの電解重
合によるポリパラフェニレンフィルｌ、が例示されてい
る。With advances in science and technology, there is a need for the development of electrical and electronic materials with new functions, especially semiconductors, and research is also being actively conducted in the field of polymers. As a result, conjugated polymers such as polyacetylene and polyphenylene, or organic semiconductors in which electron-donating compounds and electron-withdrawing compounds are added have been developed. For example, "Journal of the Chemical Society", 1985, p. 1629, by the present inventors, exemplifies polyparaphenylene fill made by electrolytic polymerization of benzene.
しかしながら、これまでに合成された高分子半導体は、
ポリアセチレンやポリピロール、ポリチオフェン、ポリ
フラン、ポリアニリン、ポリピリダジン、ポリパラフェ
ニレン及びその誘導体に限られており、アントラセンの
重合体であるポリアントラセンは報告されていない。However, the polymer semiconductors synthesized so far are
It is limited to polyacetylene, polypyrrole, polythiophene, polyfuran, polyaniline, polypyridazine, polyparaphenylene, and their derivatives, and polyanthracene, which is an anthracene polymer, has not been reported.
また、本発明のポリアントラセンの１体であるアントラ
センは有機化合物として初めて光導電性が認められたも
のであるが、この光導電性は有機半導体の代表的な特性
の一つであることが明らかとなっている。現在では、こ
の特性が電子写真、画像情報蓄積或いははデバイスホロ
グラムの分野に応用されている。しかしながら、実用に
際しては機械的強度に劣るアントラセン等の有機結晶は
用いられず、ポリビニルカルバゾール等の高分子有機半
導体、或いは無機材料であるセレンの蒸着膜等が用いら
れている。Furthermore, anthracene, one of the polyanthracenes of the present invention, is the first organic compound to be recognized as having photoconductivity, and it is clear that this photoconductivity is one of the typical properties of organic semiconductors. It becomes. Currently, this characteristic is applied to the fields of electrophotography, image information storage, and device holograms. However, in practical use, organic crystals such as anthracene, which have poor mechanical strength, are not used, but polymeric organic semiconductors such as polyvinylcarbazole, or vapor-deposited films of selenium, which is an inorganic material, are used.
現在までの研究で、高分子半導体４体の電気的・光学的
性質は、その分子構造によって大きく変化することが知
られている。しかしながら先にも述べた通り、従来報告
されている高分子半導体はポリアセチレン、ポリフェニ
レン等の繰り返し単位が比較的低分子量であるものに限
られており、光導電性等の良好な電気的・光学的特性が
期待される高分子量化合物を繰り返し単位とする高分子
半導体は得られていない。Research to date has shown that the electrical and optical properties of four polymer semiconductors vary greatly depending on their molecular structure. However, as mentioned above, conventionally reported polymer semiconductors are limited to those with relatively low molecular weight repeating units such as polyacetylene and polyphenylene, and have good electrical and optical properties such as photoconductivity. Polymer semiconductors whose repeating units are high molecular weight compounds with promising properties have not been obtained.
以上の点から、本発明は従来全く知られていなかったア
ントラセン或いはその置換体を繰り返し単位とする新規
な重合体、ポリアントラセン及びその製造法を提供する
ものである。In view of the above, the present invention provides a novel polymer, polyanthracene, which has a repeating unit of anthracene or its substituted product, which has not been previously known, and a method for producing the same.
即ち本発明は、置換基を有することもあるアントラセン
を繰り返し単位とする新規高分子化合物ポリアントラセ
ン及びその製造法に関するものである。That is, the present invention relates to a novel polymer compound polyanthracene whose repeating unit is anthracene, which may have a substituent, and a method for producing the same.
次に本発明の高分子有機半導体ポリアントラセンの詳細
について述べる。本発明の重合体は、その製造条件によ
ってフィルム、或いは粉末として得られるが、特にフィ
ルムで得られるポリアントラセンが実用に有利である。Next, details of the polymeric organic semiconductor polyanthracene of the present invention will be described. The polymer of the present invention can be obtained as a film or a powder depending on the manufacturing conditions, but polyanthracene obtained in the form of a film is particularly advantageous for practical use.
