JPH0517259B2 - - Google Patents
Info
- Publication number
- JPH0517259B2 JPH0517259B2 JP57185999A JP18599982A JPH0517259B2 JP H0517259 B2 JPH0517259 B2 JP H0517259B2 JP 57185999 A JP57185999 A JP 57185999A JP 18599982 A JP18599982 A JP 18599982A JP H0517259 B2 JPH0517259 B2 JP H0517259B2
- Authority
- JP
- Japan
- Prior art keywords
- alkyl group
- formula
- conductive material
- conductive polymer
- conductive
- 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
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
［産業上の利用分野］
本発明は導電性材料の存在下で重合して得られ
る主鎖に共役二重結合連鎖を有する導電性重合体
と該導電性材料との電導性重合体組成物に関する
ものである。
［従来の技術］および［発明が解決しようとする
問題点］
従来より重合体の導電性を上げるため重合体粉
末と導電性材料を機械的に混合した組成物は知ら
れているが、いずれの方法を採用しても混合性が
きわめて悪く、そのため組成物の機械的強度が低
くかつ組成物がもろく、組成物を応用した用途
（たとえば電池の電極）の物性に極めて悪い影響
を与える。
また、特開昭57−123659号公報に提案されてい
るように、触媒と導電性材料との混合物にアセチ
レンを接触させてフイルムを作つた場合、アセチ
レンガスが順次表面から重合するため、このフイ
ルムの構造が層状になり、結果として導電性材料
の濃度がフイルムの表面と内部とで著しく違い、
機械的強度及び電導度の低下をきたすといつたよ
うな問題点を有している。
［問題を解決するための手段］
以上のことから、本発明者らはこの問題を解決
すべく種々探索した結果、導電性材料の存在下に
単量体を攪拌下に均一に混合して重合することに
より、きわめて混合性の良い電導性重合体組成物
を得た。このように重合時に導電性材料が存在す
るとなぜ混合性が良くなるかは不明であるが、導
電性材料と重合体が共有結合のようなある程度強
固な結合を作つているものと考えられる。
すなわち本発明は、導電性重合体の下記の繰返
し単位に相当する単量体と導電性材料とを攪拌下
に均一に混合して重合せしめることを特徴とす
る、導電性材料が均一に分散し且つ下記の繰返し
単位のいずれかを有する導電性重合体を含む電導
性重合体組成物の製造方法である。
(1) ［−CR1＝CR2−］
(2)
[Industrial Application Field] The present invention relates to a conductive polymer composition comprising a conductive polymer having a conjugated double bond chain in the main chain obtained by polymerization in the presence of a conductive material, and the conductive material. It is something. [Prior Art] and [Problems to be Solved by the Invention] Compositions in which a polymer powder and a conductive material are mechanically mixed in order to increase the conductivity of the polymer have been known. Even if this method is adopted, the mixing properties are extremely poor, resulting in low mechanical strength and brittleness of the composition, which has an extremely negative effect on the physical properties of applications to which the composition is applied (for example, battery electrodes). Furthermore, as proposed in JP-A-57-123659, when a film is made by bringing acetylene into contact with a mixture of a catalyst and a conductive material, the acetylene gas polymerizes sequentially from the surface. The structure of the film becomes layered, and as a result, the concentration of the conductive material differs significantly between the surface and inside of the film.
