JPH0369366B2 - - Google Patents
Info
- Publication number
- JPH0369366B2 JPH0369366B2 JP59231158A JP23115884A JPH0369366B2 JP H0369366 B2 JPH0369366 B2 JP H0369366B2 JP 59231158 A JP59231158 A JP 59231158A JP 23115884 A JP23115884 A JP 23115884A JP H0369366 B2 JPH0369366 B2 JP H0369366B2
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- present
- oxidizing agent
- stirring
- membered heterocyclic
- 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
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Conductive Materials (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は複合導電性組成物の製造法に関する。
詳しくは、熱可塑性樹脂と複素五員環式化合物重
合体からなる複合導電性組成物の製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a composite conductive composition.
Specifically, the present invention relates to a method for producing a composite conductive composition comprising a thermoplastic resin and a five-membered heterocyclic compound polymer.
複素五員環式化合物が、酸化剤によつて不溶不
融の重合体を生成することはすでに知られてい
る。例えば、ピロール及びその誘導体は、無機
酸、塩化鉄、ベンゾキノン、オゾンなどにより酸
化され、ピロール黒、ピロール赤などの重合体に
なることがアドバンシズ イン ヘテロサイクリ
ツク ケミストリー（Advances in
Heterocyclic Chemistry）15巻67ページ（1973）
に示されている。
It is already known that five-membered heterocyclic compounds form insoluble and infusible polymers with oxidizing agents. For example, pyrrole and its derivatives can be oxidized by inorganic acids, iron chloride, benzoquinone, ozone, etc. to form polymers such as pyrrole black and pyrrole red.
Heterocyclic Chemistry) Volume 15, page 67 (1973)
is shown.
また、フランやチオフエンそれらの誘導体も同
様の反応で重合体が得られる。 Furthermore, polymers can be obtained from derivatives of furan and thiophene through similar reactions.
しかしながら、上述の反応で得られる重合体は
不溶不融の粉末又は塊りであり、有効な利用がで
きないという問題があつた。又電解重合によつて
粉末状担体物質の存在下にピロールの重合体を製
造する方法（例えば特開昭59−168010）も知られ
ているが、電解重合では特別な装置、電解質を使
用する必要があるなどの問題があつた。
However, the problem is that the polymer obtained by the above reaction is an insoluble and infusible powder or lump, and cannot be used effectively. A method of producing a pyrrole polymer in the presence of a powdered carrier material by electrolytic polymerization is also known (e.g., JP-A-59-168010), but electrolytic polymerization requires the use of special equipment and an electrolyte. There were some problems.
本発明は成形可能な、電気伝導性の良好な複合
導電性組成物を製造する簡便な方法を提供するこ
とにある。 An object of the present invention is to provide a simple method for producing a composite conductive composition that is moldable and has good electrical conductivity.
本発明者らは、上記問題を解決して簡単な装置
で成形可能な複合導電性組成物を製造する方法に
ついて鋭意検討した結果、特定の方法で複素五員
環式化合物重合体を製造することで簡単に複合導
電性組成物を製造することができることを見い出
し、本発明を完成した。
As a result of intensive study on a method for solving the above problems and manufacturing a composite conductive composition that can be molded with a simple device, the present inventors have found that a five-membered heterocyclic compound polymer can be manufactured by a specific method. The present invention was completed based on the discovery that a composite conductive composition can be easily produced using the following methods.
即ち、本発明は、熱可塑性樹脂粒子を分散した
酸化剤含有溶液に撹拌下に複素五員環式化合物を
添加して重合することを特徴とする複合導電性組
成物の製造方法である。 That is, the present invention is a method for producing a composite conductive composition, which comprises adding a five-membered heterocyclic compound to an oxidizing agent-containing solution in which thermoplastic resin particles are dispersed while stirring and polymerizing the compound.
本発明において使用する酸化剤としては、無機
酸、金属化合物が有効であり、硫酸、塩酸、硝
酸、クロルスルホン酸などが無機酸の具体例とし
て挙げられる。金属化合物としてはルイス酸とし
て知られる化合物が好ましく用いられ、アルミニ
ウム、錫、チタン、ジルコニウム、クロム、マン
ガン、鉄、銅、モリブデン、タングステン、ルテ
ニウム、パラジウム、白金等の金属の塩化物、硫
酸塩、硝酸塩、アセチルアセトナート化合物など
が具体例として挙げられる。その他の酸化剤とし
てベンゾキノン、ジアゾニウム塩などの有機化合
物も使用できる。これらの酸化剤は１種あるいは
２種以上混合して用いることも可能である。 Inorganic acids and metal compounds are effective as the oxidizing agent used in the present invention, and specific examples of the inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and chlorosulfonic acid. As the metal compound, compounds known as Lewis acids are preferably used, and metal chlorides, sulfates, etc. of aluminum, tin, titanium, zirconium, chromium, manganese, iron, copper, molybdenum, tungsten, ruthenium, palladium, platinum, etc. Specific examples include nitrates and acetylacetonate compounds. Organic compounds such as benzoquinone and diazonium salts can also be used as other oxidizing agents. These oxidizing agents may be used alone or in combination of two or more.
