JPH0751627B2 - Method for producing aniline-based polymer - Google Patents
Method for producing aniline-based polymerInfo
- Publication number
- JPH0751627B2 JPH0751627B2 JP59186254A JP18625484A JPH0751627B2 JP H0751627 B2 JPH0751627 B2 JP H0751627B2 JP 59186254 A JP59186254 A JP 59186254A JP 18625484 A JP18625484 A JP 18625484A JP H0751627 B2 JPH0751627 B2 JP H0751627B2
- Authority
- JP
- Japan
- Prior art keywords
- aniline
- based polymer
- polymerization
- carbon atoms
- polymer
- 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.)
- Expired - Lifetime
Links
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 本発明は、実質的に無水の状態で、アニリン系化合物を
酸化剤の存在下で重合することを特徴とするアニリン系
重合体の製造方法に関する。The present invention relates to a method for producing an aniline-based polymer, which comprises polymerizing an aniline-based compound in the presence of an oxidizing agent in a substantially anhydrous state.
電導性高分子は、高分子化合物がもつ、軽量性、加工性
に金属がもつ電気伝導性を付与した極めて特異な素材で
ある。ところが一般に電導性高分子は、酸素に敏感であ
るため、実用上多くの問題点を有する。この欠点を克服
せんがため数種の電導性高分子が提案され、現実に種々
の応用のための測定がなされている。しかしながら酸素
と反応し難い電導性高分子は特異な重合方法である電解
重合法でしか電導度が高いフィルムが得られず、そのた
め製造コストが高いという難点がある。一方、ポリアニ
リンは、普通の重合方法で得られる粉末を成形したシー
ト状物であっても、ドーピングすることにより、かなり
の電導度を維持し、しかも空気中で安定であるため注目
されている。ところが、現在までのポリアニリンは、水
の存在下で性能をもつ触媒でしか製造できなかったた
め、ポリマーを得るためには生じた生成物を脱水する必
要がある。一般にアニリンの様なアミン化合物から脱水
するのは困難で、この現象はポリマーにあってはその困
難性は倍加し、精製コストが飛躍的に増加するという欠
点がある。The conductive polymer is an extremely peculiar material in which a polymer compound has the light weight and the workability which imparts the electrical conductivity of a metal. However, since the conductive polymer is generally sensitive to oxygen, it has many practical problems. In order to overcome this drawback, several kinds of conductive polymers have been proposed and actually measured for various applications. However, a conductive polymer that does not easily react with oxygen has a disadvantage that a film having high conductivity can be obtained only by an electrolytic polymerization method which is a unique polymerization method, and thus the manufacturing cost is high. On the other hand, polyaniline has attracted attention because even if it is a sheet-like product obtained by molding a powder obtained by an ordinary polymerization method, it can maintain a considerable electric conductivity by doping and is stable in air. However, until now, polyaniline could only be produced with a catalyst capable of functioning in the presence of water, so that the resulting product needs to be dehydrated in order to obtain a polymer. Generally, it is difficult to dehydrate from an amine compound such as aniline, and this phenomenon doubles the difficulty in the case of a polymer, and there is a drawback that the purification cost increases dramatically.
本発明者は、一般式（１） （ここでR1〜R6は、水素、ハロゲン、炭素数５以下の飽
和炭化水素基、炭素数５以下のアルコキシ基のいずれか
であり、R1〜R5のうち少なくとも一つは水素原子であ
る。） で表されるアニリン系化合物を金属塩化物からなる酸化
剤触媒の存在下、実質的に無水の状態で重合することを
特徴とするアニリン系重合体の製造方法を見出し本発明
に到達することができた。The present inventor has found that the general formula (1) (Here, R 1 to R 6 are any of hydrogen, halogen, a saturated hydrocarbon group having 5 or less carbon atoms, and an alkoxy group having 5 or less carbon atoms, and at least one of R 1 to R 5 is a hydrogen atom. The present invention has found a method for producing an aniline-based polymer characterized by polymerizing an aniline-based compound represented by the formula (1) in a substantially anhydrous state in the presence of an oxidant catalyst composed of a metal chloride. I was able to reach it.
即ち、本発明はアニリン系化合物を金属塩化物からなる
酸化剤触媒の存在下、実質的に無水の状態で重合するこ
とを特徴とするアニリン系重合体の製造方法に関する。That is, the present invention relates to a method for producing an aniline-based polymer, which comprises polymerizing an aniline-based compound in a substantially anhydrous state in the presence of an oxidizing agent catalyst composed of a metal chloride.
