JPS61118454A - Electrically conductive polymer material having electrical anisotropy, and production thereof - Google Patents
Electrically conductive polymer material having electrical anisotropy, and production thereofInfo
- Publication number
- JPS61118454A JPS61118454A JP23955884A JP23955884A JPS61118454A JP S61118454 A JPS61118454 A JP S61118454A JP 23955884 A JP23955884 A JP 23955884A JP 23955884 A JP23955884 A JP 23955884A JP S61118454 A JPS61118454 A JP S61118454A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- polyacetylene
- conductive polymer
- substance
- electron
- 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
- 229920001940 conductive polymer Polymers 0.000 title claims description 7
- 239000002861 polymer material Substances 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 37
- 239000004973 liquid crystal related substance Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 229920001197 polyacetylene Polymers 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000758 substrate Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FNGLQNMQHOAIJQ-UHFFFAOYSA-N Cl[S](Cl)Cl Chemical compound Cl[S](Cl)Cl FNGLQNMQHOAIJQ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は、高配向ポリアセチレンから得られる電気的異
方性を有する導電性高分子材料及びその製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a conductive polymer material having electrical anisotropy obtained from highly oriented polyacetylene and a method for producing the same.
アセチレンを遷移金属化合物と有機金属化合物からなる
チーグラ・ナツメ触媒を用いて重合させる方法において
、アセチレンと重合触媒溶液との自由表面近傍の界面に
おいて重合反応を行うと、直接的に膜状ポリアセチレン
を製造することが出来る（特公昭４８−３２５８１号）
。In the method of polymerizing acetylene using a Ziegler-Natsume catalyst consisting of a transition metal compound and an organometallic compound, when the polymerization reaction is carried out at the interface near the free surface of acetylene and a polymerization catalyst solution, film-like polyacetylene is directly produced. (Special Publication No. 48-32581)
.
この膜は直径数百ムのフィブリル（繊維状微結晶）が無
秩序に集合した構造を有している。This film has a structure in which fibrils (fibrous microcrystals) with a diameter of several hundred micrometers are assembled in a disordered manner.
このポリアセチレンは有機半導体として知られ、更に電
子供与性物質あるいは電子受容性物質をドープすること
により高い電気伝導性を有する材料にすることが出来る
（特開昭５５−１２９４２６号）。一般に高分子材料に
おいては、その二次元性が材料の巨視構造に反映される
と、すなわち−軸配向を有すると材料特性が向上するこ
とが知られている。上記ポリアセチレンは加熱しても溶
融せず、またこのポリマーを溶解する溶媒も見出されて
いない。このため、高配向化したポリアセテレ／を得る
方法としては以下の５通りが提案されている。This polyacetylene is known as an organic semiconductor, and can be made into a material with high electrical conductivity by doping it with an electron-donating substance or an electron-accepting substance (Japanese Patent Laid-Open No. 129426/1983). Generally, in polymeric materials, it is known that the material properties are improved when the two-dimensionality is reflected in the macroscopic structure of the material, that is, when the material has a -axis orientation. The above polyacetylene does not melt even when heated, and no solvent has been found that dissolves this polymer. For this reason, the following five methods have been proposed as methods for obtaining highly oriented polyacetele/.
