JPH0710973A - Polymerization in the presence of soluble polymer compound - Google Patents
Polymerization in the presence of soluble polymer compoundInfo
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- JPH0710973A JPH0710973A JP17204193A JP17204193A JPH0710973A JP H0710973 A JPH0710973 A JP H0710973A JP 17204193 A JP17204193 A JP 17204193A JP 17204193 A JP17204193 A JP 17204193A JP H0710973 A JPH0710973 A JP H0710973A
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- polymerization
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、可溶性高分子化合物共
存下に、π共役系導電性重合体を重合する方法、および
この重合法によって得られる液状物質およびその利用方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of polymerizing a π-conjugated conductive polymer in the presence of a soluble polymer compound, a liquid substance obtained by this polymerization method, and a method of using the same.
【０００２】従来より、導電性重合体としては、ポリア
セチレン、ポリアニリン、ポリピロロール、ポリチオフ
ェン、およびこれらの誘導体などがあり〔例えば、吉村
進著「導電性ポリマー」共立出版（１９８７）、山本，
松永著「ポリマーバッテリー」共立出版（１９９
０）〕、特にポリアニリン、ポリピロール、ポリチオフ
ェン誘導体などは工業化されている。しかしながら、こ
れらの導電性重合体の多くは不溶不融であるために、成
形性に劣り用途が限られている。特に、溶媒として最も
用いやすい水に可溶な導電性重合体は例が少なく、導電
性重合体が実用化されているアルミ電解コンデンサーや
静電気防止シートなどの製作上問題があった。Conventionally, as conductive polymers, there are polyacetylene, polyaniline, polypyrrole, polythiophene, and derivatives thereof (eg, Susumu Yoshimura, "Conductive Polymer" Kyoritsu Shuppan (1987), Yamamoto,
Matsunaga "Polymer Battery" Kyoritsu Publishing (199
0)], especially polyaniline, polypyrrole, polythiophene derivatives and the like have been industrialized. However, since many of these conductive polymers are insoluble and infusible, their moldability is poor and their applications are limited. In particular, there are few examples of a water-soluble conductive polymer that is most easily used as a solvent, and there is a problem in manufacturing an aluminum electrolytic capacitor, an antistatic sheet or the like in which the conductive polymer is put into practical use.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記従来技
術の課題を背景になされたもので、得られる導電性重合
体を実質的に溶存状態で存在させることが可能な導電性
重合体の重合法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and provides a conductive polymer capable of allowing the resulting conductive polymer to exist in a substantially dissolved state. It is intended to provide a polymerization method.
【０００４】[0004]
【課題を解決するための手段】本発明は、重合によりπ
共役系導電性重合体となり得る単量体（以下「単量体」
ということがある）から選ばれた少なくとも１種を、
（Ａ）遷移金属元素もしくはその化合物、（Ｂ）過酸化
物および酸、ならびに（Ｃ）重合溶媒および該重合溶媒
に可溶な高分子化合物（以下「可溶性高分子化合物」と
いうことがある）の存在下で重合することを特徴とする
可溶性高分子化合物共存下の重合法、得られる重合体を
コロイド状態またはエマルジョン状態で含有する液状物
質、該重合体を含有する導電性コーティング材、を提供
するものである。SUMMARY OF THE INVENTION The present invention is based on the polymerization of π
A monomer that can be a conjugated conductive polymer (hereinafter referred to as "monomer")
At least one selected from
(A) transition metal element or compound thereof, (B) peroxide and acid, and (C) polymerization solvent and polymer compound soluble in the polymerization solvent (hereinafter sometimes referred to as “soluble polymer compound”) Provided are a polymerization method in the presence of a soluble polymer compound, which is characterized by polymerizing in the presence, a liquid substance containing the obtained polymer in a colloidal state or an emulsion state, and a conductive coating material containing the polymer. It is a thing.