このポリアントラセンフィルムは均一で平滑な表面を有
しており、極めて柔軟性に冨んでいる。フィルムの膜厚
は本発明の製造法により、０．０１μｍから１００μｍ
まで任意に制御可能である。This polyanthracene film has a uniform, smooth surface and is extremely flexible. The thickness of the film is from 0.01 μm to 100 μm by the manufacturing method of the present invention.
can be controlled arbitrarily up to
本発明のポリアントラセンは、それ自体、室温で１０−
’Ｓ／ｃｍの電気伝導度を有する高分子有機半導体で
あるが、リチウム、カリウム、テトラアルキルアンモニ
ウムイオン等の電子供与性物質、或いはテトラフルオロ
ホウ酸、過塩素酸、ヘキサフルオロヒ素酸イオン等の電
子吸引性物質を７昆入（ドーピング）することにより、
１Ｏ−９Ｓ／ｃｍからＩ Ｓ／ｃｍまで任意に電気伝導
度を制御することができる。得られたフィルムは０．１
μ信の薄膜に於いても十分な機械的強度を有しており、
アセトンやメタノール等の通常用いられる全ての有機溶
媒に不溶で、化学的安定性に優れている。本発明のポリ
アントラセンの赤外吸収スペクトルは、１０５１０５Ｏ
’と７７０ｃｍ−’の２本のバンドが９，１０−ジ置換
アントラセン環に帰属される。The polyanthracene of the present invention itself has 10-
It is a polymeric organic semiconductor with an electrical conductivity of 'S/cm. By doping 7 electron-withdrawing substances,
The electrical conductivity can be arbitrarily controlled from 10-9S/cm to IS/cm. The obtained film was 0.1
It has sufficient mechanical strength even in the thin film of μ-rays.
It is insoluble in all commonly used organic solvents such as acetone and methanol, and has excellent chemical stability. The infrared absorption spectrum of the polyanthracene of the present invention is 105105O
The two bands at ' and 770 cm-' are assigned to the 9,10-disubstituted anthracene ring.
本発明のポリアントラセンは他の高分子半導体と同様に
電気化学的方法及び化学的方法で可逆的にドープ、脱ド
ープすることができ、任意の電荷移動状態とすることが
できる。それに伴って電気的性質のみならず光学的性質
も大きく変化する。The polyanthracene of the present invention, like other polymer semiconductors, can be reversibly doped and dedoped by electrochemical and chemical methods, and can be put into any charge transfer state. Along with this, not only the electrical properties but also the optical properties change greatly.
本発明のポリアントラセンは置換基を有することもある
アントラセンを電気化学的陽極酸化法で重合（電解重合
）させることにより製造される。置換基を有するアント
ラセンとしては、２−メチルアントラセン等の９，１０
位を除く位置がアルキル基、ハロゲン等で置換されたア
ントラセン化合物が挙げられる。電解重合は電解質を含
む極性溶媒中で行われるが、塩化第２銅、塩化アルミニ
ウム等のルイス酸を発生するイオン化合物を含む系で行
うのが有利であり、好ましくは塩化第２銅を含む系で行
うのが有利である。この際の極性溶媒としては、アセト
ニトリル、ニトロベンゼン、ニトロメタン、テトラヒド
ロフラン、ジメチルホルムアミド、オルトジクロルベン
ゼン等が挙げられるが、単量体及び電解質の溶解度の面
からオルトジクロルベンゼンが好ましく選ばれる。The polyanthracene of the present invention is produced by polymerizing anthracene, which may have a substituent, by an electrochemical anodic oxidation method (electrolytic polymerization). As the anthracene having a substituent, 9,10 such as 2-methylanthracene
Examples include anthracene compounds substituted with alkyl groups, halogens, etc. at positions other than position. Electrolytic polymerization is carried out in a polar solvent containing an electrolyte, but it is advantageous to carry out in a system containing an ionic compound that generates a Lewis acid such as cupric chloride or aluminum chloride, preferably a system containing cupric chloride. It is advantageous to do so. Examples of the polar solvent in this case include acetonitrile, nitrobenzene, nitromethane, tetrahydrofuran, dimethylformamide, ortho-dichlorobenzene, and ortho-dichlorobenzene is preferably selected from the viewpoint of solubility of the monomer and electrolyte.
電解重合の電極材料には金属をはじめとして、通常の導
電性物質がすべて用いられる。All conventional conductive substances, including metals, can be used as electrode materials for electrolytic polymerization.