It has problems such as a decrease in mechanical strength and electrical conductivity. [Means for Solving the Problem] Based on the above, the present inventors have conducted various searches to solve this problem. As a result, the inventors have discovered that monomers are uniformly mixed under stirring in the presence of a conductive material and then polymerized. By doing so, a conductive polymer composition with extremely good miscibility was obtained. Although it is unclear why the presence of a conductive material during polymerization improves the mixing properties, it is thought that the conductive material and the polymer form a somewhat strong bond such as a covalent bond. That is, the present invention is characterized in that monomers corresponding to the following repeating units of a conductive polymer and a conductive material are uniformly mixed and polymerized under stirring, so that the conductive material is uniformly dispersed. Moreover, it is a method for producing a conductive polymer composition containing a conductive polymer having any of the following repeating units. (1) [-CR 1 = CR 2 -] (2)
【式】 (3)【formula】 (3)
【式】または (4)[expression] or (Four)
【式】
（但し、式中、R1，R2は夫々、水素原子、ハ
ロゲン原子、炭素数が５以下のアルキル基または
フエニル基（低級アルキル基で置換されていても
良い）を、R3はイミノ基（炭素数が５以下のア
ルキル基で置換されていても良い）または硫黄原
子を、また、R4，R5，R6，R7は夫々、水素原子
または炭素数が５以下のアルキル基を表し、ｎは
０または１である。）
本発明に使用される導電性材料としては、金属
微粉、金属繊維、金属網またはカーボンブラツ
ク、アセチレンブラツク、炭素繊維、黒鉛等の如
き炭素及びそれらの混合物、および合成樹脂と前
記導電性材料との複合体を挙げることができる。
これらの導電性材料の電気伝導度は10-5Ω-1・cm
−１以上、好ましくは10-3Ω-1・cm-1、特に好まし
くは、10-1Ω-1・cm-1以上である。
また本発明で合成して得られる主鎖に共役二重
結合連鎖を有する導電性重合体としては、下記の
繰返し単位のいずれかを有する重合体である；
(1) ［−CR1＝CR2−］
(2)[Formula] (In the formula, R 1 and R 2 each represent a hydrogen atom, a halogen atom, an alkyl group having 5 or less carbon atoms, or a phenyl group (which may be substituted with a lower alkyl group), and R 3 represents an imino group (optionally substituted with an alkyl group having 5 or less carbon atoms) or a sulfur atom, and R 4 , R 5 , R 6 , and R 7 each represent a hydrogen atom or a hydrogen atom or a sulfur atom having 5 or less carbon atoms. (Represents an alkyl group, and n is 0 or 1.) Examples of the conductive material used in the present invention include metal fine powder, metal fiber, metal mesh, carbon black, acetylene black, carbon fiber, graphite, etc. Mixtures thereof and composites of synthetic resins and the electrically conductive materials can be mentioned.