本発明において上述の酸化剤は適当な溶媒に溶
解して用いられる。溶媒としては上記酸化剤を溶
解し、しかも使用する下記の熱可塑性樹脂粒子を
実質的に溶解せずしかも使用する酸化剤と実質的
に反応しないものであれば良く、酸化剤と熱可塑
性樹脂の組み合せによつて適当な溶媒が選択され
る。安価な溶媒として水を採用することも可能で
あるが、熱可塑性樹脂が疎水性のものであるとき
には、界面活性剤を併用すると酸化剤溶液が熱可
塑性樹脂に良く侵透し効果的である。 In the present invention, the above-mentioned oxidizing agent is used after being dissolved in a suitable solvent. The solvent may be any solvent as long as it dissolves the oxidizing agent, does not substantially dissolve the following thermoplastic resin particles used, and does not substantially react with the oxidizing agent used. A suitable solvent is selected depending on the combination. Although it is possible to use water as an inexpensive solvent, when the thermoplastic resin is hydrophobic, it is effective to use a surfactant in combination so that the oxidizing agent solution can penetrate well into the thermoplastic resin.
本発明において熱可塑性樹脂粒子としては公知
のどのようなものも使用でき、ペレツト、パウダ
ー、ビーズなどどのような形状であつても良い。
好ましくは、酸化剤溶液が侵透しやすい形状のも
のである。熱可塑性樹脂としては例えば、ポリプ
ロピレン、ポリエチレン、ポリスチレン、ポリ塩
化ビニル、スチレン−アクリロニトリル共重合
体、ポリエステル、ポリカーボネート、ポリアミ
ド、ポリイソプレンなど工業的に入手できるもの
が挙げられる。 In the present invention, any known thermoplastic resin particles can be used, and they may be in any shape such as pellets, powder, beads, etc.
Preferably, the shape is such that the oxidizing agent solution can easily penetrate therethrough. Examples of the thermoplastic resin include those that are industrially available, such as polypropylene, polyethylene, polystyrene, polyvinyl chloride, styrene-acrylonitrile copolymer, polyester, polycarbonate, polyamide, and polyisoprene.
本発明において使用する複素五員環式化合物と
しては、ピロール、フラン、チオフエン及びそれ
らの誘導体が挙げられる。 The five-membered heterocyclic compounds used in the present invention include pyrrole, furan, thiophene, and derivatives thereof.
本発明においては上記複素五員環式化合物を添
加する際には、熱可塑性樹脂粒子の酸化剤含有溶
液スラリーは撹拌されている必要がある。この撹
拌の方法については、特に限定はなく、スラリー
が均一に分散する程度の撹拌が行えればよく、通
常の撹拌羽根による方法或いは、ポンプによつて
スラリーを循環する方法でもよい。要は複素五員
環式化合物の反応中、継続して撹拌しておくこと
である。 In the present invention, the oxidizing agent-containing solution slurry of thermoplastic resin particles needs to be stirred when the five-membered heterocyclic compound is added. There are no particular limitations on the method of stirring, as long as the stirring can be carried out to the extent that the slurry is uniformly dispersed, and a method using an ordinary stirring blade or a method in which the slurry is circulated using a pump may be used. The key is to continuously stir the five-membered heterocyclic compound during the reaction.
反応温度についても特に制限はなく室温で充分
反応は進行する。通常は０℃〜溶媒の沸点程度で
行えば充分である。 There is no particular restriction on the reaction temperature, and the reaction proceeds satisfactorily at room temperature. Usually, it is sufficient to carry out the reaction at a temperature of 0°C to the boiling point of the solvent.
熱可塑性樹脂と複素五員環式化合物の量比は酸
化剤量、添加複素五員環式化合物の量によつて制
御可能であり、所望の導電性となるように、添加
量を変えれば良い。 The ratio of the thermoplastic resin to the five-membered heterocyclic compound can be controlled by the amount of the oxidizing agent and the amount of the five-membered heterocyclic compound added, and the amount added can be changed to achieve the desired conductivity. .
