JPH07165892A - Method for producing aqueous solution of conductive polymer colloid - Google Patents
Method for producing aqueous solution of conductive polymer colloidInfo
- Publication number
- JPH07165892A JPH07165892A JP34096293A JP34096293A JPH07165892A JP H07165892 A JPH07165892 A JP H07165892A JP 34096293 A JP34096293 A JP 34096293A JP 34096293 A JP34096293 A JP 34096293A JP H07165892 A JPH07165892 A JP H07165892A
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- JP
- Japan
- Prior art keywords
- aqueous solution
- conductive polymer
- acid
- colloid
- polymer colloid
- 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.)
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
(57)【要約】
【構成】 複素５員環式化合物例えばチオフェン、ピロ
ール、フラン又はそれらの誘導体を、アルギン酸、ポリ
アクリル酸、ポリスチレンスルホン酸等の高分子酸の存
在下に水性媒質中で化学酸化重合させることによる導電
性高分子コロイド水溶液の製造方法。
【効果】 このコロイド水溶液はキャスト、塗工等の成
形加工性に優れ、容易に高性能導電性被膜を作成し得
る。(57) [Summary] [Structure] A 5-membered heterocyclic compound such as thiophene, pyrrole, furan or a derivative thereof is chemically reacted in an aqueous medium in the presence of a polymeric acid such as alginic acid, polyacrylic acid or polystyrenesulfonic acid. A method for producing a conductive polymer colloid aqueous solution by oxidative polymerization. [Effect] This colloidal aqueous solution has excellent moldability such as casting and coating, and can easily form a high-performance conductive coating.
Description
【０００１】[0001]
【産業上の利用分野】本発明は導電性高分子コロイド水
溶液の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing an aqueous solution of a conductive polymer colloid.
【０００２】[0002]
【従来の技術】近年、導電性高分子は軽量で優れた導電
性を示す高分子素材として帯電防止材料、電磁波遮蔽材
料、エレクトロニクス素子、軽量電池等種々の分野への
応用が検討されている。導電性高分子を製造する方法と
しては電解酸化重合法と化学酸化重合が知られている。2. Description of the Related Art In recent years, conductive polymers have been studied for application in various fields such as antistatic materials, electromagnetic wave shielding materials, electronic devices, and lightweight batteries as polymeric materials that are lightweight and exhibit excellent conductivity. As a method for producing a conductive polymer, electrolytic oxidative polymerization and chemical oxidative polymerization are known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、電解酸
化重合法は製造コストが高くかつ基材上に直接重合する
ため、成形体の形状が限定されるという欠点を有し、一
方、化学酸化重合法は安価で大量生産が可能であるが、
重合体は一般に不溶不融の粉末として得られ、成形加工
が困難であるという欠点を有している。However, the electrolytic oxidative polymerization method has the drawbacks of high manufacturing cost and direct polymerization on the substrate, which limits the shape of the molded body. On the other hand, the chemical oxidative polymerization method is disadvantageous. Is cheap and can be mass-produced,
The polymer is generally obtained as an insoluble and infusible powder, and has the drawback that molding is difficult.
【０００４】[0004]
【課題を解決するための手段】本発明は上記課題を解決
するために、成形加工性の優れた導電性高分子コロイド
水溶液を容易に製造する方法を提供するものである。す
なわち、本発明者らは複素５員環式化合物を水溶液中で
高分子酸の存在下で化学酸化重合することにより、容易
に導電性高分子コロイド水溶液を作製し得ることを見出
し、本発明に至ったものである。In order to solve the above problems, the present invention provides a method for easily producing an aqueous solution of a conductive polymer colloid having excellent moldability. That is, the present inventors have found that a conductive polymer colloid aqueous solution can be easily prepared by chemically oxidatively polymerizing a 5-membered heterocyclic compound in an aqueous solution in the presence of a polymeric acid. It has come.
【０００５】本発明は、一般式The present invention has the general formula
【化２】 （式中、Ｘは−Ｏ−、−Ｓ−又は−ＮＲ3 −、Ｒ1 及び
Ｒ2 は水素原子、ハロゲン原子又は１価の有機基、Ｒ3
は水素原子又は１価の有機基を示す）で表される複素５
員環式化合物を、高分子酸の存在下で化学酸化重合する
ことを特徴とする導電性高分子コロイド水溶液の製造方
法である。[Chemical 2] (In the formula, X is —O—, —S— or —NR 3 —, R 1 and R 2 are hydrogen atom, halogen atom or monovalent organic group, R 3
Represents a hydrogen atom or a monovalent organic group) 5
A method for producing an aqueous solution of a conductive polymer colloid, which comprises subjecting a membered cyclic compound to chemical oxidative polymerization in the presence of a polymer acid.