支持電解質としては、テトラフルオロホウ酸テトラブチ
ルアンモニウム、過塩素酸テトラブチルアンモニウム等
のハロゲン化合物アニオンとテトラアルキルアンモニウ
ムカチオンとの塩、及びテトラフルオロホウ酸リチウム
、ヘキサフルオロヒ素酸リチウム等のハロゲン化合物ア
ニオンとアルカリ金属との塩などが挙げられる。As the supporting electrolyte, salts of halogen compound anions such as tetrabutylammonium tetrafluoroborate and tetrabutylammonium perchlorate and tetraalkylammonium cations, and halogen compound anions such as lithium tetrafluoroborate and lithium hexafluoroarsenate are used. and alkali metal salts.
電解液は上記の支持電解質を含む極性溶媒から構成され
るが、好ましくは塩化第２銅を添加して用いられる。最
も好ましい電解液の組成は、溶媒としてオルトジクロル
ベンゼン、電解質としてテトラフルオロホウ酸テトラブ
チルアンモニウム及び塩化第２銅からなる系である。The electrolytic solution is composed of a polar solvent containing the above-mentioned supporting electrolyte, and is preferably used with the addition of cupric chloride. The most preferred composition of the electrolytic solution is a system consisting of orthodichlorobenzene as a solvent and tetrabutylammonium tetrafluoroborate and cupric chloride as electrolytes.
電解重合は室温を中心として、溶媒の凝固点以上、沸点
以下の広い温度範囲で行うことができ、定電圧電解又は
定電流電解で行われる。フィルムは陽極表面上に形成さ
れ、通電時間を調節することで膜厚が制御される。生成
物は使用した支持電解質中のアニオンがドーピングされ
た構造で得られ、これは次に逆電圧を印加したり、アン
モニア蒸気に接触させたりすることによりアニオンが脱
離、或いは中和して脱ドープされる。Electrolytic polymerization can be carried out in a wide temperature range from room temperature to above the freezing point and below the boiling point of the solvent, and is carried out by constant voltage electrolysis or constant current electrolysis. A film is formed on the surface of the anode, and the film thickness is controlled by adjusting the current application time. The product is obtained in a structure in which the anions in the supporting electrolyte used are doped, and the anions are then desorbed or neutralized by applying a reverse voltage or coming into contact with ammonia vapor. Be doped.
生成したポリアントラセンフィルムは、目的に応じて電
極に付着したまま、或いは電極から引き剥がしたフィル
ムの形で使用される。The produced polyanthracene film is used either as it is attached to the electrode or in the form of a film that is peeled off from the electrode, depending on the purpose.
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例のみ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１
ガラス容器中にオルトジクロルベンゼンを入れ、これに
アントラセン、テトラフルオロホウ酸テトラブチルアン
モニウム、塩化第２銅をそれぞれ１．Ｏｍｏｌ／ ｌ、
０．１ｍｏｌ／ １２．０．１ｍｏｌ／ ｌの濃度とな
るように添加して溶液を攪拌し、電解液とした。この電
解液に陽極としてインジウム、スズ酸化膜を被覆した導
電性ガラス、陰極としてニッケル板を浸漬して室温で電
解重合を行った。両電極間に２０Ｖの定電圧を印加した
ところ、陽極上にテトラフルオロホウ酸イオンがドーピ
ングされた青色フィルムが得られた。１０分間反応後、
生成したフィルムを取り出し、ベンゼンで洗浄、乾燥後
、電気伝導度を測定したところ、室温で０．１Ｓ／ｃｍ
の電気伝導度を持つ半導体であった。Example 1 Orthodichlorobenzene was placed in a glass container, and 1.0% each of anthracene, tetrabutylammonium tetrafluoroborate, and cupric chloride were added thereto. Omol/l,
It was added to give a concentration of 0.1 mol/12.0.1 mol/l, and the solution was stirred to obtain an electrolytic solution. Electrolytic polymerization was carried out at room temperature by immersing a conductive glass coated with an indium and tin oxide film as an anode and a nickel plate as a cathode in this electrolyte solution. When a constant voltage of 20 V was applied between both electrodes, a blue film doped with tetrafluoroborate ions was obtained on the anode. After reacting for 10 minutes,
The produced film was taken out, washed with benzene, dried, and then its electrical conductivity was measured, and it was found to be 0.1 S/cm at room temperature.