The electrical conductivity of these conductive materials is 10 -5 Ω -1 cm
−1 or more, preferably 10 −3 Ω −1 ·cm −1 , particularly preferably 10 −1 Ω −1 ·cm −1 or more. Further, the conductive polymer having a conjugated double bond chain in the main chain synthesized in the present invention is a polymer having any of the following repeating units; (1) [-CR 1 = CR 2 -] (2)
【式】 (3)【formula】 (3)
【式】または (4)[expression] or (Four)
【式】
但し、式中、R1，R2は夫々、水素原子、ハロ
ゲン原子、炭素数が５以下のアルキル基またはフ
エニル基（低級アルキル基で置換されていても良
い）を、R3はイミノ基（炭素数が５以下のアル
キル基で置換されていても良い）または硫黄原子
を、また、R4，R5，R6，R7は夫々、水素原子ま
たは炭素数が５以下のアルキル基を表し、ｎは０
または１である。
(1)で表される繰返し単位を有する重合体の代表
例としては、ポリアセチレン、ポリフエニルアセ
チレン、ポリメチルアセチレン、ポリジメチルア
セチレン、ポリジフエニルアセチレン、ポリプロ
パルギルクロリドがあげられる。
(2)で表される繰返し単位を有する重合体の代表
例としては、ポリ（１，６−ヘプタジイン）があ
げられる。
(3)で表される繰返し単位を有する重合体の代表
例としては、ポリピロール、ポリ（Ｎ−メチルピ
ロール）、ポリ（３−メチルピロール）、ポリ
（２，５−チエニレン）、ポリ（３−メチル−２，
５−チエニレン）があげられる。
(4)で表される繰返し単位を有する重合体の代表
例としては、ポリパラフエニレン、ポリメタフエ
ニレン、ポリ（パラフエニレンビニレン）があげ
られる。
これらの代表例の中で好ましいものとしては、
ポリアセチレン、ポリフエニルアセチレン、ポリ
メチルアセチレン、ポリ（２，５−チエニレン）、
ポリ（３−メチルチエニレン）、ポリパラフエニ
レン、ポリピロールをあげることができる。
また、電導性重合体組成物中の導電性材料の割
合は、１〜90重量％であり、好ましくは、３〜80
重量％、特に好ましくは５〜70重量％である。
また、重合触媒、重合溶媒、重合の制御法、後
処理方法については本製造方法固有の制限はな
く、公知のすべての方法を適用することができ
る。重合反応器は、攪拌が十分できるような形態
のものを必要とする。
以下実施例によつて本発明をさらにくわしく説
明するが、組成物の機械的強度は次の方法で測定
した。一辺30mmのステンレス製の100メツシユ金
網に、組成物約500mgを3.5Kg／cm2の圧力でプレス
しフイルムを得る。このフイルムをテンシロンの
チエツクにはさみ、１cm／分の速度で縮めてい
く。フイルムは、湾曲し、あるチヤツク間距離の
ところでフイルムにクラツクが生じる。このクラ
ツクを光学顕微鏡で観察する。クラツクが生じる
ときの縮みのパーセントを機械的強度と定義しパ
ーセントが大きいほど強度が高い。
実施例 １
攪拌機を備えた１の耐圧ガラス製反応容器に
トルエンを200ml、テトラブチルチタネートを2.8
ml（8.2mmol）、トリエチルアルミニウムを1.2ml
（8.8mmol）、ケツチエンブラツク（電気伝導度
4x10-1Ｓ／cm）0.4ｇを入れ、40℃の温度でアセ
チレンガスを分圧で0.9Kg／cm2に保ち攪拌下に２
時間重合した。２時間後、内容ガスを放出して重
合を終え、重合物にトルエン100mlを加え濾過後
30℃の温度で乾燥した。その結果、８ｇの電導性
重合体組成物を得た。機械的強度は、32％で、電
気伝導度は8x10-2Ｓ／cmであつた。
実施例 ２
300mlの三つ口フラスコにヘプタン100ml、マグ
ネシウムエチラート10ｇ（87mmol）、テトラブ
トキシチタニウム１ｇ（3mmol）を入れ70℃で
２時間攪拌を行なつた。得られた固形物を濾別し
た後、ヘプタンを使つて濾液中にチタン原子が認
められなくなるまで洗浄をくり返した。この固形
物を40℃の温度で乾燥することにより、粉末状の
固体触媒成分を得た。実施例１でテトラブチルチ
タネートの代りにこの固体触媒成分を１ｇ使用
し、ケツチエンブラツクの代りに銅粉を0.8ｇ使
用した以外は実施例１と全く同様に重合、洗浄お
よび乾燥したところ10ｇの電導性重合体組成物を
得た。機械的強度は20％で、電気伝導度は9x10-1
Ｓ／cmであつた。
実施例 ３
J.Polym.Sci.，Polym.Lett.Ed.，18，８（1980）
に記載されている方法でポリ（２，５−チエニレ
ン）を製造するときに、アセチレンブラツク（電
気伝導度1x10-1Ｓ／cm）を１ｇ入れて重合するこ
とにより電導性重合体組成物を10ｇ得た。機械的
強度は30％で、電気伝導度は5x10-2Ｓ／cmであつ
た。
実施例 ４
Bull.Chem.Soc.Japan.51，2091（1978）に記載
されている方法でポリ（パラフエニレン）を製造
するときに、ケツチエンブラツクを１ｇ入れて重
合することにより電導性重合体組成物を８ｇ得
た。機械的強度は28％で、電気伝導度は、7x10-2
Ｓ／cmであつた。
比較例 １
実施例１で使用した触媒を使つてポリアセチレ
