JPH044221A - Production of conductive polymer by fluorine gas reaction - Google Patents
Production of conductive polymer by fluorine gas reactionInfo
- Publication number
- JPH044221A JPH044221A JP2106839A JP10683990A JPH044221A JP H044221 A JPH044221 A JP H044221A JP 2106839 A JP2106839 A JP 2106839A JP 10683990 A JP10683990 A JP 10683990A JP H044221 A JPH044221 A JP H044221A
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- fluorine gas
- pyrrole
- reaction
- gas
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、フッ素ガスと重合性単量体との反応による導
電性重合体の簡便な製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a simple method for producing a conductive polymer by reacting fluorine gas with a polymerizable monomer.
（従来技術とその問題点）
導電性高分子として例えば、ポリアセチレン、ポリピロ
ール、ポリパラフェニレンなどのπ共役系ポリマーがあ
り、これらをＡ ｓ Ｆ ｓ、Ｉ２などによりドープす
ることにより導電性を示すようになる。(Prior art and its problems) Examples of conductive polymers include π-conjugated polymers such as polyacetylene, polypyrrole, and polyparaphenylene, which can be doped with A s F s, I2, etc. to exhibit conductivity. become.
この有機高分子の導電性を利用してポリマーバッテリー
、エレクトロクロミンク材料（表示装置）、太陽電池、
トランジスタ・ダイオード、センサなど巾広い用途が考
えられる。Utilizing the conductivity of this organic polymer, polymer batteries, electrochromic materials (display devices), solar cells,
A wide range of applications are possible, including transistors, diodes, and sensors.
しかしながら、現在開発中の導電性高分子材料は、耐環
境性に劣るもの、脆性が大きく加工性が乏しいもの等が
多いのが現状である。However, the current situation is that many of the conductive polymer materials currently under development have poor environmental resistance, are highly brittle, and have poor workability.
導電性重合体の製造方法としては、白金などの電極表面
に重合膜を形成させる電解重合法が一般的に行われてい
る。重合中にドーピングも可能になっている。この他に
も、塩化第二鉄を樹脂などの基板に分散させ、ピロール
などの重合性単量体の蒸気と接触させる方法があるが、
操作に手間がかかるとともに反応時間もかかる、という
問題がある。As a method for producing conductive polymers, an electrolytic polymerization method is generally used in which a polymer film is formed on the surface of an electrode such as platinum. Doping during polymerization is also possible. Another method is to disperse ferric chloride in a substrate such as a resin and bring it into contact with the vapor of a polymerizable monomer such as pyrrole.
There are problems in that the operation is time-consuming and the reaction time is also long.
（発明の目的）
本発明は、上記の事情に鑑み、より簡便な装置、手法で
、短時間にフィルム状、あるいは、粉末状の導電性重合
体を容易に製造し得る、導電性重合体の製造方法を提供
することを目的とする。(Objective of the Invention) In view of the above circumstances, the present invention has been developed to produce a conductive polymer that can be easily produced in the form of a film or powder in a short time using simpler equipment and methods. The purpose is to provide a manufacturing method.
本発明者らは、上記の目的を達成すべく、研究を重ねた
結果、低温で重合性単量体とフッ素ガスとを直接反応さ
せることにより、目的を達成し得ることを見出し１本発
明に到達した。As a result of repeated research in order to achieve the above object, the present inventors discovered that the object could be achieved by directly reacting a polymerizable monomer with fluorine gas at low temperature. Reached.
（発明の構成）
本発明は、フッ素ガスと重合性単量体とを反応させるこ
とからなる導電性重合体の製造法を提供する。(Structure of the Invention) The present invention provides a method for producing a conductive polymer, which comprises reacting fluorine gas and a polymerizable monomer.
本発明はまた、前記製造方法であって、単量体がピロー
ル、チオフェン、フランからなる群から選ばれるもので
ある方法を提供する。The present invention also provides the above manufacturing method, wherein the monomer is selected from the group consisting of pyrrole, thiophene, and furan.
本発明はまた。前記の製造方法であって、重合を０〜−
８０℃の温度で実施する方法を提供する。The present invention also includes: The production method described above, wherein the polymerization is carried out from 0 to -
A method is provided which is carried out at a temperature of 80°C.
本発明はまた、前記の製造方法であって、チツ素ガスで
５〜２０容量％に希釈したフッ素ガスを用いる方法を提
供する。The present invention also provides the above manufacturing method, which uses fluorine gas diluted to 5 to 20% by volume with nitrogen gas.
