JPS58187432A - Preparation of electrically conductive or electrically semiconductive polymeric composition - Google Patents
Preparation of electrically conductive or electrically semiconductive polymeric compositionInfo
- Publication number
- JPS58187432A JPS58187432A JP7005482A JP7005482A JPS58187432A JP S58187432 A JPS58187432 A JP S58187432A JP 7005482 A JP7005482 A JP 7005482A JP 7005482 A JP7005482 A JP 7005482A JP S58187432 A JPS58187432 A JP S58187432A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytically
- benzene
- dopant
- heterocyclic
- electrically
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、導電性ないし半導性重合体組成物の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a conductive or semiconductive polymer composition.
従来、たとえば Ｋ 、 Ｋｅ ｉ ｊ ｉ Ｋａｎａ
ｚａｗａ ｅｊ。Conventionally, for example, K, Ke ij i Kana
zawa ej.
ａｌ、 、 Ｊ、Ｃｈｅｍ、Ｓｏｃ 、Ｃｈｅｍ、Ｃｏ
ｍ、、 ８５４（１９７９） などにたとえば、ホウ弗
化テトラエチルアンモニウムなどの支持電解質の存在下
でピロールを電解酸化して重合体組成物を製造する方法
が挙げられている。これらの組成物は大きな導電率をも
ち、たとえば、導電体な゛どとして有用である。しかし
、こうして得た組成物は、一般に多孔質でもチ＜、実際
的な使用には難点をもっている。al, , J, Chem, Soc, Chem, Co
For example, a method for producing a polymer composition by electrolytically oxidizing pyrrole in the presence of a supporting electrolyte such as tetraethylammonium fluoride borofluoride is mentioned in J. M., 854 (1979). These compositions have high electrical conductivity and are useful, for example, as electrical conductors. However, the compositions obtained in this manner are generally porous and have difficulties in practical use.
また、電解酸化の手法を用いて種々の化合物から導電性
または半導電性重合体組成物が得られることも知られて
いなかった。Furthermore, it was not known that conductive or semiconductive polymer compositions could be obtained from various compounds using electrolytic oxidation techniques.
これらの事情を考慮して、本発明は、後述の化合物を電
解酸化して、導電性または半導電性重合体組成物を製造
する簡便で効率のよい方法を提供するものである。In consideration of these circumstances, the present invention provides a simple and efficient method for producing a conductive or semiconductive polymer composition by electrolytically oxidizing the compound described below.
本発明の方法は、電解酸化物質（本発明による組成物を
得るために電解酸化される物質をこう呼ぶ）をドーパン
トとの共存下で電解酸化することを特徴とする。電解酸
化物質とドーパントが共に固体の場合は、これらを適当
な溶媒に溶解させて電解酸化する。共に液体かどちらか
一方が液体の場合は、両者の混合または分散によって電
解酸化し得る。The method of the present invention is characterized in that an electrolytically oxidized substance (the substance to be electrolytically oxidized to obtain the composition according to the invention is called this) is electrolytically oxidized in the presence of a dopant. When the electrolytically oxidized substance and the dopant are both solid, they are dissolved in a suitable solvent and electrolytically oxidized. When both or one of them is liquid, electrolytic oxidation can be performed by mixing or dispersing the two.
本発明で用いる電解酸化物質は、次のような化合物であ
る。The electrolytically oxidized substance used in the present invention is the following compound.