【０００５】以下、本発明を詳細に説明する。本発明に
おいて、重合によりπ共役系導電性重合体となり得る単
量体としては、複素５員環化合物、芳香族アミン化合物
が挙げられる。このうち、複素５員環化合物としては、
ピロール、チオフェン、フランなどが挙げられるが、こ
れらのなかでは、ピロールが好ましい。また、これらの
誘導体としてピロールを例にとれば、Ｎ−メチルピロー
ル、Ｎ−エチルピロール、Ｎ−フェニルピロール、３−
メチルピロール、３−エチルピロール、３−メトキシピ
ロール、３−エトキシピロール、３−フェノキシピロー
ル、３−アミノピロール、３−メチルフェニルアミノピ
ロール、３，４−ジメチルピロール、３，４−ジフェニ
ルピロール、Ｎ−メチル−３−メチルピロール、Ｎ−フ
ェニル−３−メチルピロールなどが挙げられる。The present invention will be described in detail below. In the present invention, examples of the monomer that can be converted into a π-conjugated conductive polymer by polymerization include a hetero 5-membered ring compound and an aromatic amine compound. Among these, as the hetero 5-membered ring compound,
Pyrrole, thiophene, furan and the like can be mentioned, but of these, pyrrole is preferable. When pyrrole is taken as an example of these derivatives, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, 3-
Methylpyrrole, 3-ethylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-phenoxypyrrole, 3-aminopyrrole, 3-methylphenylaminopyrrole, 3,4-dimethylpyrrole, 3,4-diphenylpyrrole, N -Methyl-3-methylpyrrole, N-phenyl-3-methylpyrrole and the like can be mentioned.
【０００６】また、芳香族アミン化合物の例としては、
アニリン、ｐ−フェニレンジアミン、ｍ−フェニレンジ
アミン、トルエン−２，５−ジアミン、ｐ−アミノフェ
ノール、ｍ−アミノフェノール、２，６−ジアミノピリ
ジン、およびこれらの塩などが挙げられる。Further, examples of the aromatic amine compound include
Examples thereof include aniline, p-phenylenediamine, m-phenylenediamine, toluene-2,5-diamine, p-aminophenol, m-aminophenol, 2,6-diaminopyridine, and salts thereof.
【０００７】次に、（Ａ）遷移金属元素もしくはその化
合物は、π共役系導電性重合体となり得る単量体を酸化
剤で酸化重合する反応における触媒としての作用をなす
ものである。ここで、（Ａ）遷移金属元素もしくはその
化合物としては、原子番号２１〜３０、３９〜４８、５
７〜８０、および８９以上の元素、ならびにこれらの酸
化物、塩、キレート化合物などの遷移金属元素化合物が
挙げられる。これらの中では、遷移金属元素化合物が好
ましい。これらの遷移金属元素のうち好ましいものは、
チタン、バナジウム、クロム、マンガン、鉄、コバル
ト、ニッケル、銅、イットリウム、ジルコニウム、モリ
ブデン、ルテニウムなどであり、特に好ましいものは、
鉄、銅である。Next, the transition metal element (A) or its compound serves as a catalyst in a reaction of oxidatively polymerizing a monomer which can be a π-conjugated conductive polymer with an oxidizing agent. Here, as the (A) transition metal element or compound thereof, atomic numbers 21 to 30, 39 to 48, 5
7-80, and 89 or more elements, and transition metal element compounds such as oxides, salts, and chelate compounds thereof. Of these, transition metal element compounds are preferable. Among these transition metal elements, preferred ones are
Titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, molybdenum, ruthenium and the like, particularly preferable ones are
Iron and copper.
【０００８】遷移金属元素の、酸化物としては二酸化マ
ンガンなどが、塩としては硫酸、塩酸、硝酸、酢酸など
の塩が好ましく、その好ましい例としては硫酸鉄、硫酸
銅、塩化鉄、塩化銅、塩化モリブデン、塩化タングステ
ン、硝酸鉄、硝酸銅などを挙げることができる。また、
遷移金属元素のキレート化合物としては、各種遷移金属
元素と、エチレンジアミン四酢酸、ニトリロ三酢酸、ジ
メチルグリオキシム、ジチゾン、オキシン、アセチルア
セトン、グリシンなどのキレート剤を組み合わせた化合
物が挙げられる。これらの（Ａ）成分のうち、好ましく
は塩であり、特に硫酸鉄（II) 、硫酸鉄（III)、塩化鉄
（II) 、塩化鉄（III)、硫酸銅（II) 、塩化銅（II) な
どが好ましい。As the oxide of the transition metal element, manganese dioxide and the like are preferable, and as the salt, salts such as sulfuric acid, hydrochloric acid, nitric acid and acetic acid are preferable, and preferable examples thereof are iron sulfate, copper sulfate, iron chloride, copper chloride, Examples thereof include molybdenum chloride, tungsten chloride, iron nitrate and copper nitrate. Also,
Examples of the chelate compound of a transition metal element include compounds in which various transition metal elements are combined with a chelating agent such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, dimethylglyoxime, dithizone, oxine, acetylacetone, and glycine. Of these (A) components, salts are preferable, and especially iron (II) sulfate, iron (III) sulfate, iron (II) chloride, iron (III) chloride, copper (II) sulfate, copper (II) chloride ) And the like are preferable.