【０００６】導電性高分子コロイド水溶液の作製法につ
いてはすでに各種の方法が研究されており、例えばピロ
ールを高分子量ポリエチレンオキサイドの存在下で化学
酸化重合する方法（Ｂ．Ｖｉｎｃｅｎｔ ｅｔ ａ
ｌ．，Ｃｏｌｌｏｉｄｓ ａｎｄＳｕｒｆａｃｅｓ，５
１（１９９０）２３９−２５３）等が報告されている。
しかし、これらの方法によるコロイド水溶液は一般に未
反応モノマーや酸化重合触媒を精製除去することが容易
でない。しかしながら、本発明による方法によれば、重
合終了後に系のｐＨを上げることにより高分子酸がメタ
ノール等の水溶性有機溶剤に難溶となるため、これらの
有機溶剤に対する再沈法による精製を容易に行なうこと
ができる。Various methods have already been studied for the preparation of a conductive polymer colloid aqueous solution, for example, a method of chemically oxidatively polymerizing pyrrole in the presence of high molecular weight polyethylene oxide (B. Vincent et a.
l. , Colloids and Surfaces, 5
1 (1990) 239-253) and the like have been reported.
However, it is generally not easy to purify and remove unreacted monomers and oxidative polymerization catalysts from the colloidal aqueous solution obtained by these methods. However, according to the method of the present invention, by raising the pH of the system after the completion of the polymerization, the polymeric acid becomes hardly soluble in a water-soluble organic solvent such as methanol. Can be done
【０００７】以下本発明についてさらに詳しく説明す
る。本発明による導電性高分子コロイド水溶液は以下の
ようにして得ることができる。すなわち、高分子酸及び
酸化重合触媒を含む水溶液に複素５員環式化合物を添加
するか、あるいは複素５員環式化合物及び高分子酸を含
む水溶液に酸化重合触媒を添加することにより、複素５
員環式化合物を化学酸化重合させて、導電性高分子コロ
イド水溶液を得ることができる。この時必要ならば、得
られたコロイド水溶液を上記再沈法や透析法等により精
製することができる。The present invention will be described in more detail below. The conductive polymer colloidal aqueous solution according to the present invention can be obtained as follows. That is, a hetero 5-membered cyclic compound is added to an aqueous solution containing a polymeric acid and an oxidative polymerization catalyst, or an oxidative polymerization catalyst is added to an aqueous solution containing a 5-membered heterocyclic compound and a polymeric acid.
A membered cyclic compound can be chemically oxidatively polymerized to obtain a conductive polymer colloid aqueous solution. At this time, if necessary, the obtained colloidal aqueous solution can be purified by the above-mentioned reprecipitation method or dialysis method.
【０００８】複素５員環式化合物の置換基Ｒ1 、Ｒ2 、
Ｒ3 のための１価の有機基の例としてはメチル基、エチ
ル基等の炭素数１〜５のアルキル基，メトキシ基，エト
キシ基等の炭素数２〜６のアルコシキ基、フェニル基，
トリル基等の炭素数６〜９のアリール基、又はベンジル
基，フェネチル基等の炭素数７〜１０のアラルキル基等
が挙げられ、それぞれ水酸基等の置換基を有していても
よい。これらの複素５員環式化合物を単独で使用しても
二種以上を併用してもよい。Substituents R 1 , R 2 of the 5-membered heterocyclic compound,
Examples of the monovalent organic group for R 3 include an alkyl group having 1 to 5 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 2 to 6 carbon atoms such as a methoxy group and an ethoxy group, a phenyl group,
Examples thereof include an aryl group having 6 to 9 carbon atoms such as a tolyl group, and an aralkyl group having 7 to 10 carbon atoms such as a benzyl group and a phenethyl group, each of which may have a substituent such as a hydroxyl group. These 5-membered heterocyclic compounds may be used alone or in combination of two or more.