（１） 上記ポリアセチレンを加熱下で機械的操作に
よシ延伸する（ ８ｙｎｔｈ＠ｔｉｃ Ｍ＠ｔａ１ｇ、
第１巻ｆＪｃ１７５〜１８４頁（１９７９／１９８Ｇ）
：１（２） シイアーク０−下でポリアセチレンを合
成する（ ＭｏＬ ０ｒｙｓｔ、 Ｌｉｑ、 ０ｒｙｓ
ｔ、、第７７巻第１３７〜１４６頁（１９８１））
（３） ビフェニル等の有機物結晶上でエピタキシャ
ル形成する（ 、Ｔ、 Ｐｏｌｙｍ、 ８ａｉ、 ：
Ｐｏｌｙｍ、 ＩＩ６ｔｔ−ｍａ。第２０巻第３０５〜
５０８頁（１９８２））これらの方法で得られた材料は
電気的異方性を示し、配向軸方向の電気抵抗は延伸して
いないものの半分以下になる。この電気的異方性は電子
供与性物質あるいは電子受容性物質（よる処理後でも保
持される。しかしながら、これらの材料はそれぞれ以下
の欠点を有し、実用上好しくない。（１）の方法ではフ
ィブリルの切断を伴い、かつ初期の試料形状が維持出来
ない等の欠点を持つ。（２）の方法で得られるポリアセ
チレンの膜厚は極端に小さく、取扱い難い欠点を持つ。(1) The above polyacetylene is stretched by mechanical operation under heating (8ynth@tic M@talg,
Volume 1 fJc pages 175-184 (1979/198G)
:1(2) Synthesize polyacetylene under siearch 0- (MoL 0ryst, Liq, 0rys
t, Vol. 77, pp. 137-146 (1981)) (3) Epitaxial formation on organic crystals such as biphenyl (T, Polym, 8ai,:
Polym, II6tt-ma. Volume 20, No. 305~
508 (1982)) The materials obtained by these methods exhibit electrical anisotropy, and the electrical resistance in the orientation axis direction is less than half that of the unstretched material. This electrical anisotropy is maintained even after treatment with an electron-donating substance or an electron-accepting substance. However, each of these materials has the following drawbacks and is not practical. Method (1) This method involves the cutting of fibrils and has disadvantages such as the inability to maintain the initial sample shape.The polyacetylene film obtained by method (2) has an extremely small thickness and is difficult to handle.
（３）の方法では微少面積の試料しか得られない。With method (3), only a small area of the sample can be obtained.
本発明者らは先に、上記以外の方法で高配向ポリアセチ
レン膜を得る方法として、液晶媒体中でアセチレンを重
合する方法を見出した（特願昭５８−１２９４０８号）
。その方法で得られる膜は、その形状を自由に選択する
ことが可能である。また、膜厚も上記（２）と比較する
と、かなシ厚く作製することが出来る。更に、その面積
は合成する際に用いる反応器の大きさく依存し、実質的
くけ制限がないと言える。これらのことから、液晶媒体
中で合成された高配向ポリアセチレンは、実用に適した
材料と言える。The present inventors previously discovered a method of polymerizing acetylene in a liquid crystal medium as a method for obtaining a highly oriented polyacetylene film by a method other than the above (Japanese Patent Application No. 129408/1982).
. The shape of the membrane obtained by this method can be freely selected. Furthermore, the film thickness can be made significantly thicker than in (2) above. Furthermore, the area depends on the size of the reactor used during synthesis, and it can be said that there is no substantial limitation on the area. For these reasons, highly oriented polyacetylene synthesized in a liquid crystal medium can be said to be a material suitable for practical use.
しかし、それでも改良の余地はある。However, there is still room for improvement.
本発明の目的は、液晶物質を用いて合成した高配向ポリ
アセチレンを、更に改質した電気的異方性を有する導電
性高分子材料及びその製造方法を提供することくある。An object of the present invention is to provide a conductive polymer material having electrical anisotropy, which is obtained by further modifying highly oriented polyacetylene synthesized using a liquid crystal substance, and a method for producing the same.
本発明を概説すれば、本発明の第１の発明は電気的異方
性を有する導電性高分子材料に関する発明であって、ド
ーパントを含有する高配向ポリアセチレンを包含するこ
とを特徴とする。To summarize the present invention, the first aspect of the present invention relates to a conductive polymer material having electrical anisotropy, and is characterized in that it includes highly oriented polyacetylene containing a dopant.
また、本発明の第２の発明は上記高分子材料の製造方法
に関する発明であって、液晶物質を重合媒体として用い
アセチレンを重合させることにより得た高配向ポリアセ
チレンを、電子受容性物質又は電子供与性物質で処理す
ることを特徴とする。Further, the second invention of the present invention relates to a method for producing the above-mentioned polymeric material, in which highly oriented polyacetylene obtained by polymerizing acetylene using a liquid crystal substance as a polymerization medium is used as an electron-accepting substance or an electron-donating substance. It is characterized by treatment with sexual substances.