【０００９】次に、（Ｂ）過酸化物および酸は、π共役
系導電性重合体となり得る単量体を酸化重合する反応に
おける、酸化剤および酸化促進剤としての作用をなすも
のである。（Ｂ）成分のうち、過酸化物としては、過酸
化水素のほか、過酸化ベンゾイル、過酸化ラウリルなど
のジアシルパーオキサイド、クメンハイドロパーオキサ
イド、ｔ−ブチルハイドロパーオキサイド、ｐ−メンタ
ンハイドロパーオキサイドなどのハイドロパーオキサイ
ド、ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキ
サイドなどのジアルキルパーオキサイド、ｔ−ブチルパ
ーオキシエチルヘキサノエートなどのパーオキシエステ
ルなどの有機過酸化物が挙げられる。また、過硫酸アン
モニウム、過硫酸ナトリウム、過硫酸カリウムなどのペ
ルオキソ酸塩も使用することができる。これらの過酸化
物のうち、最も活性が良く好ましい過酸化物は、過酸化
水素である。Next, the (B) peroxide and the acid function as an oxidant and an oxidation accelerator in the reaction of oxidatively polymerizing the monomer which can be the π-conjugated conductive polymer. Among the components (B), peroxides include hydrogen peroxide, diacyl peroxides such as benzoyl peroxide and lauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide. Examples thereof include hydroperoxides, dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide, and organic peroxides such as peroxyesters such as t-butylperoxyethylhexanoate. Further, peroxo acid salts such as ammonium persulfate, sodium persulfate and potassium persulfate can also be used. Among these peroxides, hydrogen peroxide is the most active and preferable peroxide.
【００１０】また、（Ｂ）成分のうち、酸としては、塩
酸、硫酸、硝酸、臭化水素などの無機酸、アルキルベン
ゼンスルホン酸、アルキルナフタレンスルホン酸などの
有機酸が挙げられる。これらの酸のうち、好ましいもの
としては、塩酸、硫酸、臭化水素が挙げられる。Among the components (B), examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and hydrogen bromide, and organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid. Among these acids, preferred are hydrochloric acid, sulfuric acid and hydrogen bromide.
【００１１】ピロールなどの上記単量体は、（Ａ）成
分、（Ｂ）成分の単独使用でも重合することができる
が、少量の触媒量で短時間に重合でき、かつ合成された
微粒子の溶媒中でのコロイド的な分散安定化効果の点か
ら、本発明では、（Ａ）成分と（Ｂ）成分とを併用す
る。この結果、安全性、生成導電性重合体の安定性、廃
棄物の処理の容易さなどに優れた重合体を製造すること
ができる。The above-mentioned monomers such as pyrrole can be polymerized by using the component (A) and the component (B) alone, but they can be polymerized in a short time with a small amount of catalyst, and the solvent of the synthesized fine particles. In the present invention, the component (A) and the component (B) are used together from the viewpoint of colloidal dispersion stabilizing effect. As a result, it is possible to produce a polymer excellent in safety, stability of the produced conductive polymer, and ease of disposal of waste.
【００１２】（Ａ）成分および（Ｂ）成分の使用量は、
上記単量体１モルに対し、（Ａ）成分が好ましくは０．
００１〜０．５モル、さらに好ましくは０．００２〜
０．２モル、特に好ましくは０．００３〜０．１モル、
（Ｂ）成分が好ましくは０．１〜２０モル、さらに好ま
しくは０．２〜１０モル、特に好ましくは０．３〜５モ
ルである。（Ａ）成分が０．００１モル未満では、触媒
としての作用が不充分のため酸化重合がきわめて長時間
を要し、生産性の点で欠点となり、一方０．５モルを超
えると、生成した重合体に遷移金属イオンが不純物とし
て残留し、導電性の安定性の面から欠点となり、またコ
ーティング材を作製する場合、多量の遷移金属イオンが
存在すると、他のバインダーポリマー液を凝固不安定化
するため、混合できない欠点もある。また、（Ｂ）成分
が０．１モル未満では、酸化剤が不足し重合転化率が低
くなってしまい、一方２０モルを超えると、過剰の酸化
剤が残留し、導電性の性能が経時的に劣化してくるとい
う問題がある。The amounts of components (A) and (B) used are
The component (A) is preferably 0.