【０００９】高分子酸としては反応媒体中に複素５員環
式化合物の重合体を安定分散し得るものであれば特に制
限はなく、具体的にはアルギン酸、ポリアクリル酸、ポ
リスチレンスルホン酸、ポリビニルスルホン酸、ポリア
リルスルホン酸、ポリビニル硫酸等が挙げられ、単独で
使用しても二種以上を併用してもよい。これらの高分子
酸は酸基の一部がナトリウム塩、カリウム塩、アンモニ
ウム塩のような中和塩の形になっていてもよい。あるい
は一部がエステル化していてもよい。これらの高分子酸
の量は複素５員環式化合物１モルに対し、フリーの酸基
が０．０１〜２０当量、より好ましくは０．１〜５当量
となるように用いる。０．０１当量以下の場合は得られ
る導電性高分子が沈降性の粉末状となり、２０当量以上
の場合は成形後の導電性が不満足となる。The polymeric acid is not particularly limited as long as it can stably disperse the polymer of the 5-membered heterocyclic compound in the reaction medium. Specific examples thereof include alginic acid, polyacrylic acid, polystyrene sulfonic acid, and polyvinyl acid. Examples thereof include sulfonic acid, polyallyl sulfonic acid, and polyvinyl sulfuric acid, which may be used alone or in combination of two or more kinds. Some of the acid groups of these polymeric acids may be in the form of neutral salts such as sodium salts, potassium salts and ammonium salts. Alternatively, a part may be esterified. The amount of these polymeric acids used is 0.01 to 20 equivalents, more preferably 0.1 to 5 equivalents, of the free acid groups per 1 mol of the 5-membered heterocyclic compound. When the amount is 0.01 equivalent or less, the obtained conductive polymer is in the form of a sedimentary powder, and when the amount is 20 equivalents or more, the conductivity after molding becomes unsatisfactory.
【００１０】酸化重合媒触媒としては複素５員環式化合
物を重合し得るものであればよく、例えば過硫酸アンモ
ニウム、塩化第二鉄、重クロム酸カリウム、過マンガン
酸カリウム等あるいは過酸化水素−第一鉄塩等のレドッ
クス触媒等が好ましく用いられる。これらの酸化重合触
媒は単独で使用しても２種以上を併用してもよい。これ
らの酸化重合触媒の量は複素５員環式化合物１モルに対
し、０．０１〜１０酸化当量、より好ましくは０．１〜
５酸化当量となるように用いる。０．０１酸化当量以下
では重合収率が低く、１０酸化当量以上では酸化剤が不
必要に消費され、好ましくない。The oxidative polymerization medium catalyst may be any one capable of polymerizing a 5-membered heterocyclic compound, such as ammonium persulfate, ferric chloride, potassium dichromate, potassium permanganate, or hydrogen peroxide-secondary catalyst. Redox catalysts such as monoiron salts are preferably used. These oxidation polymerization catalysts may be used alone or in combination of two or more kinds. The amount of these oxidative polymerization catalysts is 0.01 to 10 oxidative equivalents, more preferably 0.1 to 10 mol, relative to 1 mol of the 5-membered heterocyclic compound.
It is used so as to have 5 oxidation equivalents. If it is less than 0.01 oxidation equivalent, the polymerization yield is low, and if it is more than 10 oxidation equivalent, the oxidizing agent is consumed unnecessarily, which is not preferable.
【００１１】反応終了後、コロイド水溶液をアルカリ性
とし、アルコール例えばメタノール、エタノール、イソ
プロピルアルコール等に投入し、生じた沈澱物を水に再
分散する等の精製を行ってもよい。本発明による導電性
高分子コロイド水溶液は必要ならば形成したコロイド粒
子の再凝集や沈殿に対する安定性を向上させるために各
種の界面活性剤、増粘剤等を併用することができる。
又、溶剤の蒸発促進等の目的で水と相溶性のある有機溶
剤を添加することもできる。又、成形後の機能改質を目
的として各種の高分子や可塑剤、酸化防止剤、難燃剤、
着色剤、安定剤、架橋剤、ドープ剤等を添加することも
できる。これらの添加剤のコロイド水溶液作製過程にお
ける添加時期及び添加量は任意である。After completion of the reaction, the colloidal aqueous solution may be made alkaline, and the colloid may be added to alcohol such as methanol, ethanol or isopropyl alcohol, and the resulting precipitate may be redispersed in water for purification. The conductive polymer colloidal aqueous solution according to the present invention may be used in combination with various surfactants, thickeners and the like, if necessary, in order to improve the stability of the formed colloidal particles against re-aggregation and precipitation.
Further, an organic solvent compatible with water may be added for the purpose of promoting evaporation of the solvent. Also, for the purpose of functional modification after molding, various polymers, plasticizers, antioxidants, flame retardants,
Colorants, stabilizers, cross-linking agents, dope agents and the like can also be added. The timing and amount of addition of these additives in the colloidal aqueous solution preparation process are arbitrary.