ンを９ｇを得た。このポリアセチレン９ｇとケツ
チエンブラツク0.5ｇを振動ボールミル用の容器
（ステンレス製の円筒型、内容積300ml、直径が８
mmのステンレスボールを見かけ容積で約50％充
填）に入れた。これを振幅が６mm、振動数が30Hz
の振動ボールミルに取付け、20時間共粉砕するこ
とによつて電導性高分子組成物を得た。機械的強
度は８％で、電気伝導度は4x10-3Ｓ／cmであつ
た。
比較例 ２
実施例４の文献どおりポリ（パラフエニレン）
を８ｇ製造し、これにケツチエンブラツクを１
ｇ、ヘキサンを２ml入れて、メノウばち中で攪拌
混合し、乾燥後電導性高分子組成物を得た。機械
的強度は６％で、電気伝導度は1x10-3Ｓ／cmであ
つた。
比較例 ３
１のシユレンクフラスコにトルエンを７ml、
テトラブチルチタネート１ml（2.9mmol）、トリ
エチルアルミニウム１ml（7.31mmol）およびカ
ーボンブラツク0.01ｇを入れ静置した。
この状態でアセチレンガスにさらした。２時間
後重合を止めトルエンで重合物を洗浄した後、乾
燥しフイルム0.1ｇを得た。このフイルムの機械
的強度は８％で電気伝導度は2x10-6Ｓ／cmであつ
た。
［効果］
本発明によれば、下記のごとき効果が生じる。
すなわち、本発明の製造法による組成物中に存在
する導電静材料と重合体の混合性がきわめて良
く、そのため組成物の機械的強度が高い。このた
め、たとえば組成物を電池の電極に使用した場
合、導電性材料と重合体の単なる機械的混合によ
る組成物に比較して一次電池の場合、（）放電
容量が大きい、（）電圧の平坦性が良好である、
（）自己放電性が少ない、という利点を有し、
一方、二次電池の場合には、（）エネルギー密
度が大きい、（）電圧の平坦性が良好である、
（）自己放電が少ない、（）繰返しの寿命が長
い、という利点を有する。これらのことは理由が
かならずしも明らかではないが、本発明の組成物
はその混合性が良いため均一に導電性材料が分布
しているからか、組成物の電導性を発現する部分
が一部の所に局在せず全体に表れること、また機
械的強度が高いことから、電極から組成物の脱落
が少ないことのためと想像できる。[Formula] However, in the formula, R 1 and R 2 each represent a hydrogen atom, a halogen atom, an alkyl group having 5 or less carbon atoms, or a phenyl group (which may be substituted with a lower alkyl group), and R 3 represents An imino group (optionally substituted with an alkyl group having 5 or less carbon atoms) or a sulfur atom, and R 4 , R 5 , R 6 , and R 7 are each a hydrogen atom or an alkyl group having 5 or less carbon atoms. represents a group, n is 0
or 1. Representative examples of polymers having repeating units represented by (1) include polyacetylene, polyphenylacetylene, polymethylacetylene, polydimethylacetylene, polydiphenylacetylene, and polypropargyl chloride. A typical example of a polymer having a repeating unit represented by (2) is poly(1,6-heptadiyne). Typical examples of polymers having repeating units represented by (3) include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(2,5-thienylene), poly(3-methylpyrrole), Methyl-2,
5-thienylene). Typical examples of polymers having the repeating unit represented by (4) include polyparaphenylene, polymetaphenylene, and poly(paraphenylenevinylene). Among these representative examples, preferred ones are:
Polyacetylene, polyphenylacetylene, polymethylacetylene, poly(2,5-thienylene),
Examples include poly(3-methylthienylene), polyparaphenylene, and polypyrrole. Further, the proportion of the conductive material in the conductive polymer composition is 1 to 90% by weight, preferably 3 to 80% by weight.