001-0.5 mol, more preferably 0.002-
0.2 mol, particularly preferably 0.003 to 0.1 mol,
The component (B) is preferably 0.1 to 20 mol, more preferably 0.2 to 10 mol, and particularly preferably 0.3 to 5 mol. When the amount of the component (A) is less than 0.001 mol, the action as a catalyst is insufficient, so that the oxidative polymerization takes a very long time, which is a drawback in terms of productivity. On the other hand, when the amount exceeds 0.5 mol, it is generated. Transition metal ions remain as impurities in the polymer, which is a drawback from the viewpoint of stability of conductivity, and when a large amount of transition metal ions are present when preparing a coating material, other binder polymer liquids are destabilized and solidified. Therefore, there is a drawback that they cannot be mixed. On the other hand, if the amount of the component (B) is less than 0.1 mol, the oxidant will be insufficient and the polymerization conversion will be low. On the other hand, if it exceeds 20 mol, an excessive amount of the oxidant will remain and the electroconductivity will deteriorate with time. There is a problem of deterioration.
【００１３】また、（Ａ）成分と（Ｂ）成分のうちの過
酸化物の使用割合は、過酸化物１モルに対し、（Ａ）成
分０．０００２〜０．２モル、好ましくは０．００１〜
０．１モル、特に好ましくは０．００２〜０．０５モル
である。過酸化物１モルに対し、（Ａ）成分が、０．０
００２モル未満では、酸化重合に長時間を要し、生産上
欠点となり、一方０．２モルを超えると、残留遷移金属
イオンが導電性に悪影響となり性能上好ましくない。The proportion of the peroxide used in the components (A) and (B) is 0.0002 to 0.2 mol, preferably 0.002 mol, per 1 mol of the peroxide. 001-
0.1 mol, particularly preferably 0.002 to 0.05 mol. The component (A) is 0.0 per mol of the peroxide.
If it is less than 002 mol, oxidative polymerization will take a long time, which will be a drawback in production.
【００１４】さらに、（Ｂ）成分としては、過酸化物ま
たは酸の各々単独の使用でもよいが、両者を組み合わせ
て使用する方が、高い重合転化率が得られる点ので、本
発明では、過酸化物と酸とを併用する。過酸化物と酸の
使用割合は、好ましくは過酸化物１モルに対し、酸を
０．１〜１０モル、さらに好ましくは０．２〜５モルで
ある。０．１モル未満では、重合転化率が低くなる欠点
があり、一方１０モルを超えると、酸が残留し、導電性
の性能上不安定となる。Further, as the component (B), a peroxide or an acid may be used alone, but a combination of the two may give a higher polymerization conversion rate. An oxide and an acid are used together. The use ratio of the peroxide and the acid is preferably 0.1 to 10 mol, more preferably 0.2 to 5 mol of the acid with respect to 1 mol of the peroxide. If it is less than 0.1 mol, there is a drawback that the polymerization conversion rate becomes low, while if it exceeds 10 mol, the acid remains and the conductivity becomes unstable.
【００１５】次に、（Ｃ）成分のうち、重合溶媒として
は特に制限はないが、水、メタノール、エタノール、ア
セトン、アセトニトリルなどが挙げられるが、特に好ま
しくは水である。重合溶媒の使用量は、上記単量体１０
０重量部に対し、好ましくは１，０００〜１００，００
０重量部、好ましくは２，０００〜５０，０００重量部
程度である。Next, of the component (C), the polymerization solvent is not particularly limited, and examples thereof include water, methanol, ethanol, acetone, acetonitrile and the like, and water is particularly preferable. The amount of the polymerization solvent used is the above-mentioned monomer 10.
It is preferably 1,000 to 100,000 with respect to 0 parts by weight.
The amount is 0 parts by weight, preferably about 2,000 to 50,000 parts by weight.