【００１２】本発明において導電性高分子がコロイド粒
子として得られる理由としては生成する導電性高分子が
介在する高分子酸アニオンに補促され、凝集が妨げられ
ることによると推察される。又、この時一部の高分子酸
は生成した導電性高分子のコロイド粒子に対して、保護
コロイドとして働き、コロイド安定性に寄与しているも
のと推察される。It is speculated that the reason why the conductive polymer is obtained as colloidal particles in the present invention is that the generated conductive polymer is promoted by the polymeric acid anion mediated by the conductive polymer to prevent aggregation. In addition, at this time, it is speculated that a part of the polymer acid acts as a protective colloid for the generated conductive polymer colloid particles and contributes to the colloid stability.
【００１３】本発明による導電性高分子コロイド水溶液
はキャストや塗工等の加工性に優れ、容易に高性能導電
性被膜を作製し得る。又、高分子ラテックス等の各種の
水系成形前駆体と自由に混合可能であり、得られた成形
体に導電性等の機能を付与することができる。又、水溶
液であるため、実際の成形加工工程において防火上ある
いは労働衛生上の安全性に優れている。The conductive polymer colloid aqueous solution according to the present invention is excellent in workability such as casting and coating, and can easily form a high-performance conductive coating. Further, it can be freely mixed with various water-based molding precursors such as polymer latex, and it is possible to impart a function such as conductivity to the obtained molding. Further, since it is an aqueous solution, it is excellent in fire safety and occupational health safety in the actual molding process.
【００１４】[0014]
【実施例】次に実施例により、本発明を説明するが、本
発明が該実施例に限定されるものではない。 実施例１ 水２００ｍｌにアルギン酸５ｇ、１規定カセイソーダ１
０ｍｌ、過硫酸アンモニウム４ｇを溶解する。これに室
温で攪拌しながらピロール２ｍｌをゆっくり滴下（滴下
時間、１時間）し、３時間反応させ、ポリピロールコロ
イド水溶液を得た。得られたコロイド水溶液をアンモニ
ア水（２５％）でｐＨを１０．０とした後、メタノール
で再沈、濾過し、濾物を水２００ｍｌに再分散させ、精
製コロイド水溶液を得た。得られた精製コロイド水溶液
は常温で１ヵ月間沈殿を認めなかった。又、この液１ｍ
ｌをガラス板（４ｃｍ×５ｃｍ）にキャストして得たフ
ィルムの表面固有抵抗（ＳＭ−８００１抵抗計、東亜電
波工業社製）は２．３×１０4 Ωを示した。EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to the examples. Example 1 Alginic acid 5 g, 1N caustic soda 1 in 200 ml of water
Dissolve 0 ml and 4 g ammonium persulfate. While stirring at room temperature, 2 ml of pyrrole was slowly added dropwise (dripping time: 1 hour) and reacted for 3 hours to obtain a polypyrrole colloid aqueous solution. The obtained colloidal aqueous solution was adjusted to pH 10.0 with aqueous ammonia (25%), reprecipitated with methanol and filtered, and the filtered material was redispersed in 200 ml of water to obtain a purified colloidal aqueous solution. The obtained purified colloidal aqueous solution showed no precipitation for one month at room temperature. In addition, this liquid 1m
The surface specific resistance (SM-8001 resistance meter, manufactured by Toa Denpa Kogyo Co., Ltd.) of the film obtained by casting 1 on a glass plate (4 cm × 5 cm) was 2.3 × 10 4 Ω.
【００１５】実施例２ 水１００ｍｌにポリスチレンスルホン酸５．２ｇ、硫酸
第１鉄（７水和物）１ｇ、ピロール２ｍｌを溶解する。
これに室温で攪拌しながら、過酸化水素（３１％水溶
液）７．７ｇを水で１００ｍｌとしたものをゆっくり滴
下（滴下時間、１時間）し、３時間反応させ、ポリピロ
ールコロイド水溶液を得た。得られたコロイド水溶液は
常温で１ヶ月間沈殿を認めなかった。又、この液１ｍｌ
をガラス板（４ｃｍ×５ｃｍ）にキャストして得たフィ
ルムの表面固有抵抗は４．７×１０5 Ωを示した。Example 2 In 100 ml of water, 5.2 g of polystyrenesulfonic acid, 1 g of ferrous sulfate (7 hydrate) and 2 ml of pyrrole were dissolved.