% by weight, particularly preferably from 5 to 70% by weight. Furthermore, there are no limitations specific to this production method with respect to the polymerization catalyst, polymerization solvent, polymerization control method, and post-treatment method, and all known methods can be applied. The polymerization reactor must have a configuration that allows sufficient stirring. The present invention will be explained in more detail with reference to Examples below, and the mechanical strength of the composition was measured by the following method. Approximately 500 mg of the composition is pressed onto a 100-mesh stainless steel wire mesh measuring 30 mm on each side at a pressure of 3.5 kg/cm 2 to obtain a film. This film was placed in a Tensilon check and shrunk at a speed of 1 cm/min. The film warps and cracks occur in the film at a certain chuck distance. This crack is observed using an optical microscope. The percentage of shrinkage when cracks occur is defined as mechanical strength, and the larger the percentage, the higher the strength. Example 1 200 ml of toluene and 2.8 mL of tetrabutyl titanate were placed in a pressure-resistant glass reaction vessel equipped with a stirrer.
ml (8.2 mmol), triethylaluminum 1.2 ml
(8.8 mmol), Ketschen Black (electrical conductivity
4x10 -1 S/cm) was added, and the acetylene gas was heated at a temperature of 40°C with a partial pressure of 0.9 Kg/cm 2 while stirring.
Polymerized for hours. After 2 hours, the polymerization was completed by releasing the content gas, and 100 ml of toluene was added to the polymer, and after filtration.
Dry at a temperature of 30°C. As a result, 8 g of a conductive polymer composition was obtained. The mechanical strength was 32% and the electrical conductivity was 8x10 -2 S/cm. Example 2 100 ml of heptane, 10 g (87 mmol) of magnesium ethylate, and 1 g (3 mmol) of tetrabutoxytitanium were placed in a 300 ml three-necked flask and stirred at 70° C. for 2 hours. After the obtained solid was filtered off, washing was repeated using heptane until no titanium atoms were observed in the filtrate. By drying this solid at a temperature of 40°C, a powdery solid catalyst component was obtained. Polymerization, washing and drying were carried out in exactly the same manner as in Example 1, except that 1 g of this solid catalyst component was used instead of tetrabutyl titanate and 0.8 g of copper powder was used instead of Kettian black. A conductive polymer composition was obtained. Mechanical strength is 20% and electrical conductivity is 9x10 -1
It was S/cm. Example 3 J.Polym.Sci., Polym.Lett.Ed., 18, 8 (1980)
When producing poly(2,5-thienylene) by the method described in , 10 g of a conductive polymer composition is produced by adding 1 g of acetylene black (electrical conductivity 1x10 -1 S/cm) and polymerizing it. Obtained. The mechanical strength was 30% and the electrical conductivity was 5x10 -2 S/cm. Example 4 When producing poly(paraphenylene) by the method described in Bull. Chem. Soc. 8g of the product was obtained. Mechanical strength is 28% and electrical conductivity is 7x10 -2
It was S/cm. Comparative Example 1 Using the catalyst used in Example 1, 9 g of polyacetylene was obtained. 9 g of this polyacetylene and 0.5 g of Ketsuchen Black were placed in a vibrating ball mill container (cylindrical stainless steel, internal volume 300 ml, diameter 8
mm stainless steel ball was placed in a container (approximately 50% filled in terms of apparent volume). The amplitude is 6mm and the frequency is 30Hz.
A conductive polymer composition was obtained by attaching the powder to a vibrating ball mill and co-pulverizing it for 20 hours. The mechanical strength was 8% and the electrical conductivity was 4x10 -3 S/cm. Comparative Example 2 Poly(paraphenylene) as per the literature in Example 4
Produce 8 g of
g and 2 ml of hexane were added and mixed with stirring in an agate jar, and after drying, a conductive polymer composition was obtained. The mechanical strength was 6% and the electrical conductivity was 1x10 -3 S/cm. Comparative Example 3 7 ml of toluene was added to the Schulenk flask from 1.
1 ml (2.9 mmol) of tetrabutyl titanate, 1 ml (7.31 mmol) of triethylaluminum, and 0.01 g of carbon black were added and allowed to stand still. In this state, it was exposed to acetylene gas. After 2 hours, the polymerization was stopped, and the polymer was washed with toluene and dried to obtain 0.1 g of film. The mechanical strength of this film was 8% and the electrical conductivity was 2x10 -6 S/cm. [Effects] According to the present invention, the following effects occur.