【００１６】また、（Ｃ）成分のうち、上記重合溶媒に
可溶で、重合時に共存させる可溶性高分子化合物として
は、特に制限はない。例えば、重合溶媒として水を使用
する場合には、可溶性高分子化合物としては、ポリビニ
ルピロリドン、ポリビニルアルコール、ポリエチレンイ
ミン、ポリエチレンオキサイド、ポリアクリル酸などの
水溶性高分子を用いるのがよい。特に、ポリビニルピロ
リドンは、生成導電性重合体の実質的な分散状態の安定
性に大きな効果があり、またポリビニルアルコールは、
生成導電性重合体を含む液状物質をキャストして生成す
るフィルムの強度向上に有効である。可溶性高分子化合
物の使用量は、上記単量体１００重量部に対し、好まし
くは１〜１，０００重量部、さらに好ましくは５〜４０
０重量部であり、１重量部未満では系が不安定化し凝
集、沈澱が生じ、一方１，０００重量部を超えると、分
散液（コロイド状態またはエマルジョン状態の液状物
質）を成膜した場合、膜の導電性が不良となる。Of the component (C), the soluble polymer compound which is soluble in the above-mentioned polymerization solvent and coexists during the polymerization is not particularly limited. For example, when water is used as the polymerization solvent, a water-soluble polymer such as polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide or polyacrylic acid is preferably used as the soluble polymer compound. In particular, polyvinylpyrrolidone has a great effect on the stability of the substantially dispersed state of the resulting conductive polymer, and polyvinyl alcohol is
It is effective for improving the strength of a film produced by casting a liquid substance containing the produced conductive polymer. The amount of the soluble polymer compound used is preferably 1 to 1,000 parts by weight, more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the above-mentioned monomer.
When the amount is 0 part by weight, and the amount is less than 1 part by weight, the system becomes unstable and agglomeration and precipitation occur. The conductivity of the film becomes poor.
【００１７】重合法としては、アニリン、ピロール、チ
オフェンなどの上記単量体を、上記重合溶媒中におい
て、上記（Ａ）成分および（Ｂ）成分の存在下に酸化重
合を行う。酸化重合としては、例えば特願平１−１７０
８１９号明細書、同４−４７９２０号明細書、同５−４
０４９２号明細書、あるいはＭａｋｒｏｍｏｌ．Ｃｈｅ
ｍ．，１９３巻，１７２３頁（１９９２）、Ｓｙｎｔｈ
ｅｔｉｃ Ｍｅｔａｌｓ，３１巻，３１１頁（１９８
９）、Ｃｈｅｍ．Ｅｘｐｒｅｓｓ，１巻，６３５頁（１
９８６）などに記載されている方法に準じて行うことが
できる。As the polymerization method, the above-mentioned monomers such as aniline, pyrrole and thiophene are oxidatively polymerized in the above-mentioned polymerization solvent in the presence of the above-mentioned components (A) and (B). Examples of the oxidative polymerization include Japanese Patent Application No. 1-170.
No. 819, No. 4-47920, No. 5-4
0492, or Makromol. Che
m. , 193, 1723 (1992), Synth
etic Metals, vol. 31, p. 311 (198)
9), Chem. Express, Volume 1, Page 635 (1
986) and the like.
【００１８】なお、重合温度は、好ましくは０〜１００
℃、さらに好ましくは５〜５０℃、重合時間は、好まし
くは０．１〜５０時間、さらに好ましくは０．２〜１０
時間である。また、重合系における上記単量体濃度は、
好ましくは０．１〜１０重量％、さらに好ましくは０．
２〜５重量％程度である。The polymerization temperature is preferably 0-100.
℃, more preferably 5 to 50 ℃, the polymerization time is preferably 0.1 to 50 hours, more preferably 0.2 to 10 hours.
It's time. Further, the monomer concentration in the polymerization system,
Preferably 0.1 to 10% by weight, more preferably 0.1.
It is about 2 to 5% by weight.
【００１９】この酸化重合に際して、上記可溶性高分子
化合物を共存させると、生成した導電性重合体がある程
度長期間にわたり沈澱することなく、実質的に重合溶媒
中に安定な分散状態（コロイド状態またはエマルジョン
状態）で存在する液状物質として得られる。このよう
に、生成導電性重合体が、実質的に溶存状態で存在する
ことにより、この導電性重合体を含有する液状物質を導
電性コーティング材として、塗布法によりアルミ電解コ
ンデンサー細孔内部の電極を形成させ、また紙などにコ
ーティングして導電性材料を得ることなどが可能とな
り、応用範囲を拡げることができる。また、この導電性
重合体を利用して、各種電子・光デバイスに用いること
が可能となる。In the oxidative polymerization, when the above-mentioned soluble polymer compound is allowed to coexist, the produced conductive polymer does not precipitate for a certain period of time, and is substantially stable in the polymerization solvent (colloidal state or emulsion). It is obtained as a liquid substance existing in the (state). As described above, since the generated conductive polymer is present in a substantially dissolved state, the liquid substance containing the conductive polymer is used as the conductive coating material, and the electrode inside the pores of the aluminum electrolytic capacitor is applied by the coating method. It is also possible to form a conductive material and obtain a conductive material by coating it on paper or the like, and the range of applications can be expanded. Further, it becomes possible to use this conductive polymer for various electronic and optical devices.