本発明におけるアニリン系化合物とは、一般式（１）で
示される化合物をさす。The aniline-based compound in the present invention refers to a compound represented by the general formula (1).
〔ここでR1〜R6は、水素、ハロゲン、炭素数５以下の飽
和炭化水素基、炭素数５以下のアルコキシ基のいずれか
であり、R1〜R5のうち少なくとも一つは水素原子であ
る。〕代表例として、アニリン、Ｎ−メチルアニリン、
Ｏ−クロルアニリン、ｍ−クロルアニリン、ｐ−クロル
アニリン、Ｏ−メトキシアニリン、ｍ−メトキシアニリ
ン、ｐ−メトキシアニリン、Ｏ−エトキシアニリン、ｍ
−エトキシアニリン、ｐ−エトキシアニリン、Ｏ−メチ
ルアニリン、ｍ−メチルアニリン、ｐ−メチルアニリン
等が挙げられる。 [Wherein R 1 to R 6 are any of hydrogen, halogen, a saturated hydrocarbon group having 5 or less carbon atoms, and an alkoxy group having 5 or less carbon atoms, and at least one of R 1 to R 5 is a hydrogen atom. Is. ] As typical examples, aniline, N-methylaniline,
O-chloroaniline, m-chloroaniline, p-chloroaniline, O-methoxyaniline, m-methoxyaniline, p-methoxyaniline, O-ethoxyaniline, m
-Ethoxyaniline, p-ethoxyaniline, O-methylaniline, m-methylaniline, p-methylaniline and the like can be mentioned.
本発明における酸化剤の代表例として三塩化アルミニウ
ム、塩化亜鉛、塩化錫、塩化銅、三塩化鉄等があげられ
る。また酸化剤の量は、アニリン系化合物の重合性能に
よって変化するが、一般には、アニリン系化合物に対し
て３倍モルから1/3モルの間が好ましい。また、重合を
均一に行なうために適当な溶媒（たとえば無水のアルコ
ール類、ケトン類等の公知の溶媒）を使用しても良い。Typical examples of the oxidizing agent in the present invention include aluminum trichloride, zinc chloride, tin chloride, copper chloride, iron trichloride and the like. The amount of the oxidizing agent varies depending on the polymerization performance of the aniline-based compound, but is generally preferably 3 times to 1/3 mol with respect to the aniline-based compound. In addition, a suitable solvent (for example, a known solvent such as anhydrous alcohols and ketones) may be used to uniformly carry out the polymerization.
本発明における重合方法は、アニリン系化合物を撹拌下
に酸化剤と接触させるだけで良い。重合温度は、−80℃
から120℃の間で重合時間は24時間以下で充分である。
尚、重合収量を上げるため重合系内は、不活性ガス雰囲
気が好ましい。一般には生成した重合体を公知の方法に
より洗浄・精製し、狭雑物を除去して使用される。In the polymerization method of the present invention, it is sufficient to bring the aniline compound into contact with the oxidizing agent while stirring. Polymerization temperature is -80 ℃
A polymerization time of 24 hours or less is sufficient between 1 and 120 ° C.
In order to increase the polymerization yield, an inert gas atmosphere is preferable in the polymerization system. Generally, the produced polymer is washed and purified by a known method to remove impurities and used.
このようにして得たポリアニリン系重合体は、公知のド
ーピングにより高電導性とすることができ、空気中でも
安定であり、製造コストも安いため、工業的な利用価値
が高い。The polyaniline-based polymer thus obtained can be made highly conductive by known doping, is stable in air, and has a low manufacturing cost, and thus has a high industrial utility value.
以下実施例でもって本発明をさらに詳しく述べる。The present invention will be described in more detail with reference to the following examples.
実施例１ 三塩化鉄0.12モルをアセトン100mlに溶かした溶液にア
ニリン0.24モルとアセトン20mlの混合物を室温で滴下し
70℃で８時間重合した。重合後分液し、使用した酸化剤
とアニリンをアセトンで充分洗い、後減圧乾燥した。よ
う素ドープによる電導度は10s/cmであり、未ドープのポ
リアニリンを空気中で40時間放置しても酸化されないこ
とが赤外スペクトルからわかった。Example 1 To a solution prepared by dissolving 0.12 mol of iron trichloride in 100 ml of acetone, a mixture of 0.24 mol of aniline and 20 ml of acetone was added dropwise at room temperature.
