JPH0349288B2 - - Google Patents
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- Publication number
- JPH0349288B2 JPH0349288B2 JP24898585A JP24898585A JPH0349288B2 JP H0349288 B2 JPH0349288 B2 JP H0349288B2 JP 24898585 A JP24898585 A JP 24898585A JP 24898585 A JP24898585 A JP 24898585A JP H0349288 B2 JPH0349288 B2 JP H0349288B2
- Authority
- JP
- Japan
- Prior art keywords
- membered heterocyclic
- heterocyclic compound
- solid acid
- carrier
- 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
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- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は複素五員環式化合物重合体組成物を製
造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a five-membered heterocyclic compound polymer composition.
複素五員環式化合物重合体は絶縁体から導電体
までその電気的性質を制御できる有機化合物とし
て知られており、電気導電体あるいは半導電性材
料として使用することができる。また、その熱安
定性が良好なことから耐熱性材料としてもできる
ほか、水や有機物の光分解などの触媒や各種セン
サー用材料としても使用できるものである。
Five-membered heterocyclic compound polymers are known as organic compounds whose electrical properties can be controlled from insulators to conductors, and can be used as electrical conductors or semiconducting materials. Furthermore, because of its good thermal stability, it can be used as a heat-resistant material, and can also be used as a catalyst for photodecomposition of water and organic substances, and as a material for various sensors.
複素五員環式化合物の重合方法としては、酸化
剤との反応によつて粉末状や塊状の重合体が得ら
れることは知られている（アドバンシス オブ
ヘテロサイクリツクケミストリ 15巻 67ページ
1973年など）。また、最近電気化学的重合方法に
より電極基板の上に複素五員環式化合物の粉末や
膜が形成されるこのが報告されている（ジヤーナ
ル オブ ケミカル ソサイテイ ケミカル コ
ミユニケイシヨン 1979 635、ジヤパン ジヤ
ーナル オブ アプライド フイジツクス 21
L567（1982）、ibid 23L527（1984））。 As a polymerization method for five-membered heterocyclic compounds, it is known that powdery or bulk polymers can be obtained by reaction with an oxidizing agent (Advances of
Heterocyclic Chemistry Volume 15 Page 67
(e.g. 1973). In addition, it has recently been reported that a powder or film of a five-membered heterocyclic compound is formed on an electrode substrate by an electrochemical polymerization method (Journal of Chemical Society Chemical Communication 1979 635, Japan Journal of Applied Physics 21
L567 (1982), ibid 23 L527 (1984)).
しかしながら、これらの複素五員環式化合物重
合体と担体との複合体を合成するためには、担体
の存在下に酸化剤を用いて複素五員環式化合物モ
ノマーを重合させることによりある程度は可能で
あるが、生成する重合体が熱や溶媒に不溶不融で
るため担体との複合体と担体を含まない重合体と
を分けることが不可能であり、また、担体と重合
体との複合強度があまり強くなくて担体と重合体
が分離し易いという問題がある。
However, it is possible to some extent to synthesize composites of these five-membered heterocyclic compound polymers and carriers by polymerizing the five-membered heterocyclic compound monomers using an oxidizing agent in the presence of the carrier. However, since the polymer produced is insoluble and infusible to heat and solvents, it is impossible to separate the composite with the carrier from the polymer without the carrier, and the composite strength of the carrier and polymer is There is a problem that the carrier and polymer are easily separated because the carrier is not very strong.
本発明の目的はこれらの問題を解決した複素五
員環式化合物組成物の製造方法を提供するとにあ
る。 An object of the present invention is to provide a method for producing a five-membered heterocyclic compound composition that solves these problems.
〔問題点を解決する為の手段〕
本発明者らはこれらの問題を解決すべく鋭意検
討した結果、特定の担体を使用することにより、
担体上に強固に結合した複素五員環式化合物重合
体が得られることを見出し、本発明を完成した。[Means for Solving the Problems] As a result of intensive studies by the present inventors to solve these problems, by using a specific carrier,
The present invention was completed based on the discovery that a five-membered heterocyclic compound polymer strongly bonded to a carrier can be obtained.