【００２０】[0020]
【実施例】以下、実施例を挙げて本発明をさらに具体的
に説明する。なお、実施例中、部および％は、特に断ら
ない限り重量基準である。また、実施例中の各種評価
は、次のようにして測定した値である。EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. Further, various evaluations in the examples are values measured as follows.
【００２１】導電率 得られた分散液を基板（ガラス板を用いた）に塗布し、
自然乾燥することによりフィルム化し、三菱油化（株）
製、Ｌｏｒｅｓｔａ−ＡＰを用い、４探針法で測定し
た。重合安定性 ガラス板上に重合後の分散液を一滴落とし、凝集物の有
無を判定した。凝集物がほとんど無い状態を○、一部の
み凝集しているものを△、全体的に凝集しているものを
×とした。 Conductivity The obtained dispersion is applied to a substrate (using a glass plate),
A film is formed by natural drying, and Mitsubishi Petrochemical Co., Ltd.
Manufactured by Loresta-AP, and measured by the 4-probe method. A drop of the dispersion liquid after the polymerization was dropped on a polymerization stability glass plate, and the presence or absence of aggregates was determined. The state in which there were almost no aggregates was marked with ◯, the one in which some were aggregated was marked with Δ, and the one in which all were aggregated was marked with x.
【００２２】実施例１〜１３、比較例１〜６ ポリビニルピロリドン〔ＰＶＰ（分子量＝３６０，００
０）〕および／またはポリビニルアルコール〔ＰＶＡ
（分子量＝７３，０００）〕を溶かし込んだ水中に、室
温で単量体、酸、遷移金属化合物を加えて溶解させたの
ち、攪拌しながら１５％濃度の過酸化水素水を加えて酸
化重合を行った。過酸化水素添加後、反応系の色は暗緑
色〜黒色に変化し、重合が進行していることが確認され
た。このまま攪拌を続け、２４時間重合反応を行った。
重合終了時においても、沈澱の生成は認められなかっ
た。Examples 1 to 13 and Comparative Examples 1 to 6 Polyvinylpyrrolidone [PVP (Molecular weight = 360,00
0)] and / or polyvinyl alcohol [PVA
(Molecular weight = 73,000)] is dissolved in water at room temperature by adding a monomer, an acid and a transition metal compound, and then 15% hydrogen peroxide solution is added with stirring to perform oxidative polymerization. I went. After the addition of hydrogen peroxide, the color of the reaction system changed from dark green to black, and it was confirmed that the polymerization was proceeding. The stirring was continued as it was, and the polymerization reaction was carried out for 24 hours.
No precipitation was observed even at the end of the polymerization.
【００２３】このようにして得られた重合液を、基板上
にキャストしたのち、２４時間真空乾燥して充分な強度
を持つフィルムを得て、このフィルムについて導電率を
測定した。重合結果およびフィルムの導電率を表１〜３
に示す。また、上記重合液中に存在する微粒子状重合体
の電子顕微鏡による観察の結果、実施例１〜１３におい
ては、粒径２０〜３０ｎｍの微粒子状の重合体がさらに
集まって４００〜６００ｎｍの粒径を持つ微粒子となっ
ていることが分かった。この重合液中では、生成導電性
重合体（本実施例においては、ポリアニリン、ポリピロ
ール）が、このような微粒子状に形成され、ＰＶＰなど
の共存可溶性高分子化合物の安定化効果により、該重合
液中に実質的に溶存状態で存在するものと考えられる。The polymerization solution thus obtained was cast on a substrate and vacuum dried for 24 hours to obtain a film having sufficient strength, and the conductivity of this film was measured. The results of polymerization and the conductivity of the film are shown in Tables 1 to 3.
Shown in. In addition, as a result of observing the fine particle polymer existing in the above-mentioned polymerization liquid with an electron microscope, in Examples 1 to 13, fine particle polymers having a particle diameter of 20 to 30 nm are further gathered to have a particle diameter of 400 to 600 nm. It was found to be fine particles with. In this polymerization liquid, the resulting conductive polymer (polyaniline, polypyrrole in this example) is formed into such fine particles, and due to the stabilizing effect of the coexisting soluble polymer compound such as PVP, the polymerization liquid is formed. It is considered that the substance is present in a substantially dissolved state.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【表３】 [Table 3]
【００２７】表１〜３中、Ａ；アニリン、Ｂ；ピロー
ル、Ｃ；ＦｅＣｌ3 、Ｄ；ＦｅＳＯ4、Ｅ；ＣｕＳ
Ｏ4 、Ｆ；ＨＢｒ、Ｇ；ＨＣｌ、Ｉ；Ｈ2 ＳＯ4 を示
す。In Tables 1 to 3, A: aniline, B: pyrrole, C: FeCl 3 , D: FeSO 4 , E: CuS.