−ａ）ベンゼンまたはその誘導体、ｂ）酸素族元素を１
つ含む複素五員環化合物、Ｃ）ベンゼン環と、酸素族元
素もしくは窒素族元素を１つ含む複素五員環とよりなる
群から選んだ複数の環が直接またはエーテル、スルフィ
ド、セレニド、テルリド結合のうちどれかの結合を介し
て直鎖状に結合した化合物
具体例としてはたとえば、次のような化合物が挙げられ
る：
フェノール、チオフェノール、フラン、チオフェン、セ
レノフェン、テルロフェン （１ｇ）、ビフェニル、Ｐ
−ターフェニル、Ｏ−ターフェニル、ｐ−クォータフェ
ニル、２−ヒドロキシビフェニル、ジフェニルエーテル
、ジフェニルスルフィド、ジフェニルセレニド、ジフェ
ニルテルリド、２−（α−チェニル）チオフェン、２−
（α−チェニル）フラン、２−（２−ピロリル）ピロー
ル、２−（２〜ピロリル）チオフェン、２−フェニルチ
オフェン、α−チェニルーフェニルニエーテル、β−フ
リル−α−チェニルーセレニ）”、２−（２−ピロリル
）セレノフェン、２−（２−セレニエニル）テルロフェ
ン。-a) benzene or its derivative, b) oxygen group element 1
C) a benzene ring and a hetero five-membered ring containing one oxygen group element or one nitrogen group element; Specific examples of compounds linked in a linear chain through any one of these bonds include the following compounds: phenol, thiophenol, furan, thiophene, selenophene, tellurophene (1g), biphenyl, P
-terphenyl, O-terphenyl, p-quarterphenyl, 2-hydroxybiphenyl, diphenyl ether, diphenyl sulfide, diphenyl selenide, diphenyl telluride, 2-(α-chenyl)thiophene, 2-
2- (2-pyrrolyl)selenophene, 2-(2-selenienyl)tellophene.
ドーパントには、有機四級アンモニウム塩、無機塩、プ
ロトン酸、エステルなどの種々の化合物があり、例えば
ホウ弗化テトラエチルアンモニウム、過塩素酸テトラ−
ｎ−ブチルアンモニウム、良化テトラメチルアンモニウ
ム、過塩素酸リチウム、硝酸バリウム、硫酸アンモニウ
ム、硫酸などが慣げられる。Dopants include various compounds such as organic quaternary ammonium salts, inorganic salts, protic acids, and esters, such as tetraethylammonium borofluoride, tetraethylammonium perchlorate, etc.
Useful examples include n-butylammonium, improved tetramethylammonium, lithium perchlorate, barium nitrate, ammonium sulfate, and sulfuric acid.
本発明は一見して、前述のＫａｎａｚａｗａらの方法と
類似しているようにみえるが、とくに緻密で・ト滑な重
合体組成物を与える点で従来の方法とは全くちがった効
果をもっている。これは用いた電解酸化物質がピロール
に比べて電解酸化されやすいために脱水素による重合反
応が起こりやすく、重合度が高まることによると解釈し
うる。なかでも、電解酸化物質が環上にイオウ、セレン
、テルルのうちどれかをもつ複素五員環を含むときは、
本発明の方法できわめて緻密で強じんなフィルム状の重
合体組成物を得ることも容易である。これは、イオウ、
セレン、テルルの電気陰性度が低く、とくに電解酸化さ
４やすいためと解される。さらに、ドーパントがたとえ
ば、テトラフルオロボレートイオウなどのホウノ・ロゲ
ン化イオン、バークロレートイオンなどのパーツ・ロゲ
ネートイオンや硫酸イオンなどを含む化合物から選ばれ
たときも同様の効果を生む。At first glance, the present invention appears to be similar to the aforementioned method of Kanazawa et al., but it has an effect completely different from conventional methods in that it provides a particularly dense and smooth polymer composition. This can be interpreted to be because the electrolytically oxidized substance used is more easily electrolytically oxidized than pyrrole, so that a polymerization reaction due to dehydrogenation occurs more easily, increasing the degree of polymerization. In particular, when the electrolytically oxidized substance contains a five-membered hetero ring having one of sulfur, selenium, and tellurium on the ring,
It is also easy to obtain extremely dense and strong film-like polymer compositions using the method of the present invention. This is sulfur,
This is thought to be because selenium and tellurium have low electronegativity and are particularly susceptible to electrolytic oxidation. Furthermore, a similar effect can be produced when the dopant is selected from compounds containing, for example, borogenate ions such as sulfur tetrafluoroborate, partrogenate ions such as barchlorate ions, and sulfate ions.
次に実施例を挙げて本発明をさらに詳しく説明する。Next, the present invention will be explained in more detail with reference to Examples.