すなわち、本発明は、複素五員環式化合物を固
体酸と接触することにより、固体酸上に複素五員
環式化合物重合体を生成せしめることを特徴とす
る複素五員環式化合物重合体組成物の製造方法で
ある。 That is, the present invention provides a five-membered heterocyclic compound polymer composition, characterized in that the five-membered heterocyclic compound is brought into contact with a solid acid to form a polymer of the five-membered heterocyclic compound on a solid acid. It is a method of manufacturing something.
本発明において担体と複素五員環式化合物重合
体との複合体を生成せしめるためには、担体とし
て固体酸を使用して複素五員環式化合物モノマー
をその固体酸と接触せしめれば良い。 In the present invention, in order to produce a composite of the carrier and the five-membered heterocyclic compound polymer, a solid acid may be used as the carrier and the five-membered heterocyclic compound monomer may be brought into contact with the solid acid.
本発明において使用する固体酸としては、酸性
白土、ベントナイト、カオリン、モンモリロナイ
ト、クジリツト、フロリジンなどの天然の粘土鉱
物、シリカゲルやアルミナに硫酸、リン酸、マロ
ン酸などを付着焼合せしめた固形化酸、陽イオン
交換樹脂、シリカ・アルミナ、シリカ・マグネシ
ア、シリカ・ボリア、各種ゼオライト、ヘテロポ
リ酸、酸化亜鉛、酸化アルミ、酸化チタン、５酸
化バナジル、酸化ケイソなどの酸化物などが例示
できる。 The solid acids used in the present invention include natural clay minerals such as acid clay, bentonite, kaolin, montmorillonite, cicada, and phlorizin, solidified acids prepared by adhering and sintering sulfuric acid, phosphoric acid, malonic acid, etc. to silica gel or alumina. , cation exchange resins, silica/alumina, silica/magnesia, silica/boria, various zeolites, heteropolyacids, zinc oxide, aluminum oxide, titanium oxide, vanadyl pentoxide, silica oxide, and other oxides.
本発明において複素五員環式化合物として、ピ
ロール、フラン、チオフエン、セレノフエン、テ
ルロフエンおよびこれらの誘導体があげられる。 In the present invention, examples of the five-membered heterocyclic compound include pyrrole, furan, thiophene, selenophene, tellurophene, and derivatives thereof.
複素五員環式化合物重合体組成物の製造せしめ
る方法としては、複素五員環式化合物を固体酸と
接触させるだけでよく、他の酸化剤などを使用す
る必要はないため、その製造操作は極めて容易で
ある。 The method for producing a five-membered heterocyclic compound polymer composition requires only contacting the five-membered heterocyclic compound with a solid acid, and there is no need to use other oxidizing agents. It's extremely easy.
具体的には、複素五員環式化合物モノマーある
いはそれを溶媒で希釈したモノマー組成物中で固
体酸と接触処理したり、固体酸を流動層に入れた
中にモノマーガスを流通させて固体酸とモノマー
を接触処理したり、あるいは、ボールミル中の固
体酸とモノマーを入れて粉砕混合することにより
接触処理するなどである。 Specifically, a five-membered heterocyclic compound monomer or a monomer composition prepared by diluting it with a solvent is contacted with a solid acid, or a solid acid is placed in a fluidized bed and monomer gas is passed through the solid acid. The solid acid and the monomer may be brought into contact with each other, or the solid acid and the monomer may be placed in a ball mill and then ground and mixed.
なお、反応時間や反応温度は、複素五員環式化
合物種類および反応条件により適宜決定すればよ
い。 The reaction time and reaction temperature may be appropriately determined depending on the type of five-membered heterocyclic compound and reaction conditions.
固体酸と複素五員環式化合物モノマーとを接触
処理した後余分なモノマーを除くだけで、特別な
処理をすることなしに複素五員環式化合物重合体
組成物が得られる。 A five-membered heterocyclic compound polymer composition can be obtained without any special treatment by simply removing the excess monomer after contacting the solid acid and the five-membered heterocyclic compound monomer.