That is, the miscibility of the conductive electrostatic material and the polymer present in the composition produced by the production method of the present invention is extremely good, and therefore the composition has high mechanical strength. For this reason, for example, when the composition is used in a battery electrode, compared to a composition made by simply mechanically mixing a conductive material and a polymer, in the case of a primary battery, it has () a larger discharge capacity, and () a flat voltage. good quality,
() Has the advantage of low self-discharge,
On the other hand, in the case of secondary batteries, () high energy density, () good voltage flatness,
It has the advantages of () low self-discharge and () long repeated life. The reasons for these problems are not entirely clear, but it may be because the conductive material is evenly distributed in the composition of the present invention due to its good mixability. It can be assumed that this is because the composition is less likely to fall off from the electrode because it appears all over the place without being localized in one place and has high mechanical strength.
Claims (1)
単量体と導電性材料とを攪拌下に均一に混合して
重合せしめることを特徴とする、導電性材料が均
一に分散し且つ下記の繰返し単位のいずれかを有
する導電性重合体を含む導電性重合体組成物の製
造方法； (1) ［−CR1＝CR2−］ (2)【式】 (3)【式】または (4)【式】 但し、式中、R1，R2は夫々、水素原子、ハロ
ゲン原子、炭素数が５以下のアルキル基またはフ
エニル基（低級アルキル基で置換されていても良
い）を、R3はイミノ基（炭素数が５以下のアル
キル基で置換されていても良い）または硫黄原子
を、また、R4，R5，R6，R7は夫々、水素原子ま
たは炭素数が５以下のアルキル基を表し、ｎは０
または１である。[Claims] 1. A method for producing a uniformly conductive material, characterized in that monomers corresponding to the following repeating units of a conductive polymer and a conductive material are uniformly mixed and polymerized under stirring. Method for producing a conductive polymer composition containing a conductive polymer dispersed and having any of the following repeating units; (1) [−CR 1 =CR 2 −] (2) [Formula] (3) [ [Formula] or (4) [Formula] However, in the formula, R 1 and R 2 are each a hydrogen atom, a halogen atom, an alkyl group having 5 or less carbon atoms, or a phenyl group (which may be substituted with a lower alkyl group) ), R 3 is an imino group (optionally substituted with an alkyl group having 5 or less carbon atoms) or a sulfur atom, and R 4 , R 5 , R 6 , and R 7 are each a hydrogen atom or a carbon atom. Represents an alkyl group of 5 or less, n is 0
or 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18599982A JPS5975943A (en) | 1982-10-25 | 1982-10-25 | Production of electrically conductive polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18599982A JPS5975943A (en) | 1982-10-25 | 1982-10-25 | Production of electrically conductive polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5975943A JPS5975943A (en) | 1984-04-28 |
| JPH0517259B2 true JPH0517259B2 (en) | 1993-03-08 |
Family
ID=16180595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18599982A Granted JPS5975943A (en) | 1982-10-25 | 1982-10-25 | Production of electrically conductive polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5975943A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0832770B2 (en) * | 1986-02-05 | 1996-03-29 | 松下電器産業株式会社 | Electrolytic organic polymer membrane |
| JPH0830107B2 (en) * | 1986-02-05 | 1996-03-27 | 松下電器産業株式会社 | Electropolymerization of organic polymers |
| US6627117B2 (en) | 1998-06-09 | 2003-09-30 | Geotech Chemical Company, Llc | Method for applying a coating that acts as an electrolytic barrier and a cathodic corrosion prevention system |
| US5976419A (en) * | 1998-06-09 | 1999-11-02 | Geotech Chemical Company | Method for applying a coating that acts as an electrolytic barrier and a cathodic corrosion prevention system |
| EP1509929A4 (en) * | 2002-05-23 | 2007-03-21 | Columbian Chem | CARBON-CONDUCTIVE MATERIAL GRAFTED ON A POLYMER FOR FUEL CELL APPLICATIONS |