本発明の方法で得られた複合体は、ろ過などの
方法で分離可能であり、必要に応じて酸化剤を洗
浄除去することも可能である。 The complex obtained by the method of the present invention can be separated by a method such as filtration, and if necessary, the oxidizing agent can be removed by washing.
本発明の方法を実施することによつて熱可塑性
樹脂に対して比較的多い量比の複素五員環式化合
物重合体を分散させることが可能であり、電気電
導度の高い複合導電性組成物が得られると考えら
れる。
By carrying out the method of the present invention, it is possible to disperse a relatively large amount of the hetero5-membered cyclic compound polymer in the thermoplastic resin, thereby creating a composite conductive composition with high electrical conductivity. is considered to be obtained.
以下に実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
容量100mlのビーカーに蒸留水50mlを入れ、三
塩化鉄0.8ｇを溶解したあと、ポリプロピレンパ
ウダー0.209ｇ、ラウリン酸ナトリウム0.3ｇを加
え、窒素ガスで置換したあと、窒素中で長さ２cm
のスターラーチツプで100rpmで撹拌しながらピ
ロール0.4mlを加え、さらに撹拌しながら反応さ
せた。2.5時間後、撹拌を止めた。生成物はポリ
プロピレン粒子にポリピロールが結合した黒色の
複合体であつた。この生成物を過し、蒸留水で
洗浄した後、メタノールで洗浄し、減圧下で乾燥
した。得られた複合体の重量は0.597ｇであつた。
この値から試料中に65.0％のポリピロールが含ま
れていることになる。Example 1 Put 50 ml of distilled water into a 100 ml beaker, dissolve 0.8 g of iron trichloride, add 0.209 g of polypropylene powder and 0.3 g of sodium laurate, replace the mixture with nitrogen gas, and prepare a beaker with a length of 2 cm in nitrogen.
While stirring at 100 rpm with a stirrer tip, 0.4 ml of pyrrole was added, and the mixture was reacted with further stirring. After 2.5 hours, stirring was stopped. The product was a black composite in which polypyrrole was bound to polypropylene particles. The product was filtered and washed with distilled water followed by methanol and dried under reduced pressure. The weight of the resulting composite was 0.597g.
This value indicates that the sample contains 65.0% polypyrrole.
この試料0.1ｇを加熱溶融成形して厚さ0.16mm
のフイルム状としたのち、比抵抗を測定したとこ
ろ4.3×10-1Ω・cmであつた。 0.1g of this sample was heated and melted to a thickness of 0.16mm.
After forming into a film, the specific resistance was measured and found to be 4.3×10 -1 Ω·cm.
実施例 ２
実施例１と同様にして、ポリプロピレンの量を
0.471ｇに変えたところ、生成試料中のポリピロ
ール含量が、38.1％の複合体が得られた。この生
成物を加熱溶融成形して比抵抗を測定したとこ
ろ、2.1Ω・cmであつた。Example 2 In the same manner as in Example 1, the amount of polypropylene was
When the amount was changed to 0.471 g, a composite with a polypyrrole content of 38.1% in the produced sample was obtained. When this product was heated and melt-molded and its specific resistance was measured, it was 2.1 Ω·cm.
実施例 ３
容量100mlのビーカーにメタノール50mlを入れ
三塩化鉄0.5ｇを溶解したあとアクリロニトリル
系熱可塑性樹脂“バレツクス210レジン”（商品名
ソハイオ・ケミカルズ社製）1.461ｇを加え、撹
拌しながらピロール0.4mlを加え、さらに撹拌し
ながら反応させた。４時間後、撹拌を止めた。生
成物は、バレツクス210レジンにポリピロールが
結合した黒色の複合体であつた。この生成物をメ
タノールで洗浄し、減圧下で乾燥した。生成した
複合体の重量は1.471ｇであつた。この値から試
料中に0.66％のポリピロールが含まれていること
になる。この試料0.15ｇを加熱溶融成型して厚さ
0.42mmのフイルム状としたのち比抵抗を測定した
ところ9.9×103Ω・cmであつた。Example 3 Pour 50 ml of methanol into a 100 ml beaker, dissolve 0.5 g of iron trichloride, add 1.461 g of acrylonitrile-based thermoplastic resin "Barrex 210 Resin" (trade name, manufactured by Sohio Chemicals), and add 0.4 g of pyrrole while stirring. ml was added, and the reaction was continued with further stirring. After 4 hours, stirring was stopped. The product was a black composite of polypyrrole bound to Barex 210 resin. The product was washed with methanol and dried under reduced pressure. The weight of the resulting composite was 1.471 g. This value indicates that the sample contains 0.66% polypyrrole. Heat and melt 0.15g of this sample to form the thickness.