本発明に用いられる重合性単量体は、ピロール、チオフ
ェン、フラン等が挙げられる。通常は、ピロールが最も
好ましく用いられる２
すなわち、本発明によれば、ピロールをアセトニトリル
、ジクロロメタン、四塩化炭素などの有機溶媒に溶かし
、−ｇｏ−ｏ℃の温度範囲で、チツ素ガスなどの不活性
ガスで希釈した５〜ｂのフッ素ガスと短時間反応させる
ことにより、容易に導電性重合体を生成させることを特
徴とする導電性重合体の製造方法が得られる。本発明方
法におけるチッ素等の不活性ガス雰囲気下におけるフッ
素ガス濃度は、５〜ｂ
より好ましくは１０容量％前後である。フッ素ガス濃度
が５容量％未満では、反応終了に時間がかかり導電率が
低い。２０容量％を越えると、反応が激しくなり、重合
の他に分解も起るため、導電率も低くなる。例えば、フ
ッ素１０容量％−チッ素りｏ容量％で、ピロールと２時
間反応させた場合には、ポリピロールの電導率が１０−
”Ｓ−ｃｍ−”のオーダーであるのに対し、 １０−”
Ｓ−ｃｍ−”のオーダーの導電性重合体が得られる。ま
た、反応速度は、フッ素ガスの反応性を抑制する意味か
らも一８０〜０℃の範囲が望ましい。より好ましくは、
−８０〜−４０℃の範囲である。−８０℃よりも反応速
度が低いと重合体の生成に時間がかかり、０℃を越える
と、反応が激しくなり、導電率も低くなる。Examples of the polymerizable monomer used in the present invention include pyrrole, thiophene, and furan. Generally, pyrrole is most preferably used2. That is, according to the present invention, pyrrole is dissolved in an organic solvent such as acetonitrile, dichloromethane, or carbon tetrachloride, and then dissolved in an organic solvent such as nitrogen gas at a temperature range of -go-o°C. A method for producing a conductive polymer is obtained, which is characterized in that the conductive polymer is easily produced by reacting with fluorine gas 5 to b diluted with an active gas for a short period of time. In the method of the present invention, the concentration of fluorine gas in an atmosphere of an inert gas such as nitrogen is preferably 5 to 10% by volume. When the fluorine gas concentration is less than 5% by volume, it takes time to complete the reaction and the conductivity is low. If it exceeds 20% by volume, the reaction becomes intense and decomposition occurs in addition to polymerization, resulting in a decrease in electrical conductivity. For example, when reacting with pyrrole for 2 hours at 10% by volume of fluorine and 0% by volume of nitrogen, the electrical conductivity of polypyrrole becomes 10% by volume.
While it is on the order of “S-cm-”, 10-”
A conductive polymer on the order of "S-cm-" can be obtained. Also, the reaction rate is preferably in the range of -80 to 0°C from the viewpoint of suppressing the reactivity of fluorine gas. More preferably,
It is in the range of -80 to -40°C. If the reaction rate is lower than -80°C, it will take time to produce the polymer, and if it exceeds 0°C, the reaction will be intense and the electrical conductivity will be low.
本発明によれば、ガラス板などの基板を反応溶液中に侵
せきし、フッ素ガスと反応させることにより、ガラス板
などの基板上に重合膜が生成する。According to the present invention, a polymeric film is produced on a substrate such as a glass plate by immersing the substrate such as a glass plate in a reaction solution and reacting with fluorine gas.
また、ガラス板などの基板にピロールを塗布し、これと
フッ素ガスとを短時間接触させることにより、容易に均
一な導電性重合膜を形成することもできる。Furthermore, a uniform conductive polymer film can be easily formed by applying pyrrole to a substrate such as a glass plate and bringing it into contact with fluorine gas for a short time.
したがって、本発明方法により、従来法に比べて簡便に
導電性重合体を製造できる。さらに、本発明によれば、
同時に導電性重合膜と導電性重合粉体を得ることもでき
る。Therefore, by the method of the present invention, a conductive polymer can be produced more easily than the conventional method. Furthermore, according to the present invention,
At the same time, a conductive polymer film and a conductive polymer powder can be obtained.
（発明の具体的開示）
次に、本発明を実施例により具体的に説明するが、これ
らの実施例は１本発明の範囲を規定するものではない。(Specific Disclosure of the Invention) Next, the present invention will be specifically explained using Examples, but these Examples do not define the scope of the present invention.
また、実施例においては、容量％を％で示す。導電率の
測定は、四端子法によりおこなった。Further, in the examples, capacity % is expressed in %. The electrical conductivity was measured using the four-terminal method.