It was a semiconductor with an electrical conductivity of .
実施例２
実施例１と同様の電解液を用いて、同様の条件で電解重
合を行って青色フィルム状生成物を得た。１０分間の反
応後、直ちに電流の向きを逆にするとテトラフルオロホ
ウ酸イオンがフィルムより脱離し、淡黄色のフィルムが
得られた。Example 2 Using the same electrolytic solution as in Example 1, electrolytic polymerization was carried out under the same conditions to obtain a blue film-like product. Immediately after 10 minutes of reaction, the direction of the current was reversed, and the tetrafluoroborate ions were desorbed from the film, yielding a pale yellow film.
ベンゼンで洗浄後、乾燥して電気伝導度を測定したとこ
ろ、室温で１０−９Ｓ／ｃａａの電気伝導度を持つ半導
体であった。このポリアントラセンフィルムの赤外吸収
スペクトルを第１図に示す。After washing with benzene, drying and measuring the electrical conductivity, it was found that the semiconductor had an electrical conductivity of 10-9 S/caa at room temperature. The infrared absorption spectrum of this polyanthracene film is shown in FIG.
また、電解重合してアニオンを脱離させた淡黄色フィル
ムを、電極に付着させたまま０．１ｍｏｌ／ Ｉ！掘度
の過塩素酸リチウムを含む炭酸プロピレン溶液に浸漬し
、ニッケル板を対極として電圧を印加したところ、フィ
ルムの色相は電圧の上昇に伴って淡黄色から青色に変化
した。この時の吸収スペクトルの変化を第２図に示す。In addition, a pale yellow film that was electrolytically polymerized to remove anions was left attached to the electrode at a rate of 0.1 mol/I! When the film was immersed in a propylene carbonate solution containing lithium perchlorate and a voltage was applied using a nickel plate as a counter electrode, the color of the film changed from pale yellow to blue as the voltage increased. Figure 2 shows the change in the absorption spectrum at this time.
この変化は可逆的であり、印加する電圧を調節すること
でフィルムの色相を淡黄色と青色の間で繰り返し変える
ことができた。This change was reversible, and the hue of the film could be repeatedly changed between pale yellow and blue by adjusting the applied voltage.
実施例３
実施例１において、テトラフルオロホウ酸テトラブチル
アンモニウムの代わりに過塩素酸テトラブチルアンモニ
ウムを用いたほかは同様な操作を行った。２０Ｖの定電
流で１０分間反応させたところ、過塩素酸イオンがドー
ピングされた青色フィルムが得られた。このフィルムの
室温での電気伝導度は０．２５／ｃｍであり、実施例２
と同様の方法で脱ドーすると１０−９Ｓ／ｃｍとなった
。Example 3 The same operation as in Example 1 was carried out except that tetrabutylammonium perchlorate was used instead of tetrafluoroborate tetrabutylammonium. When the reaction was carried out for 10 minutes at a constant current of 20 V, a blue film doped with perchlorate ions was obtained. The electrical conductivity of this film at room temperature was 0.25/cm, and Example 2
Dedoping was performed in the same manner as above, and the result was 10-9 S/cm.
実施例４
実施例１において、塩化第２銅の代わりに塩化アルミニ
ウムを用いたほかは同様な操作を行った。２０ｖの定電
流で１０分間反応させたところ、テトラフルオロホウ酸
イオンがドーピングされた青色フィルムが得られた。こ
のフィルムの室温での電気伝導度は２ Ｘ １０−’Ｓ
／ｃｍであった。Example 4 The same operation as in Example 1 was performed except that aluminum chloride was used instead of cupric chloride. When the reaction was carried out for 10 minutes at a constant current of 20 V, a blue film doped with tetrafluoroborate ions was obtained. The electrical conductivity of this film at room temperature is 2 x 10-'S
/cm.
実施例５
実施例１において、アントラセンの代わりに２−メチル
アントラセンを用いたほかは同様な操作を行った。３０
Ｖの定電流で２０分間反応させたところ、テトラフルオ
ロホウ酸イオンがドーピングされた黒色フィルムが得ら
れた。このフィルムの室温での電気伝導度はＩ Ｘ １
０− ’Ｓ／ｃｍであった。Example 5 The same operation as in Example 1 was performed except that 2-methylanthracene was used instead of anthracene. 30
When the reaction was carried out for 20 minutes at a constant current of V, a black film doped with tetrafluoroborate ions was obtained. The electrical conductivity of this film at room temperature is I x 1
It was 0-'S/cm.