While stirring at room temperature, 7.7 g of hydrogen peroxide (31% aqueous solution) made up to 100 ml with water was slowly added dropwise (dripping time: 1 hour) and reacted for 3 hours to obtain a polypyrrole colloid aqueous solution. No precipitation was observed in the obtained aqueous colloid solution at room temperature for one month. Also, 1 ml of this liquid
The surface resistivity of the film obtained by casting on a glass plate (4 cm × 5 cm) was 4.7 × 10 5 Ω.
【００１６】実施例３ 水１００ｍｌにポリアクリル酸２ｇ、塩化第２鉄（６水
和物）６．８ｇを溶解し、７０℃に保った。これに攪拌
しながら、チオフェン２ｍｌをゆっくり滴下（滴下時
間、１時間）し、６時間反応させ、ポリチオフェンコロ
イド水溶液を得た。得られたコロイド水溶液をアンモニ
ア水（２５％）でｐＨ１０．０とした後、イソプロピル
アルコールで再沈、濾過し、濾物を水２００ｍｌで再分
散させ、精製コロイド水溶液を得た。得られた精製コロ
イド水溶液は常温で１ヵ月間沈殿を認めなかった。又、
この液１ｍｌをガラス板（４ｃｍ×５ｃｍ）にキャスト
して得たフィルムの表面固有抵抗は２．３×１０5 Ωを
示した。Example 3 2 g of polyacrylic acid and 6.8 g of ferric chloride (hexahydrate) were dissolved in 100 ml of water and kept at 70 ° C. While stirring, 2 ml of thiophene was slowly added dropwise (dropping time, 1 hour) and reacted for 6 hours to obtain a polythiophene colloid aqueous solution. The obtained aqueous colloid solution was adjusted to pH 10.0 with aqueous ammonia (25%), reprecipitated with isopropyl alcohol, filtered, and the filtered material was redispersed with 200 ml of water to obtain a purified aqueous colloid solution. The obtained purified colloidal aqueous solution showed no precipitation for one month at room temperature. or,
A film obtained by casting 1 ml of this solution on a glass plate (4 cm × 5 cm) had a surface specific resistance of 2.3 × 10 5 Ω.
【００１７】[0017]
【発明の効果】本発明によれば成形加工性の優れた導電
性高分子コロイド水溶液を容易に製造することができ
る。EFFECTS OF THE INVENTION According to the present invention, a conductive polymer colloidal aqueous solution having excellent moldability can be easily produced.
Claims (2)
Ｒ2 は水素原子、ハロゲン原子又は１価の有機基、Ｒ3
は水素原子又は１価の有機基を示す）で表される複素５
員環式化合物を、高分子酸の存在下で化学酸化重合する
ことを特徴とする導電性高分子コロイド水溶液の製造方
法。1. A general formula: (In the formula, X is —O—, —S— or —NR 3 —, R 1 and R 2 are hydrogen atom, halogen atom or monovalent organic group, R 3
Represents a hydrogen atom or a monovalent organic group) 5
A method for producing an aqueous solution of a conductive polymer colloid, which comprises subjecting a membered cyclic compound to chemical oxidative polymerization in the presence of a polymer acid.
とする請求項１の方法。2. The method according to claim 1, wherein the chemical oxidative polymerization is carried out in an aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34096293A JP3515799B2 (en) | 1993-12-10 | 1993-12-10 | Method for producing conductive polymer colloid aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34096293A JP3515799B2 (en) | 1993-12-10 | 1993-12-10 | Method for producing conductive polymer colloid aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07165892A true JPH07165892A (en) | 1995-06-27 |
| JP3515799B2 JP3515799B2 (en) | 2004-04-05 |
Family
ID=18341920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34096293A Expired - Lifetime JP3515799B2 (en) | 1993-12-10 | 1993-12-10 | Method for producing conductive polymer colloid aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3515799B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5965062A (en) * | 1996-08-16 | 1999-10-12 | Nec Corporation | Electrically-conductive polymer and production method thereof, and solid-electrolytic capacitor |
| JP2000052495A (en) * | 1998-08-06 | 2000-02-22 | Teijin Ltd | Release film |
| US6203727B1 (en) | 1997-10-15 | 2001-03-20 | The Dow Chemical Company | Electronically-conductive polymers |
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-
1993
- 1993-12-10 JP JP34096293A patent/JP3515799B2/en not_active Expired - Lifetime
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| US5965062A (en) * | 1996-08-16 | 1999-10-12 | Nec Corporation | Electrically-conductive polymer and production method thereof, and solid-electrolytic capacitor |
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| JP2007529609A (en) * | 2004-03-17 | 2007-10-25 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Water dispersible polypyrrole for electronic applications produced using polymeric acid colloids |
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