以下、本発明を具体的に説明する。The present invention will be specifically explained below.
本発明に訃いて用いられる電子供与性物質の例には、リ
チウム、ナトリウム、カリウム、ルビジウム及びセシウ
ム等のアルカリ金属がある。Examples of electron-donating substances that can be used in the present invention include alkali metals such as lithium, sodium, potassium, rubidium, and cesium.
他方、電子受容性物質の例には、ノ１０ゲン（例えばフ
ッ素、塩素、臭素及びヨウ素等）、ルイス酸（例えば五
フッ化リン、五フッ化ヒ素、五フフ化アンチモン、三フ
ッ化ホウ素、三塩化ホウ素、三臭化ホウ素、塩化第二鉄
、塩化アルミニウム及び三塩化硫黄等）、及びプロトン
酸（例えばフッ酸、塩酸、臭化水素、過塩素酸、硫酸及
び硝酸等）が挙げられる。以下、これら処理剤をドーパ
ントと総称する。On the other hand, examples of electron-accepting substances include nitrogen (e.g. fluorine, chlorine, bromine and iodine), Lewis acids (e.g. phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride, boron trifluoride, boron trichloride, boron tribromide, ferric chloride, aluminum chloride, sulfur trichloride, etc.), and protonic acids (eg, hydrofluoric acid, hydrochloric acid, hydrogen bromide, perchloric acid, sulfuric acid, nitric acid, etc.). Hereinafter, these processing agents will be collectively referred to as dopants.
ポリアセチレンを電子供与性物質あるいは電子受容性物
質で処理する方法としては、（１）ドーパントが気体の
場合、ポリマーを気体にさらす。The method for treating polyacetylene with an electron-donating substance or an electron-accepting substance is as follows: (1) When the dopant is a gas, the polymer is exposed to the gas.
（２）ドーパントが液体の場合、ポリマーを液体中に浸
漬する。（３）ドーパントが固体の場合、ドーパントを
適切な溶媒に溶かした溶液中にポリマーを浸漬する。（
４）ドーパントがアルカリ金属の場合、アルカリ金属−
ナフタレン錯体のテトラヒドロ７ラン（ＴＨＦ）溶液中
にポリマーを浸漬する等の方法が挙げられる。(2) If the dopant is a liquid, immerse the polymer in the liquid. (3) If the dopant is a solid, the polymer is immersed in a solution of the dopant in a suitable solvent. (
4) When the dopant is an alkali metal, the alkali metal -
Examples of methods include immersing the polymer in a solution of a naphthalene complex in tetrahydro7rane (THF).
高配向ポリアセチレン薄膜を得るＫは、チーグラ・ナツ
メ触媒を液晶物質中に溶解させ、かつこの液晶物質を配
向させ、その自由表面にてアセチレンを重合して製造す
る。液晶物質を配向させる方法としては（１）表面処理
した基板を用いる。（２）外場印加を用いるの２種類に
大別される。（１）の方法には高分子塗付、ラビング、
斜方蒸着、グレーティングの表面処理が含まれる。K for obtaining a highly oriented polyacetylene thin film is produced by dissolving a Ziegler-Natsume catalyst in a liquid crystal material, aligning the liquid crystal material, and polymerizing acetylene on its free surface. As a method for aligning a liquid crystal substance, (1) a surface-treated substrate is used; (2) There are two types: (2) using external field application; Method (1) includes polymer coating, rubbing,
Includes oblique deposition and grating surface treatment.