本発明を実施することにより、電子デバイス分野に用い
られる半導体材料として有用な新規高分子化合物ポリア
ントラセンを提供することができ、工業的価値がある。By implementing the present invention, it is possible to provide a novel polymer compound polyanthracene useful as a semiconductor material used in the field of electronic devices, which has industrial value.
第１図は実施例２で得られたポリアントラセンフィルム
の赤外吸収スペクトル、第２図は電気化学的にドーピン
グしたポリアントラセンフィルムの各ドープ電圧におけ
る吸収スペクトルである。FIG. 1 shows the infrared absorption spectrum of the polyanthracene film obtained in Example 2, and FIG. 2 shows the absorption spectrum of the electrochemically doped polyanthracene film at various doping voltages.
Claims (1)
物ポリアントラセン。 ２ 置換基を有することもあるアントラセンを電気化学
的に陽極酸化重合することを特徴とするポリアントラセ
ンの製造方法。 ３ 陽極酸化重合が、ルイス酸を発生する化合物のイオ
ンを含む電解液中で行われるものである特許請求の範囲
第２項記載のポリアントラセンの製造方法。 ４ 電解液が、ハロゲンを含むアニオンとテトラアルキ
ルアンモニウムカチオンとの塩を電解質とするオルトジ
クロルベンゼン溶液である特許請求の範囲第３項記載の
ポリアントラセンの製造方法。[Claims] 1. A novel polymer compound polyanthracene having anthracene as a repeating unit. 2. A method for producing polyanthracene, which comprises electrochemically anodic oxidation polymerization of anthracene that may have a substituent. 3. The method for producing polyanthracene according to claim 2, wherein the anodic oxidation polymerization is carried out in an electrolytic solution containing ions of a compound that generates a Lewis acid. 4. The method for producing polyanthracene according to claim 3, wherein the electrolytic solution is an orthodichlorobenzene solution containing a salt of a halogen-containing anion and a tetraalkylammonium cation as an electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16338786A JPS6320326A (en) | 1986-07-11 | 1986-07-11 | Polyanthracene and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16338786A JPS6320326A (en) | 1986-07-11 | 1986-07-11 | Polyanthracene and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6320326A true JPS6320326A (en) | 1988-01-28 |
Family
ID=15772921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16338786A Pending JPS6320326A (en) | 1986-07-11 | 1986-07-11 | Polyanthracene and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6320326A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012136003A1 (en) * | 2011-04-07 | 2012-10-11 | Tongji University | Polyanthrylene materials and methods for their preparation and use |
| JP2013534936A (en) * | 2010-06-04 | 2013-09-09 | トンジ ユニバーシティ | Method for producing polyanthracene and use thereof |
| CN107973900A (en) * | 2017-11-06 | 2018-05-01 | 华南理工大学 | A kind of poly- anthracene compound and its preparation method and application |
-
1986
- 1986-07-11 JP JP16338786A patent/JPS6320326A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013534936A (en) * | 2010-06-04 | 2013-09-09 | トンジ ユニバーシティ | Method for producing polyanthracene and use thereof |
| US8735537B2 (en) | 2010-06-04 | 2014-05-27 | Tongji University | Methods of producing polyanthracene and uses thereof |
| EP2576652A4 (en) * | 2010-06-04 | 2014-09-03 | Univ Tongji | Methods of producing polyanthracene and uses thereof |
| US9290610B2 (en) | 2010-06-04 | 2016-03-22 | Tongji University | Methods of producing polyanthracene and uses thereof |
| WO2012136003A1 (en) * | 2011-04-07 | 2012-10-11 | Tongji University | Polyanthrylene materials and methods for their preparation and use |
| US8735166B2 (en) | 2011-04-07 | 2014-05-27 | Tongji University | Polyanthrylene materials and methods for their preparation and use |
| US9063109B2 (en) | 2011-04-07 | 2015-06-23 | Tongji University | Polyanthrylene materials and methods for their preparation and use |
| CN107973900A (en) * | 2017-11-06 | 2018-05-01 | 华南理工大学 | A kind of poly- anthracene compound and its preparation method and application |
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