以下、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
酸性白土（200℃で３時間乾燥したもの）10ｇ
にピロール３mlを加え、均一に混合した。酸性白
土の表面はしだいに黒色に変化した。40時間後未
反応のピロールを150℃で減圧乾燥して除き、黒
色の複合体を得た。Example 1 10g of acid clay (dried at 200℃ for 3 hours)
3 ml of pyrrole was added to the mixture and mixed uniformly. The surface of the acid clay gradually turned black. After 40 hours, unreacted pyrrole was removed by drying under reduced pressure at 150°C to obtain a black composite.
元素分析した結果、この複合体には５重量％の
ポリピロールが含まれていた。 As a result of elemental analysis, this composite contained 5% by weight of polypyrrole.
実施例 ２
固体酸として、陽イオン交換樹脂
“DOWEX50W”（商標）を用い、ピロール蒸気
と接触させたところ、１時間で陽イオン交換樹脂
は黒色になり、24時間後に減圧乾燥して重量変化
を調べたところ10重量％のポリピロールが生成し
ていた。Example 2 When a cation exchange resin "DOWEX50W" (trademark) was used as a solid acid and brought into contact with pyrrole vapor, the cation exchange resin turned black in 1 hour, and was dried under reduced pressure after 24 hours to check the weight change. Upon investigation, it was found that 10% by weight of polypyrrole was produced.
実施例 ３〜６
ピロールに代えて、フラン（実施例３）、チオ
フエン（実施例４）、セレノフエン（実施例５）
またはテルロフエン（実施例６）を用いる外は実
施例１と同様にして重合を行い、それぞれポリフ
ラン８重量％、ポリチオフエン７重量％、ポリセ
レノフエン７重量％、ポリテルロフエン４重量％
を含有する複合体を得た。Examples 3 to 6 Instead of pyrrole, furan (Example 3), thiophene (Example 4), selenophene (Example 5)
Alternatively, polymerization was carried out in the same manner as in Example 1 except for using tellurofene (Example 6), and 8% by weight of polyfuran, 7% by weight of polythiophene, 7% by weight of polyselenophene, and 4% by weight of polytellofene, respectively.
A complex containing the following was obtained.
本発明により得られる組成物は、導電性のフイ
ラーとして、また、複素五員環式化合物重合体の
触媒効果を利用した担体触媒として使用ができ、
その産業上の利用価値は大きい。
The composition obtained according to the present invention can be used as a conductive filler and as a carrier catalyst utilizing the catalytic effect of a five-membered heterocyclic compound polymer.
Its industrial value is great.
Claims (1)
により、固体酸上に複素五員環式化合物重合体を
生成せしめることを特徴とする複素五員環式化合
物重合体組成物の製造方法。1. A method for producing a five-membered heterocyclic compound polymer composition, which comprises contacting the five-membered heterocyclic compound with a solid acid to produce a five-membered heterocyclic compound polymer on a solid acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24898585A JPS62109820A (en) | 1985-11-08 | 1985-11-08 | Production of heterocyclic five-membered ring compound polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24898585A JPS62109820A (en) | 1985-11-08 | 1985-11-08 | Production of heterocyclic five-membered ring compound polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62109820A JPS62109820A (en) | 1987-05-21 |
| JPH0349288B2 true JPH0349288B2 (en) | 1991-07-29 |
Family
ID=17186310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24898585A Granted JPS62109820A (en) | 1985-11-08 | 1985-11-08 | Production of heterocyclic five-membered ring compound polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62109820A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2521110B2 (en) * | 1987-10-12 | 1996-07-31 | 東海ゴム工業株式会社 | Method for producing conductive resin composition |
| FR2682115B1 (en) * | 1991-10-08 | 1993-12-24 | Thomson Csf | CONDUCTIVE MATERIAL, PAINT AND SENSOR USING THE SAME. |
| JP7083991B2 (en) * | 2018-03-05 | 2022-06-14 | 群馬県 | How to improve the properties of light oil |
-
1985
- 1985-11-08 JP JP24898585A patent/JPS62109820A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62109820A (en) | 1987-05-21 |
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