（２）の方法には電場、磁場、せん断応力等の外場印加
が含まれる。これらの中で、（２）の方法では液晶物質
を２枚のガラス基板で挾む必要があるなめ、アセチレン
の拡散が充分起らない。これに対し、（１）の方法では
一枚のガラス基板で重合が行えるため、最も好しい方法
となる。ただし、（２）の中のせん断心力印加では、一
枚の基板で行うことが可能である。つまり、基板上に重
合触媒を含んだ液晶物質を塗付し、重合直前に斜めに傾
け、液晶物質の流動によるせん断芯力を利用する方法で
ある。液晶物質を配向させる方法としては、上述の組合
せ、例えば高分子塗付膜をラビングした基板等を使うこ
と等が挙げられる。これらの組合せの方法では、液晶物
質の配向がよシ促進される。The method (2) includes applying an external field such as an electric field, a magnetic field, and shear stress. Among these methods, method (2) requires that the liquid crystal material be sandwiched between two glass substrates, so that sufficient diffusion of acetylene does not occur. On the other hand, method (1) is the most preferred method because polymerization can be performed using a single glass substrate. However, the application of shearing force in (2) can be performed using a single substrate. In other words, this is a method in which a liquid crystal material containing a polymerization catalyst is applied onto a substrate, and the substrate is tilted at an angle just before polymerization, thereby utilizing the shear core force caused by the flow of the liquid crystal material. Examples of methods for orienting the liquid crystal material include the use of a combination of the above, for example, a substrate rubbed with a polymer coating. A combination of these methods will enhance the alignment of the liquid crystal material.
液晶物質としては、重合触媒との関係において触媒を溶
解しやすく、かつ触媒と化学反応しないものが望ましい
。すなわち、液晶物質の分子構造について見ると、重合
触媒に対して活性な置換基を有していない方が望ましい
。また、原料であるアセチレンは気体であるため、アセ
チレンガスが拡散しやすい液晶物質であることが望まし
い。＊にネマチック液晶はよシ好ましい。The liquid crystal material is preferably one that easily dissolves the polymerization catalyst and does not chemically react with the catalyst. That is, when looking at the molecular structure of a liquid crystal substance, it is preferable that it does not have a substituent that is active with respect to a polymerization catalyst. Furthermore, since acetylene, which is a raw material, is a gas, it is desirable to use a liquid crystal material in which acetylene gas can easily diffuse. *A nematic liquid crystal is more preferable.
以下、実施例により本発明を更に具体的に説明するが、
本発明はこれら実施例に限定されない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.
実施例１
窒素雰囲気下で１０−のガラス容器に４−（トランス−
４−ｎ−”ｆロピルシクロヘキシル）−二トキシベンゼ
ンと４−（）ランス−４−ｎ−プロピルシクロヘキシル
）−ブトキシベンゼンの等モル混合物を３―加えた。こ
の液晶混合物のネマチック液晶相から等方性液体相への
転移温度は３５℃である。この液晶混合物くテトラ−ｎ
−ブトキシチタニウム５１μｌ及びトリエチルアルミニ
ウム６１μｌを加え、３０分間かくはんすることＫよシ
触媒を熟成した。上記転移温度はチーグラ・ナツタ触媒
の混入にょシ、２７℃まで下った。Example 1 4-(trans-
An equimolar mixture of 4-n-"f-propylcyclohexyl)-nitoxybenzene and 4-()lance-4-n-propylcyclohexyl)-butoxybenzene was added. From the nematic liquid crystal phase of this liquid crystal mixture, The transition temperature to the orthotropic liquid phase is 35°C.
51 .mu.l of -butoxytitanium and 61 .mu.l of triethylaluminum were added and stirred for 30 minutes to age the catalyst. The above transition temperature decreased to 27° C. due to the inclusion of the Ziegler-Natsuta catalyst.