O 4, F; HBr, G ; HCl, I; shows the H 2 SO 4.
【００２８】表１〜２から明らかなように、実施例１〜
１３においては、得られるキャストフィルムの導電性が
良好で、重合転化率も高く、重合安定性も優れており、
本発明の効果を奏していることが分かる。これに対し、
表３から明らかなように、比較例１は（Ｂ）成分の酸の
添加がないため、得られるキャストフィルムの導電性が
悪く、重合転化率も低いうえ、重合安定性も悪い。比較
例２は、（Ｂ）成分中に過酸化水素が添加されていない
ため、得られるキャストフィルムの導電性が悪く、重合
転化率も低いうえ、重合安定性も悪い。比較例３は、重
合系中に可溶性高分子化合物を共存させていないため、
成膜が不可能で、重合安定性も極めて悪い。比較例４
は、重合系に（Ｂ）成分を添加していないため、得られ
るキャストフィルムの導電性が悪く、重合転化率も極め
て低いうえ、重合安定性が極めて悪い。比較例５は、重
合系に（Ａ）成分を添加していないため、導電性が悪
く、重合転化率も低く、また重合安定性も悪い。比較例
６は、重合系に（Ａ）成分および（Ｂ）成分中に過酸化
水素を添加していない例であり、導電性が悪く、重合転
化率も低く、また重合安定性も悪い。As is clear from Tables 1 and 2, Examples 1 to 1
In No. 13, the cast film obtained has good conductivity, high polymerization conversion rate, and excellent polymerization stability.
It can be seen that the effects of the present invention are exhibited. In contrast,
As is clear from Table 3, in Comparative Example 1, since the component (B) acid was not added, the cast film obtained had poor conductivity, low polymerization conversion, and poor polymerization stability. In Comparative Example 2, since hydrogen peroxide was not added to the component (B), the cast film obtained had poor conductivity, low polymerization conversion, and poor polymerization stability. In Comparative Example 3, since the soluble polymer compound does not coexist in the polymerization system,
Film formation is not possible and polymerization stability is extremely poor. Comparative Example 4
Since the component (B) is not added to the polymerization system, the obtained cast film has poor conductivity, the polymerization conversion rate is extremely low, and the polymerization stability is extremely poor. In Comparative Example 5, since the component (A) was not added to the polymerization system, the conductivity was poor, the polymerization conversion rate was low, and the polymerization stability was poor. Comparative Example 6 is an example in which hydrogen peroxide was not added to the components (A) and (B) in the polymerization system, and the conductivity was poor, the polymerization conversion rate was low, and the polymerization stability was poor.
【００２９】[0029]
【発明の効果】本発明によれば、π共役系導電性重合体
となり得る単量体を、特定の触媒系を用いて可溶性高分
子化合物の存在下に酸化重合することにより、重合転化
率が高く、得られる重合液の分散性が安定し、成膜性が
良好で、コーティング材としても有用な液状物質を得る
ことができ、アルミ電解コンデンサー、静電気防止シー
トなどの各種の用途に利用することが可能である。INDUSTRIAL APPLICABILITY According to the present invention, a monomer capable of becoming a π-conjugated conductive polymer is oxidatively polymerized in the presence of a soluble polymer compound by using a specific catalyst system, whereby the polymerization conversion rate is improved. High, stable dispersibility of the obtained polymerization liquid, good film-forming property, and can be used as a coating material to obtain a liquid substance that can be used in various applications such as aluminum electrolytic capacitors and antistatic sheets. Is possible.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 179/00 ＰＬＵ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area C09D 179/00 PLU
Claims (4)
得る単量体から選ばれた少なくとも１種を、（Ａ）遷移
金属元素もしくはその化合物、（Ｂ）過酸化物および
酸、ならびに（Ｃ）重合溶媒および該重合溶媒に可溶な
高分子化合物の存在下で重合することを特徴とする可溶
性高分子化合物共存下の重合法。1. At least one selected from monomers that can be converted into a π-conjugated conductive polymer by polymerization is (A) a transition metal element or a compound thereof, (B) a peroxide and an acid, and (C). ) A polymerization method in the presence of a soluble polymer compound, which comprises polymerizing in the presence of a polymerization solvent and a polymer compound soluble in the polymerization solvent.