種々の電解酸化物質をドーパントとともに各種の溶媒に
溶解または分散させ、さまざまな条件で電解酸化物質を
酸化し、白金陽極上に導電性または半導電性重合体組成
物を得た。これをメタノールで洗浄した後に一昼夜真空
乾燥して試料とした。Various electrolytically oxidized substances were dissolved or dispersed together with dopants in various solvents, and the electrolytically oxidized substances were oxidized under various conditions to obtain conductive or semiconductive polymer compositions on a platinum anode. This was washed with methanol and then dried under vacuum for a day and night to be used as a sample.
塊状試料の場合は、さらに粉末状に粉砕した後、１閣厚
のディスク状に加圧成形し、両面に銀塗料を塗布して導
電率測定用試料とした。フィルム状の試料の場合は、幅
１５咽、長さ１１ｏＩＩＩＩ＋１の試料を４枚つくり、
２枚は銀塗料を塗布して四端子法による導電率測定用試
料とし、他の２枚はＪＩＳＰ８１１５−１９６０の耐折
強さ試験用試料とした。In the case of a lump sample, it was further ground into a powder, then pressure-molded into a disk shape of one thickness, and both sides were coated with silver paint to prepare a sample for conductivity measurement. For film-like samples, make four samples with a width of 15mm and a length of 11oIII+1.
Two sheets were coated with silver paint and used as samples for measuring electrical conductivity using the four-probe method, and the other two sheets were used as samples for bending strength testing according to JISP8115-1960.
次表に、電解酸化物質、ドーパントの種類と計、溶媒の
種類、電解酸化の条件および導電率の値とを示す。なお
、電解酸化物質の初期の仕込み量は１、／、溶媒量は１
００ｍ／！に統一し、ドーパントのけはカッコ内に初期
の仕込量をβ単位で表す。また、表の導電率の値は２試
料の平均値である。The following table shows the types and amounts of electrolytic oxidizing substances, dopants, types of solvents, electrolytic oxidation conditions, and conductivity values. In addition, the initial charge amount of electrolytic oxidation substance is 1, the amount of solvent is 1
00m/! The initial amount of dopant is expressed in β units in parentheses. Furthermore, the conductivity values in the table are the average values of two samples.
以）゛余白
また、耐折強さ試験でどのフィルムも５０回以上の折り
曲げ回数を記録した。従来例として、ピロール１ｇとホ
ウ弗化テトラ−ｎ−ブチルアンモニウム０．１．９とを
アセトニトリル１００ｍ／に溶解し、２０Ｖ、５ｍＡ／
ｃｉ で１０分間通電して得た重合体組成物の折り曲
げ回数は１０以下であった。゛Margin In addition, in the folding strength test, each film was folded 50 times or more. As a conventional example, 1 g of pyrrole and 0.1.9 g of tetra-n-butylammonium borofluoride were dissolved in 100 m/a of acetonitrile, and the mixture was heated at 20 V and 5 mA/a.
The number of bends of the polymer composition obtained by applying current for 10 minutes at ci was 10 or less.
上記実施例以外の電解酸化物質を用い、本発明の方法で
得た重合体組成物は、いずれも１Ｏ−１２（Ω・ｃｍ）
以上の導電率の値を示した。また、ドーパントの
種類や量、溶媒の種類や電解酸化の条件を適当に選んで
緻密なフィルム状の重合体組成物を得ることができた。All of the polymer compositions obtained by the method of the present invention using electrolytic oxidation substances other than those in the above examples had a resistance of 1O-12 (Ω・cm).
The above conductivity values were shown. Furthermore, by appropriately selecting the type and amount of dopant, type of solvent, and electrolytic oxidation conditions, it was possible to obtain a dense film-like polymer composition.
このようにして得られたもののうち、とくにフィルム状
の重合体組成物はたとえば電子材料などの素材として有
用である。Among those obtained in this way, film-like polymer compositions are particularly useful as raw materials for electronic materials and the like.