After forming into a 0.42 mm film, the specific resistance was measured and found to be 9.9×10 3 Ω·cm.
実施例 ４
実施例１のピロールをフランに代えた他は同様
に重合を行つた。同様に成形したフイルムの比抵
抗を測定したところ1.2×104Ω・cmであつた。Example 4 Polymerization was carried out in the same manner as in Example 1 except that pyrrole was replaced with furan. When the specific resistance of a similarly molded film was measured, it was 1.2×10 4 Ω·cm.
実施例 ５
実施例１のピロールにかえてチオフエンを用い
た他は同様に重合し成形したフイルムの比抵抗を
測定したところ3.2×103Ω・cmであつた。Example 5 The specific resistance of a film polymerized and molded in the same manner as in Example 1 except that thiophene was used in place of pyrrole was 3.2×10 3 Ω·cm.
本発明の方法を実施することによつて成形可能
な導電性組成物を製造することが可能となり工業
的に極めて価値がある。
By carrying out the method of the present invention, it is possible to produce a moldable conductive composition, which is extremely valuable industrially.
Claims (1)
に、撹拌下に、複素五員環式化合物を添加して重
合することを特徴とする複合導電性組成物の製造
方法。1. A method for producing a composite conductive composition, which comprises adding a five-membered heterocyclic compound to an oxidizing agent-containing solution in which thermoplastic resin particles are dispersed, while stirring, and polymerizing the compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23115884A JPS61111325A (en) | 1984-11-05 | 1984-11-05 | Production of composite electroconductive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23115884A JPS61111325A (en) | 1984-11-05 | 1984-11-05 | Production of composite electroconductive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61111325A JPS61111325A (en) | 1986-05-29 |
| JPH0369366B2 true JPH0369366B2 (en) | 1991-10-31 |
Family
ID=16919208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23115884A Granted JPS61111325A (en) | 1984-11-05 | 1984-11-05 | Production of composite electroconductive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61111325A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0778116B2 (en) * | 1987-02-09 | 1995-08-23 | 住友化学工業株式会社 | Method for producing aqueous dispersion of polypyrrole |
| FR2616790A1 (en) * | 1987-06-22 | 1988-12-23 | Rhone Poulenc Chimie | Dispersions of composite particles based on an electrically conductive polymer and process for their preparation |
| US5916627A (en) * | 1997-12-31 | 1999-06-29 | Kemet Electronics Corp. | Conductive polymer using self-regenerating oxidant |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3223545A1 (en) * | 1982-06-24 | 1983-12-29 | Basf Ag, 6700 Ludwigshafen | PYRROL COPOLYMERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| JPS59172539A (en) * | 1983-03-22 | 1984-09-29 | Showa Denko Kk | Production of highly electroconductive polymer composition |
-
1984
- 1984-11-05 JP JP23115884A patent/JPS61111325A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61111325A (en) | 1986-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0564970B2 (en) | ||
| JPH0369366B2 (en) | ||
| JPS61127737A (en) | Production of electrically conductive resin composite | |
| JPH0556367B2 (en) | ||
| JPS61127736A (en) | Production of electrically conductive resin composite | |
| JPH05148320A (en) | Preparation of polyindoles, conductive compositions containing them and device and use of polyindoles | |
| JPS62106923A (en) | Production of five-membered heterocyclic compound polymer | |
| JP2844122B2 (en) | Polymer thermometer | |
| JPS6211730A (en) | Production of electrically conductive composite material | |
| JPH0460506B2 (en) | ||
| JPH0348934B2 (en) | ||
| JPH03234733A (en) | Microcapsuled composite conductive material, its production and its conductive molded article | |
| JP2000268634A (en) | Conductive expanded particles and method for producing the same | |
| JPH01261471A (en) | Conductive polymer having improved solubility | |
| JPH0443110B2 (en) | ||
| JPH04253744A (en) | Conductive polymeric material and its production | |
| JPS6131133B2 (en) | ||
| JPH06101243B2 (en) | Method for manufacturing composite conductive film | |
| KR920007048B1 (en) | A prepared method and composition of polyalkylether and aromatic hetero polymer | |
| JP2544739B2 (en) | Method for producing electrically conductive resin composition molded article | |
| JPH0369369B2 (en) | ||
| JPH0464532B2 (en) | ||
| JPS6116765B2 (en) | ||
| JPS61266460A (en) | Electrically conductive polyamide composition | |
| JP3017563B2 (en) | Conductive polymer solution composition |