これとは別ｔｔｃｓａａ−のガラス容器にガラス基板（
３０■Ｘ６Ｑ■）を入れ、窒素雰囲気下でこの基板上に
上記の触媒を含んだ液晶物質を滴下した。この容器を重
合装置に取付け、真空ポンプで窒素を排気した。重合直
前に容器を傾け、ガラス基板上の液晶物質に流動を与え
、瞬時にアセチレンガスを吹込むと直ちにポリアセチレ
ンが形成された。５分後に未反応のアセチレンガスを除
去し、ガラス容器を重合装置からはずし窒素を導入した
。生成したポリアセチレン膜ヲトルエン→塩酸メタノー
ル溶液→トルエンの順で洗浄をし、液晶物質と触媒を取
除く。In addition to this, a glass substrate (
30 x 6 Q)), and the liquid crystal material containing the above catalyst was dropped onto this substrate under a nitrogen atmosphere. This container was attached to a polymerization apparatus, and nitrogen was evacuated using a vacuum pump. Immediately before polymerization, the container was tilted to give fluidity to the liquid crystal material on the glass substrate, and acetylene gas was instantly blown into the container, resulting in the immediate formation of polyacetylene. After 5 minutes, unreacted acetylene gas was removed, the glass container was removed from the polymerization apparatus, and nitrogen was introduced. The generated polyacetylene film is washed in the order of toluene → hydrochloric acid methanol solution → toluene to remove the liquid crystal substance and catalyst.
最後に真空乾燥して、ガラス基板と同面積の高配向ポリ
アセテレ／薄膜を得た。Finally, it was vacuum dried to obtain a highly oriented polyacetate/thin film with the same area as the glass substrate.
この−軸配向ポリアセチレンを空気のもれのない真空容
器に入れ、ヨウ素蒸気に５分間さらした。この試料の電
気伝導度（直流四端子法）はフィブリルの配向軸に平行
方向で４８９ ！−’、垂直方向で２１Ｅｌα−！であ
った。This -axially oriented polyacetylene was placed in an airtight vacuum container and exposed to iodine vapor for 5 minutes. The electrical conductivity of this sample (DC four-probe method) is 489 in the direction parallel to the fibril orientation axis! -', in the vertical direction 21Elα-! Met.
実施例２
実施例１で得られた高配向ポリアセチレンを三塩化鉄の
ニトロメタン溶液（１５モル／／）Ｋ３Ｇ秒間浸漬した
後、トルエンで洗浄し真空乾燥した。この試料の電気伝
導度はフィブリルの配向軸に平行方向で１２６８ （Ｆ
ｌｌ−”、垂直方向で７０８ｃＷ１−墓であった。Example 2 The highly oriented polyacetylene obtained in Example 1 was immersed in a nitromethane solution of iron trichloride (15 mol//) K3G for seconds, then washed with toluene and vacuum dried. The electrical conductivity of this sample is 1268 (F
ll-'', vertically 708 cW1-grave.
実施例３
実施例１で得られ九−軸配向ポリアセチレンをナトリウ
ム・す７タレン錯体のテトラヒトミフラン溶液（１１モ
ル／／）［１０分間浸漬した後、トルエンで洗浄し真空
乾−した。この試料の電気伝導度はフィブリルの配向軸
に平行方向で４−２ Ｂ ６１１−’１垂直方向で１．
７ ｅ ｃｍ−テｈ ツタ。Example 3 The nine-axis oriented polyacetylene obtained in Example 1 was immersed in a solution of sodium/s7talene complex in tetrahtomifuran (11 mol//) for 10 minutes, then washed with toluene and dried in vacuum. The electrical conductivity of this sample is 4-2 in the direction parallel to the fibril orientation axis and 1 in the perpendicular direction.
7 e cm-teh ivy.
実施例４
実施例１で示したと同様の方法で、触媒を含んだ液晶を
調製した。Example 4 A liquid crystal containing a catalyst was prepared in the same manner as shown in Example 1.
３００−のガラス容器にラビング処理したポリエチレン
基板（３ｏｗｘ６ｏｍ）を入れ、窒素雰囲気下で基板上
に触媒を含む液晶物質を注射器で数滴加える。その後、
ガラス容器を若干傾け、液晶を基板上に一様に広げる。A rubbed polyethylene substrate (3ow x 6om) is placed in a 300mm glass container, and a few drops of a liquid crystal material containing a catalyst is added onto the substrate with a syringe under a nitrogen atmosphere. after that,
Tilt the glass container slightly and spread the liquid crystal evenly over the substrate.
