JPS63243136A - Production of polythionaphthene - Google Patents
Production of polythionaphtheneInfo
- Publication number
- JPS63243136A JPS63243136A JP62074271A JP7427187A JPS63243136A JP S63243136 A JPS63243136 A JP S63243136A JP 62074271 A JP62074271 A JP 62074271A JP 7427187 A JP7427187 A JP 7427187A JP S63243136 A JPS63243136 A JP S63243136A
- Authority
- JP
- Japan
- Prior art keywords
- polythionaphthene
- thionaphthene
- supporting electrolyte
- electrolytic polymerization
- electrolytic solution
- 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
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はポリチオナフテンの製造方法に関し、さらに詳
しくは、優れた導電性及び透明性を有するポリチオナフ
テンの製造方法に閃する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polythionaphthene, and more particularly, to a method for producing polythionaphthene having excellent conductivity and transparency.
従来、導電性高分子物質としては種々のものが知られて
いる１例えば、ポリアセチレン、ポリパラフェニレン、
ポリピロール、ポリチオフェン等があるが、このうちポ
リピロール、ポリチオフェン等の複索５貝環系ポリマー
は電解重合によって製造され、空気中での安定性も良好
であることが知られている。しかし、従来提案されでい
る導電性ポリマーからつくられたフィルムは多くのもの
が不透明であり、その利用分野に制限がある。Conventionally, various conductive polymer substances have been known. For example, polyacetylene, polyparaphenylene,
Polypyrrole, polythiophene, etc. are available, and among these, polypyrrole, polythiophene, and other polyphonic pentacyclic polymers are produced by electrolytic polymerization, and are known to have good stability in air. However, many of the films made from conductive polymers that have been proposed so far are opaque, which limits their field of use.
また、チオナフテンについても、Ｂｕ、ＮＣｌ０１を支
持電解質としアセトニトリル中に溶解した電解液中で電
解重合することによりポリマー化することは既に報告さ
れている［ Ｊ 、Ｐ ｈｙｓ、 Ｃｈｅｍ、、１９８
４．８８，４３４４参照］が、生成するポリマーは脆い
沈澱吻状のものであり、実用的価値に乏しいものである
。Furthermore, it has already been reported that thionaphthene can be polymerized by electrolytic polymerization in an electrolytic solution dissolved in acetonitrile using Bu and NClO1 as supporting electrolytes [J, Phys, Chem, 198
4.88, 4344], but the resulting polymer is a brittle precipitate-like substance and has little practical value.
そこで、本発明者らは、導電性及び透明性に優れ且つフ
ィルム状となしうるポリチオナフテンを得るべく、支持
電解質等の電解重合条件を種々検討した結果、支持電解
質としてホウフッ化リチウムを用いると導電性及び透明
性に優れたポリチオナフテンフィルムが得られることを
見い出し本発明を完成するに至った。Therefore, in order to obtain polythionaphthene that has excellent conductivity and transparency and can be made into a film, the present inventors investigated various electrolytic polymerization conditions such as supporting electrolyte, and found that using lithium borofluoride as the supporting electrolyte. The present inventors have discovered that a polythionaphthene film with excellent conductivity and transparency can be obtained, and have completed the present invention.
しかして、本発明によれば、ホウ７ツ化リチウムを支持
電解質として含有する電解液中でチオナフテンを電解重
合することを特徴とするポリチオナフテンの製造方法が
提供される。According to the present invention, there is provided a method for producing polythionaphthene, which comprises electrolytically polymerizing thionaphthene in an electrolytic solution containing lithium borosulfide as a supporting electrolyte.
本発明に従うチオナフテンの電解、重合は、ホウ７ツ化
リチウムを支持電解質として含有する電解液中で行なわ
れる。該電解液はホウ７ツ化リチウム（ＬｉＢＦ＝）を
適当な溶媒中に溶解することにより！ｉｌ！！！される
。使用しうる溶媒としてはアセトニトリル及びベンゾニ
トリルのようなニトリル系溶媒が挙げられ、特にベンゾ
ニトリルが好適である。The electrolysis and polymerization of thionaphthene according to the present invention is carried out in an electrolytic solution containing lithium boro7tride as a supporting electrolyte. The electrolyte is prepared by dissolving lithium borosulfide (LiBF=) in a suitable solvent! Il! ! ! be done. Examples of solvents that can be used include nitrile solvents such as acetonitrile and benzonitrile, with benzonitrile being particularly preferred.
ベンゾニトリルを溶媒として用いる場合には、アセトン
との混合溶媒の形で使用するのが望ましく、その場合の
ベンゾニトリル／アセトンの混合割合は一般に重量化で
１００／１〜１０／１の範囲内とするのが有利である。When benzonitrile is used as a solvent, it is preferable to use it in the form of a mixed solvent with acetone, and in this case, the mixing ratio of benzonitrile/acetone is generally within the range of 100/1 to 10/1 by weight. It is advantageous to do so.