実施例１
攪はん子の入った１００ｍ１２の３０フラスコに ピロ
ール１．５０ｇ（０，０２２−Ｆ−ル）、ジクロロメタ
ン５ｏ、０４ｇ（０，５９モル）を入れ、−７８℃まで
冷却する。フッ素１０％−チッ素９０％の混合ガスを１
４０ｃｃ／分の流速で２時間導入した。反応終了後、チ
ツ素ガスをバブリングさせ、反応溶液中のフッ素ガスを
除去した。Example 1 1.50 g (0,022-F-1) of pyrrole and 50,04 g (0,59 mol) of dichloromethane are placed in a 100 m 30 flask containing a stirrer and cooled to -78°C. 10% fluorine-90% nitrogen mixed gas
It was introduced for 2 hours at a flow rate of 40 cc/min. After the reaction was completed, nitrogen gas was bubbled to remove fluorine gas from the reaction solution.
フラスコ壁に生成したポリピロール膜を剥して導電率を
測定したところ、 ８．Ｉ Ｘ １Ｏ−２Ｓ−ｃｔａ−
’であった。また、同時に生成したポリピロール粉末を
圧粉体にして、その導電率を測定したところ、５．７
Ｘ１０−’Ｓ−ｃｍ−”であった。When the polypyrrole film formed on the flask wall was peeled off and the conductivity was measured, 8. I X 1O-2S-cta-
'Met. In addition, when the polypyrrole powder produced at the same time was made into a green compact and its electrical conductivity was measured, it was found to be 5.7.
X10-'S-cm-''.
実施例２
実施例１と同様の実験装置を用い、アセトニトリル（１
，２２モル）中で反応温度−４０”Ｃにしてピロール（
０，０３０モル）とフッ素ガスとの反応を行った。Example 2 Using the same experimental equipment as in Example 1, acetonitrile (1
, 22 mol) at a reaction temperature of -40"C.
(0,030 mol) was reacted with fluorine gas.
得られたポリピロール膜の導電率を測定したところ、１
．４ Ｘ １０”−２Ｓ−ｃｍ−”であった。When the electrical conductivity of the obtained polypyrrole film was measured, it was found to be 1
．． It was 4 x 10''-2S-cm-''.
実施例３
実施例１と同様の実験装置を用い、ガラス板を反応溶液
中（溶媒ニアセトニトリル）に浸しておき。Example 3 Using the same experimental apparatus as in Example 1, a glass plate was immersed in a reaction solution (solvent niacetonitrile).
−４０℃で１時間反応を行った。ガラス板上に生成した
ポリピロール膜の導電率を測定したところ。The reaction was carried out at -40°C for 1 hour. Measurement of the electrical conductivity of a polypyrrole film formed on a glass plate.
１．２ Ｘ １０−”Ｓ−ｃ＋ａ−”であった。It was 1.2X10-"S-c+a-".
実施例４
ガラス板にピロールを塗布しておき、これをあらかじめ
−４０℃に冷却したガラス製反応容器に入れ、フッ素１
０％−チッ素９０％の混合ガスを５分間接触させたとこ
ろ、導電率２．５ Ｘ １０１０−３５−ａ”のポリピ
ロール膜が得られた。Example 4 A glass plate was coated with pyrrole, placed in a glass reaction vessel pre-cooled to -40°C, and fluorine 1
When a mixed gas of 0%-90% nitrogen was contacted for 5 minutes, a polypyrrole film with a conductivity of 2.5 x 1010-35-a'' was obtained.
比較例１
実施例１と同様な方法で、アセトニトリル中、−４０℃
で、フッ素３０％−チッ素７０％の混合ガスでピロール
と反応を行ったところ、激しい反応となり、得られたポ
リピロール膜の導電率も６．５ Ｘ １０−１０−５Ｓ
−”と低くなった。Comparative Example 1 In the same manner as Example 1, at -40°C in acetonitrile.
When a reaction was carried out with pyrrole in a mixed gas of 30% fluorine and 70% nitrogen, a violent reaction occurred and the conductivity of the resulting polypyrrole film was 6.5 x 10-10-5S.
-” and became low.
比較例２
実施例１と同様な方法で、アセトニトリル中、−４０°
Ｃで、フッ素１％−チッ素９９％の混合ガスでピロール
と４時間反応を行ったところ、導電率８．４Ｘ １０−
’Ｓ−ｃｍ−”のポリピロール膜が得られた。Comparative Example 2 In the same manner as Example 1, in acetonitrile at -40°
When reacting with pyrrole for 4 hours in a mixed gas of 1% fluorine and 99% nitrogen, the electrical conductivity was 8.4X 10-
A polypyrrole film of 'S-cm-' was obtained.