Claims (3)
だ物質をドーパントの共存下で電解酸化することａ）ベ
ンゼンもしくはその誘導体 ｂ）酸素族元素を１つ含む複素６員環化合物Ｃ）ベンゼ
ン環と、酸素族元素もしくは窒素族元素の少なくとも一
方を含む複素６員環とちｂずれかの結合を介して直鎖状
に結合した化合物(1) Electrolytically oxidizing a substance selected from the compound group consisting of a, b, and C in the presence of a dopant a) Benzene or its derivative b) a six-membered heterocyclic compound containing one oxygen group element C) benzene A compound in which a ring and a six-membered hetero ring containing at least one of an oxygen group element or a nitrogen group element are bonded in a straight chain via a bond.
りなる群から選んだものである特許請求の範囲第盟９貢
伝０(2) The oxygen group element is selected from the group consisting of sulfur, selenium, and tellurium.
ー・・ロゲネートイオンまたは硫酸イオンを含む化合物
から選ばれた特許請求の範囲第１項または第２項記載の
導電性ないし半導電性重合体組成物の製） 造法。 ハ(3) The conductive or semiconductive polymer composition according to claim 1 or 2, wherein the dopant is selected from compounds containing borogenate ion, barrogenate ion, or sulfate ion. manufacturing method). Ha
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7005482A JPS58187432A (en) | 1982-04-26 | 1982-04-26 | Preparation of electrically conductive or electrically semiconductive polymeric composition |
| US06/488,598 US4501686A (en) | 1982-04-26 | 1983-04-25 | Anion-doped polymers of five-membered oxygen family heterocyclic compounds and method for producing same |
| US06/675,644 US4582587A (en) | 1982-04-26 | 1984-11-28 | Anion-doped polymers of five-membered oxygen family heterocyclic compounds and method for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7005482A JPS58187432A (en) | 1982-04-26 | 1982-04-26 | Preparation of electrically conductive or electrically semiconductive polymeric composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58187432A true JPS58187432A (en) | 1983-11-01 |
| JPH0520449B2 JPH0520449B2 (en) | 1993-03-19 |
Family
ID=13420453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7005482A Granted JPS58187432A (en) | 1982-04-26 | 1982-04-26 | Preparation of electrically conductive or electrically semiconductive polymeric composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58187432A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6162520A (en) * | 1984-09-03 | 1986-03-31 | Res Dev Corp Of Japan | Production of electrically conductive polymer |
| JPS6162521A (en) * | 1984-09-03 | 1986-03-31 | Res Dev Corp Of Japan | Production of electrically conductive polymer |
| JPS62169820A (en) * | 1986-01-22 | 1987-07-27 | Res Dev Corp Of Japan | Polymer of five-membered heterocyclic compound |
| JPH0515415A (en) * | 1991-11-05 | 1993-01-26 | Sanyo Electric Co Ltd | Leg device of frame body |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0035713A2 (en) * | 1980-03-12 | 1981-09-16 | BASF Aktiengesellschaft | Process for preparing electrically conductive heteropolyphenylenes and their use in electrotechnics and in the antistatic equipment of synthetics |
-
1982
- 1982-04-26 JP JP7005482A patent/JPS58187432A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0035713A2 (en) * | 1980-03-12 | 1981-09-16 | BASF Aktiengesellschaft | Process for preparing electrically conductive heteropolyphenylenes and their use in electrotechnics and in the antistatic equipment of synthetics |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6162520A (en) * | 1984-09-03 | 1986-03-31 | Res Dev Corp Of Japan | Production of electrically conductive polymer |
| JPS6162521A (en) * | 1984-09-03 | 1986-03-31 | Res Dev Corp Of Japan | Production of electrically conductive polymer |
| JPH029621B2 (en) * | 1984-09-03 | 1990-03-02 | Shingijutsu Kaihatsu Jigyodan | |
| JPH029620B2 (en) * | 1984-09-03 | 1990-03-02 | Shingijutsu Kaihatsu Jigyodan | |
| JPS62169820A (en) * | 1986-01-22 | 1987-07-27 | Res Dev Corp Of Japan | Polymer of five-membered heterocyclic compound |
| JPH0515415A (en) * | 1991-11-05 | 1993-01-26 | Sanyo Electric Co Ltd | Leg device of frame body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0520449B2 (en) | 1993-03-19 |
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