支持電解質としてのホウ７ツ化リチウムはかかる溶媒中
に通常０．０１〜１モル／ｌ、特に０．０５〜０．５モ
ル／ｌの濃度で溶解するのが好都合である。Lithium boro7tride as supporting electrolyte is conveniently dissolved in such a solvent in a concentration of usually 0.01 to 1 mol/l, in particular 0.05 to 0.5 mol/l.
本発明に従うチオナフテンの電解重合は、以上に述べた
如きホウ７ツ化リチウムを含有する電解液を用いる以外
、それ自体既知の電解重合法に準じで行なうことができ
る。例えば、電極として、陽極には、ネサガラス、白金
、金、ニッケル板等を用いることができ、陰極には白金
、金、ニッケル板等を使用することができる。また、電
解重合は電解装置をドライボックス中に設＋＋’７ Ｌ
、例えばド記の条件ド：
印加電圧 ３〜７■
電流密度 ０．１−１０＋＋Ａ／ｃｍ時 間
１０分〜１０時間
で操作ｒることにより実施でき、その結果、陽極側にポ
リチオナフテンのフィルムが形成される。The electrolytic polymerization of thionaphthene according to the present invention can be carried out according to known electrolytic polymerization methods, except for using the electrolytic solution containing lithium boro7tride as described above. For example, as the electrodes, Nesa glass, platinum, gold, nickel plate, etc. can be used for the anode, and platinum, gold, nickel plate, etc. can be used for the cathode. In addition, for electrolytic polymerization, the electrolytic device is installed in a dry box.
For example, the following conditions: Applied voltage 3-7 ■ Current density 0.1-10++ A/cm Time
This can be carried out by operating for 10 minutes to 10 hours, and as a result, a polythionaphthene film is formed on the anode side.
生成するポリチオナフテンの電解重合時間に対する表面
抵抗値及び透過率の測定結果は添付の第１図及びＰＪｓ
２図に示すとおりであり、これらの図から、電解重合時
間の進行にイ゛ｒなって、生成するポリチオナフテンフ
ィルムは安定した表面抵抗値をとり、透明性も良好であ
ることがわかる。なお、フィルムの表面抵抗値は四端子
法により求めた（四端子・はアルミニウムを真空蒸着し
た）。また、透過率は手間理化研究所に−Ｋ ＭＯＤＥ
Ｌ６Ｂを用いて測定した。The measurement results of the surface resistance value and transmittance of the polythionaphthene produced with respect to the electrolytic polymerization time are shown in the attached Figure 1 and PJs.
As shown in Figure 2, it can be seen from these figures that as the electrolytic polymerization time progresses, the polythionaphthene film produced has a stable surface resistance value and good transparency. The surface resistance value of the film was determined by the four-terminal method (aluminum was vacuum-deposited for the four-terminal method). In addition, the transmittance is determined by the labor research institute -K MODE
Measured using L6B.
また、支持電解質の濃度に対する生成ポリチオナフテン
の表面抵抗値及び透過率の関係を添付のｔｔｒＪ３図及
び第４図に示す、これらの図から、支持電解質の濃度に
対して、ポリチオナフテンの表面抵抗値の変化は少なく
安定しており、透過率は濃度の増加と共に低下するが５
０％程度で安定することがわかる。In addition, the relationship between the surface resistance value and transmittance of the produced polythionaphthene with respect to the concentration of the supporting electrolyte is shown in the attached ttrJ3 and Figure 4. From these figures, it can be seen that the surface resistance value and transmittance of the polythionaphthene are The change in resistance value is small and stable, and the transmittance decreases with increasing concentration, but 5
It can be seen that it is stable at about 0%.
以上述べたとおり、本発明によれば、電解重合により容
易に安定して、導電性及び透明性に優れたポリチオナフ
テンのフィルムを＊ａすることができる。しかして、得
られるポリチオナフテンは例えば帝電防１ヒ材、電磁波
シール材、ポリマー二次電池、光スイツチング素子、半
導体、センサー等において広範に利用することができる
。As described above, according to the present invention, a polythionaphthene film *a which is easily stabilized by electrolytic polymerization and has excellent conductivity and transparency can be produced. Therefore, the obtained polythionaphthene can be widely used in, for example, Teidenbo 1H materials, electromagnetic wave sealing materials, polymer secondary batteries, optical switching devices, semiconductors, sensors, etc.
次に実施例により本発明を更に具体的に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
ベンゾニトリル７０１．１と７七トン５１１１の混合溶
媒に支持電解質としてＬ ＋ Ｂ Ｆ ４０．８ ｇを
溶解した電解液にチオナフテンを０．５ｇ加えた後、ド
ライエアー中で、陽極にネサガラス板及び陰極に白金板
を使用して印加電圧５Ｖ、電流密度０．５ｍＡ／ｅ１１
で２時間、電解重合を行った。これにより得られたポリ
マーの導電率は１５０Ｓ／ｃ＋ｏｒあり、透過率は７０
％であった。Example 1 After adding 0.5 g of thionaphthene to an electrolytic solution in which 40.8 g of L + B F as a supporting electrolyte was dissolved in a mixed solvent of benzonitrile 701.1 and 77 tons 5111, the anode was heated in dry air. Using Nesa glass plate and platinum plate as cathode, applied voltage 5V, current density 0.5mA/e11
Electrolytic polymerization was carried out for 2 hours. The conductivity of the polymer thus obtained was 150 S/c+or, and the transmittance was 70
%Met.