比較例３
実施例１と同様な方法で、アセトニトリル中、室温で、
ピロールと反応を行なったところ、かなり激しい反応と
なり、導電率１．２ Ｘ １０−’５−ｃｍ−１の不均
一なポリピロール膜が得られた。Comparative Example 3 In a similar manner to Example 1, in acetonitrile at room temperature,
When the reaction was carried out with pyrrole, the reaction was quite violent and a non-uniform polypyrrole film with a conductivity of 1.2 x 10-'5-cm-1 was obtained.
（発明の効果）
以上のように本発明の方法を実施することにより、簡便
な方法で導電性重合膜および導電性重合粉体を製造する
ことが可能であり、基板の形状を変えることにより様々
な形状に導電性膜を加工できるので工業的に極めて価値
がある。(Effects of the Invention) As described above, by carrying out the method of the present invention, it is possible to manufacture a conductive polymer film and conductive polymer powder in a simple manner, and by changing the shape of the substrate, various It is extremely valuable industrially because it allows the conductive film to be processed into various shapes.
Claims (4)
なる導電性重合体の製造法。1. A method for producing a conductive polymer comprising reacting fluorine gas and a polymerizable monomer.
から選ばれるものである請求項１に記載の導電性重合体
の製造方法。2. 2. The method for producing a conductive polymer according to claim 1, wherein the monomer is selected from the group consisting of pyrrole, thiophene, and furan.
載の導電性重合体の製造方法。3. The method for producing a conductive polymer according to claim 1, wherein the polymerization is carried out at a temperature of 0 to -80°C.
を用いる請求項１に記載の導電性重合体の製造方法。4. 2. The method for producing a conductive polymer according to claim 1, wherein fluorine gas diluted to 5 to 20% by volume with nitrogen gas is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2106839A JP2817346B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing conductive polymer using fluorine gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2106839A JP2817346B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing conductive polymer using fluorine gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH044221A true JPH044221A (en) | 1992-01-08 |
| JP2817346B2 JP2817346B2 (en) | 1998-10-30 |
Family
ID=14443867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2106839A Expired - Lifetime JP2817346B2 (en) | 1990-04-23 | 1990-04-23 | Method for producing conductive polymer using fluorine gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2817346B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62270621A (en) * | 1985-12-06 | 1987-11-25 | Showa Denko Kk | Polymer having isoindole structure and its production |
-
1990
- 1990-04-23 JP JP2106839A patent/JP2817346B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62270621A (en) * | 1985-12-06 | 1987-11-25 | Showa Denko Kk | Polymer having isoindole structure and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2817346B2 (en) | 1998-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0162864B1 (en) | Manufacturing method of soluble electrically conductive polypyrrole | |
| JP2001040168A (en) | Crosslinking agent for solid polyelectrolyte, crosslinked solid polyelectrolyte preapred using same and lithium polymer secondary cell | |
| WO1991019021A1 (en) | Polymerization of thiophene and its derivatives | |
| JP2003282141A (en) | Gel electrolyte, its production method and its use | |
| JPH0138808B2 (en) | ||
| EP0231309B1 (en) | Process for manufacturing electrically conductive polythiophene | |
| JPH044221A (en) | Production of conductive polymer by fluorine gas reaction | |
| JPH0678493B2 (en) | Method for producing conductive polymer composition | |
| JPH0138411B2 (en) | ||
| JPH026767B2 (en) | ||
| JPS61279061A (en) | secondary battery | |
| JPH029621B2 (en) | ||
| JPS612728A (en) | Pyrrole polymer powder | |
| JPH029620B2 (en) | ||
| JPS62220518A (en) | Thiophene polymer and production thereof | |
| Dong et al. | Electrochemical synthesis and characterization of polydiphenylamine | |
| JPS63199727A (en) | organic semiconductor | |
| JPH03239720A (en) | Production of conductive polymer | |
| KR920003106B1 (en) | Process for the preparation of electric conductive composition | |
| JPH03239721A (en) | Production of conductive polymer | |
| JPS63223031A (en) | Polymer having isoindole structure and production thereof | |
| JPH0645673B2 (en) | Method for producing highly conductive thiophene-based polymer | |
| JPH0620000B2 (en) | Non-aqueous secondary battery | |
| JPH0739476B2 (en) | Method for producing conductive pyrrole polymer | |
| JPS62157675A (en) | secondary battery |