| CN100339913C (en) | 2002-05-23 | 2007-09-26 | 哥伦比亚化学公司 | Sulfonated conducting polymer-grafted carbon material for fuel cell applications |
| US7390441B2 (en) | 2002-05-23 | 2008-06-24 | Columbian Chemicals Company | Sulfonated conducting polymer-grafted carbon material for fuel cell applications |
| US7241334B2 (en) | 2002-05-23 | 2007-07-10 | Columbian Chemicals Company | Sulfonated carbonaceous materials |
| US7459103B2 (en) | 2002-05-23 | 2008-12-02 | Columbian Chemicals Company | Conducting polymer-grafted carbon material for fuel cell applications |
| US6916900B1 (en) | 2003-04-03 | 2005-07-12 | Geotech Chemical Company, Llc | Catalytic effects of transition metal ions in the synthesis of polyaniline grafted lignosulfonic acid |
| US7063808B1 (en) | 2003-04-07 | 2006-06-20 | Poly One Corporation | Lignosulfonic acid-doped polyaniline composites with carbon allotropes |
| US6977050B1 (en) | 2003-04-07 | 2005-12-20 | Polyone Corporation | Synthesis of lignosulfonic acid-doped polyaniline using transition metal ion catalysts |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5889639A (en) * | 1981-11-25 | 1983-05-28 | Teijin Ltd | Polypyrrole composite and its manufacture |
-
1982
- 1982-10-25 JP JP18599982A patent/JPS5975943A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5975943A (en) | 1984-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Brédas et al. | Conjugated polymers: the novel science and technology of highly conducting and nonlinear optically active materials | |
| US5378402A (en) | Polymer compositions | |
| US5035926A (en) | Method of imparting antistatic properties to a substrate by coating the substrate with a novel polythiophene | |
| JPH0517259B2 (en) | ||
| Garnier et al. | First evidence of crystalline structure in conducting polythiophene | |
| US4665129A (en) | Electrically conductive thermoplastic mixtures of macromolecular compounds and finely divided pyrrole polymers | |
| US5407699A (en) | Electrically conductive pyrrole polymers | |
| EP0160207B1 (en) | Processable conductive polymers | |
| JPS59168010A (en) | Manufacture of electroconductive powdery pyrrole polymer | |
| US6117554A (en) | Modulated molecularly bonded inherently conductive polymers on substrates with conjugated multiple lamellae and shaped articles thereof | |
| US5028481A (en) | Electrically conductive pigmentary composites | |
| US4510024A (en) | Novel polymer composition | |
| US4764573A (en) | Electrically conductive pyrrole polymers | |
| JPH0788424B2 (en) | Method for producing film-like conductive polymer | |
| JPS62109821A (en) | Production of heterocyclic five-membered ring compound polymer composition | |
| Hassan | Alginate polyelectrolyte ionotropic gels 7. Physico-chemical studies on silver (I) alginate complex with special attention to the electrical conductance and geometrical structure | |
| JPH02283722A (en) | Manufacture of conductive polymer derived from 3-alkylthiophene, and conductive device containing said polymer | |
| US5430073A (en) | Process for preparing polymers and mouling compounds based thereon | |
| AU630161B2 (en) | Process for preparing electrically conductive polymers and polymer compositions | |
| JPS62290759A (en) | Composite material of metal complex and electrically conductive high-molecular material and production thereof | |
| EP0603381A1 (en) | Process for the preparation of a polymer composition | |
| JPS62168B2 (en) | ||
| JP2608095B2 (en) | Method for producing highly conductive organic polymer molded article | |
| Borole et al. | Studies on electrochemical, optical and electrical conductivity of conducting composite of o-anisidine, o-toluidine and their co-polymer | |
| JPS62220517A (en) | Electrically conductive polymer composition and production thereof |