実施例２
アセトニトリル７５１１１に支持′電解質とし−ＣＬ
ｉＢ Ｆ ４０ 、８ ｇを溶解した電解液にチオナフ
テンを０．５ｇ加えた後、ドライエアー中で、陽極にネ
サガラス及び陰極に白金板を使用して印加電圧５■、電
流密度０．５ｍＡ／ｅｓ＋で３０分、電解重合を行った
。これにより得られたポリマーの導電率は３０Ｓ／ａｍ
であり、透過率は５０％であった。得られたフィルムは
均一であった。Example 2 Acetonitrile 75111 as a supporting electrolyte -CL
After adding 0.5 g of thionaphthene to an electrolytic solution in which 8 g of iB F 40 was dissolved, in dry air, using Nesa glass as an anode and a platinum plate as a cathode, an applied voltage of 5 ■ and a current density of 0.5 mA/es+ were applied. Electrolytic polymerization was carried out for 30 minutes. The conductivity of the polymer thus obtained was 30 S/am.
The transmittance was 50%. The resulting film was uniform.
比較例１
ベンゾニトリル７５ｉｊ！に支持電解質としてＡｇＣｌ
Ｏ４１，Ｏｇを溶解した電解液にチオナフテンを０．５
ｇ加えた後、ドライエアー中で、陽極にネサガラス及び
陰極に白金板を使用して印加電圧５■、電流密度３．０
ｍＡ／ｃ−で２時間、電解重合を行った。これにより得
られたポリマーの導電率は３０Ｓ／ｃ■であったが、透
明率は２０〜３０％であり、フィルムは不均一で脆かっ
た。Comparative Example 1 Benzonitrile 75ij! with AgCl as supporting electrolyte
Add 0.5 thionaphthene to the electrolytic solution in which O41, Og is dissolved.
After adding g, in dry air, using Nesa glass as the anode and platinum plate as the cathode, apply voltage 5■ and current density 3.0.
Electrolytic polymerization was carried out at mA/c- for 2 hours. The electrical conductivity of the resulting polymer was 30 S/c, but the transparency was 20-30%, and the film was non-uniform and brittle.
比較例２
比較例１と同一条件下で、支持電解質としてＫＣｌＯ４
を使用して電解重合を行ったが、ポリマーの成長は極め
て微量で、フィルムは得られなかった。Comparative Example 2 Under the same conditions as Comparative Example 1, KClO4 was used as the supporting electrolyte.
Electrolytic polymerization was carried out using the following methods, but the growth of the polymer was extremely small and no film was obtained.
第１図はポリチオナフテンの電解重合時間と表面抵抗値
の関係を示すグラフであり、
第２図はポリチオナフテンの電解重合時間と透過率の関
係を示すグラフであり、
ｆｉ３図は電解重合の支持電解質濃度とポリチオナフテ
ンの表面抵抗値の関係を示すグラフであり、第４図は電
解重合の支持電解質濃度とポリチオナフテンの透過率の
関係を示すグラフである。Figure 1 is a graph showing the relationship between electrolytic polymerization time and surface resistance of polythionaphthene, Figure 2 is a graph showing the relationship between electrolytic polymerization time and transmittance of polythionaphthene, and fi3 is a graph showing the relationship between electrolytic polymerization time and surface resistance of polythionaphthene. FIG. 4 is a graph showing the relationship between the supporting electrolyte concentration in electrolytic polymerization and the surface resistance value of polythionaphthene, and FIG. 4 is a graph showing the relationship between the supporting electrolyte concentration in electrolytic polymerization and the transmittance of polythionaphthene.
Claims (1)
中でチオナフテンを電解重合することを特徴とするポリ
チオナフテンの製造方法。A method for producing polythionaphthene, which comprises electrolytically polymerizing thionaphthene in an electrolytic solution containing lithium borofluoride as a supporting electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62074271A JPH07103227B2 (en) | 1987-03-30 | 1987-03-30 | Method for producing polythionaphthene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62074271A JPH07103227B2 (en) | 1987-03-30 | 1987-03-30 | Method for producing polythionaphthene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63243136A true JPS63243136A (en) | 1988-10-11 |
| JPH07103227B2 JPH07103227B2 (en) | 1995-11-08 |
Family
ID=13542288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62074271A Expired - Lifetime JPH07103227B2 (en) | 1987-03-30 | 1987-03-30 | Method for producing polythionaphthene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07103227B2 (en) |
-
1987
- 1987-03-30 JP JP62074271A patent/JPH07103227B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07103227B2 (en) | 1995-11-08 |
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