沈澱することなく、コロイド状態またはエマルジョン状
態で存在するように重合反応を行う請求項１記載の可溶
性高分子化合物共存下の重合法。2. The polymerization method in the coexistence of a soluble polymer compound according to claim 1, wherein the polymerization reaction is carried out so that the obtained polymer is present in a colloidal state or an emulsion state without being precipitated in a polymerization solvent.
法によって得られる重合体をコロイド状態またはエマル
ジョン状態で含有する液状物質。3. A liquid substance containing the polymer obtained by the polymerization method according to claim 1 or 2 in a colloidal state or an emulsion state.
法によって得られる重合体を含有するコーティング材。4. A coating material containing the polymer obtained by the polymerization method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17204193A JP3222990B2 (en) | 1993-06-21 | 1993-06-21 | Polymerization method in the presence of soluble polymer compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17204193A JP3222990B2 (en) | 1993-06-21 | 1993-06-21 | Polymerization method in the presence of soluble polymer compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710973A true JPH0710973A (en) | 1995-01-13 |
| JP3222990B2 JP3222990B2 (en) | 2001-10-29 |
Family
ID=15934440
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17204193A Expired - Fee Related JP3222990B2 (en) | 1993-06-21 | 1993-06-21 | Polymerization method in the presence of soluble polymer compound |
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| Country | Link |
|---|---|
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Cited By (11)
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|---|---|---|---|---|
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| EP0821041A3 (en) * | 1996-07-22 | 1998-02-04 | Dsm N.V. | Aqueous coating dispersion, process for the preparation thereof and use thereof in anticorrosive paint |
| JP2005194528A (en) * | 2003-12-30 | 2005-07-21 | E I Du Pont De Nemours & Co | Polyimide base composition comprising doped polyaniline, its related method and composition |
| JP2006500461A (en) * | 2002-09-24 | 2006-01-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Water-dispersible polyaniline produced using polymer acid colloids for electronics applications |
| JP2006176753A (en) * | 2004-11-24 | 2006-07-06 | Tokai Rubber Ind Ltd | Method for producing conductive polymer solution |
| JP2007016133A (en) * | 2005-07-07 | 2007-01-25 | Nippon Soda Co Ltd | Polypyrrole and method for producing the same |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0821040A1 (en) * | 1996-07-22 | 1998-01-28 | Dsm N.V. | Aqueous coating dispersion, process for the preparation thereof and use thereof in anticorrosive paint |
| EP0821041A3 (en) * | 1996-07-22 | 1998-02-04 | Dsm N.V. | Aqueous coating dispersion, process for the preparation thereof and use thereof in anticorrosive paint |
| JP2006500461A (en) * | 2002-09-24 | 2006-01-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Water-dispersible polyaniline produced using polymer acid colloids for electronics applications |
| JP2011190452A (en) * | 2002-09-24 | 2011-09-29 | E I Du Pont De Nemours & Co | Water dispersible polyaniline made with polymeric acid colloid for electronics application |
| JP2005194528A (en) * | 2003-12-30 | 2005-07-21 | E I Du Pont De Nemours & Co | Polyimide base composition comprising doped polyaniline, its related method and composition |
| JP2006176753A (en) * | 2004-11-24 | 2006-07-06 | Tokai Rubber Ind Ltd | Method for producing conductive polymer solution |
| JP2007016133A (en) * | 2005-07-07 | 2007-01-25 | Nippon Soda Co Ltd | Polypyrrole and method for producing the same |
| JP2008127438A (en) * | 2006-11-17 | 2008-06-05 | Canon Inc | Manufacturing method of substituted polyacetylene film |
| US8618423B2 (en) | 2007-03-28 | 2013-12-31 | Sanyo Electric Co., Ltd. | Mounting board including a flat-type electrical element and capable of being reduced in size, and lead-attached electric element that is flat in shape and has a lead bonded to each electrode face |
| JP2011508954A (en) * | 2008-01-04 | 2011-03-17 | オルメコン・ゲーエムベーハー | Method for producing coating film showing high conductivity based on polythiophene and its derivatives |
| JP2010018698A (en) * | 2008-07-10 | 2010-01-28 | Nagase Chemtex Corp | Composition for electroconductive coating and aqueous dispersion containing conductive polymer |
| JP2010132757A (en) * | 2008-12-04 | 2010-06-17 | Japan Carlit Co Ltd:The | Method for producing electroconductive polymer and for producing aqueous dispersion of the same polymer |
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