この容器を゛真空ライン〈取付け、反応容器内の窒素を
真空ポンプで排気した。この容器にアセチレンを吹込む
と、ポリエチレン基板上にポリアセチレン膜が生成した
。５分後未反応のアセチレンガスを除去し、ガラス容器
を重合装置からはずし窒素を導入した。トルエン→塩酸
メタノール溶液→トルエンの順で洗浄し、液晶物質と触
媒を取除き、最後に真空乾燥して、高配向ポリアセチレ
ン膜を得た。A ``vacuum line'' was attached to this container, and nitrogen in the reaction container was evacuated using a vacuum pump. When acetylene was blown into this container, a polyacetylene film was formed on the polyethylene substrate. After 5 minutes, unreacted acetylene gas was removed, the glass container was removed from the polymerization apparatus, and nitrogen was introduced. Washing was carried out in the order of toluene → methanol solution of hydrochloric acid → toluene to remove the liquid crystal substance and catalyst, and finally vacuum drying to obtain a highly oriented polyacetylene film.
この−軸配向試料をガラス容器に入れ、空気を除去した
後、ヨウ素蒸気を導入し、５分間処理した。この試料の
電気伝導度は、フィブリルの配向軸に平行方向で９７８
５１− ％垂直方向で５５８ＣＩＩＩ−” であった。This -axis oriented sample was placed in a glass container, and after removing air, iodine vapor was introduced and treated for 5 minutes. The electrical conductivity of this sample is 978 in the direction parallel to the fibril orientation axis.
It was 558 CIII-'' in the 51-% vertical direction.
（発明の効果〕
以上説明した様に、本発明によれば、液晶媒体中で合成
した高配向ポリアセチレンを電子供与性物質あるいは電
子受容性物質で処理することにより、高い電導度を持つ
だけでなく、その異方性を有する材料を提供することが
できる。(Effects of the Invention) As explained above, according to the present invention, by treating highly oriented polyacetylene synthesized in a liquid crystal medium with an electron donating substance or an electron accepting substance, it not only has high conductivity but also , it is possible to provide a material having that anisotropy.
この様に異方性のある材料は、電気・電子素子として有
用な導電性高分子材料として使用できるばかりでなく、
ｐ／ｎ接合素子を作ることもできることから、光センサ
、太陽電池としても有用である。Materials with such anisotropy can not only be used as conductive polymer materials useful in electrical and electronic devices, but also
Since a p/n junction element can also be made, it is also useful as an optical sensor and a solar cell.
Claims (1)
することを特徴とする電気的異方性を有する導電性高分
子材料。 ２、液晶物質を重合媒体として用いアセチレンを重合さ
せることにより得た高配向ポリアセチレンを、電子受容
性物質又は電子供与性物質で処理することを特徴とする
電気的異方性を有する導電性高分子材料の製造方法。[Scope of Claims] 1. A conductive polymer material having electrical anisotropy, characterized by including highly oriented polyacetylene containing a dopant. 2. A conductive polymer having electrical anisotropy, characterized in that highly oriented polyacetylene obtained by polymerizing acetylene using a liquid crystal substance as a polymerization medium is treated with an electron-accepting substance or an electron-donating substance. Method of manufacturing the material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23955884A JPS61118454A (en) | 1984-11-15 | 1984-11-15 | Electrically conductive polymer material having electrical anisotropy, and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23955884A JPS61118454A (en) | 1984-11-15 | 1984-11-15 | Electrically conductive polymer material having electrical anisotropy, and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61118454A true JPS61118454A (en) | 1986-06-05 |
Family
ID=17046584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23955884A Pending JPS61118454A (en) | 1984-11-15 | 1984-11-15 | Electrically conductive polymer material having electrical anisotropy, and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61118454A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1354610A1 (en) * | 2002-04-16 | 2003-10-22 | BIOTRONIK Mess- und Therapiegeräte GmbH & Co Ingenieurbüro Berlin | Electrode lead made of an intrinsically conductive polymer |
-
1984
- 1984-11-15 JP JP23955884A patent/JPS61118454A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1354610A1 (en) * | 2002-04-16 | 2003-10-22 | BIOTRONIK Mess- und Therapiegeräte GmbH & Co Ingenieurbüro Berlin | Electrode lead made of an intrinsically conductive polymer |
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