Polymerization was carried out at 70 ° C. for 8 hours. After polymerization, liquid separation was performed, and the used oxidizing agent and aniline were thoroughly washed with acetone, and then dried under reduced pressure. It was found from the infrared spectrum that the conductivity with iodine doping was 10 s / cm, and that undoped polyaniline was not oxidized even when left in the air for 40 hours.
実施例２〜６ 実施例１でアニリンのかわりに表１で示されるアニリン
系化合物を使用した以外は実施例１と同様にして重合し
てアニリン系重合体を得、同様にドーピングを行ない評
価した。Examples 2 to 6 Polymerization was performed in the same manner as in Example 1 except that the aniline-based compounds shown in Table 1 were used instead of aniline to obtain aniline-based polymers, and the same doping was performed and evaluated. .
実施例７〜９ 実施例１で三塩化鉄のかわりに表２で示される酸化剤を
使用した以外は実施例１と同様にしてポリアニリンを
得、ドーピングを行ない評価した。Examples 7 to 9 Polyaniline was obtained in the same manner as in Example 1 except that the oxidizing agents shown in Table 2 were used instead of iron trichloride, and doping was performed and evaluated.
以上の結果を表１、表２に示した。The above results are shown in Tables 1 and 2.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−197728（ＪＰ，Ａ) 特表 昭60−501262（ＪＰ，Ａ) 英国特許1216549（ＧＢ，Ａ) ─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-60-197728 (JP, A) JP-A-60-501262 (JP, A) British patent 1216549 (GB, A)
Claims (1)
和炭化水素基、炭素数５以下のアルコキシ基のいずれか
であり、R1〜R5のうち少なくとも一つは水素原子であ
る。） で表されるアニリン系化合物を金属塩化物からなる酸化
剤触媒の存在下、実質的に無水の状態で重合することを
特徴とするアニリン系重合体の製造方法。1. A general formula (1) (Here, R 1 to R 6 are any of hydrogen, halogen, a saturated hydrocarbon group having 5 or less carbon atoms, and an alkoxy group having 5 or less carbon atoms, and at least one of R 1 to R 5 is a hydrogen atom. The method for producing an aniline-based polymer is characterized in that the aniline-based compound represented by the formula (1) is polymerized in a substantially anhydrous state in the presence of an oxidant catalyst composed of a metal chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186254A JPH0751627B2 (en) | 1984-09-07 | 1984-09-07 | Method for producing aniline-based polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186254A JPH0751627B2 (en) | 1984-09-07 | 1984-09-07 | Method for producing aniline-based polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6164729A JPS6164729A (en) | 1986-04-03 |
| JPH0751627B2 true JPH0751627B2 (en) | 1995-06-05 |
Family
ID=16185050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59186254A Expired - Lifetime JPH0751627B2 (en) | 1984-09-07 | 1984-09-07 | Method for producing aniline-based polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0751627B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0639525B2 (en) * | 1985-02-26 | 1994-05-25 | 日東電工株式会社 | Doping method of organic polymer |
| JP2649670B2 (en) * | 1985-05-10 | 1997-09-03 | 日東電工株式会社 | Method for producing conductive organic polymer |
| US5069820A (en) * | 1987-08-07 | 1991-12-03 | Allied-Signal Inc. | Thermally stable forms of electrically conductive polyaniline |
| JPH02500197A (en) * | 1988-02-05 | 1990-01-25 | ロッキード コーポレーション | Production of base-type conductive polymer |
| US4935163A (en) * | 1988-08-01 | 1990-06-19 | Lockheed Corporation | High service temperature conductive polymers and method of producing same |
| CN110922589B (en) * | 2019-12-06 | 2022-05-03 | 河南科技大学 | Liquid-liquid interface preparation method of micro-nano structure poly (o-ethoxyaniline) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1216549A (en) | 1967-02-20 | 1970-12-23 | Centre Nat Rech Scient | Organic electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60197728A (en) * | 1983-11-10 | 1985-10-07 | Nitto Electric Ind Co Ltd | Electroconductive organic polymer and its production |
-
1984
- 1984-09-07 JP JP59186254A patent/JPH0751627B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1216549A (en) | 1967-02-20 | 1970-12-23 | Centre Nat Rech Scient | Organic electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6164729A (en) | 1986-04-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |