JPS61276818A - Tellurophene polymer and production thereof - Google Patents
Tellurophene polymer and production thereofInfo
- Publication number
- JPS61276818A JPS61276818A JP60118745A JP11874585A JPS61276818A JP S61276818 A JPS61276818 A JP S61276818A JP 60118745 A JP60118745 A JP 60118745A JP 11874585 A JP11874585 A JP 11874585A JP S61276818 A JPS61276818 A JP S61276818A
- Authority
- JP
- Japan
- Prior art keywords
- tellurophene
- polymer
- oxidizing agent
- dopant
- polymerizing
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規な重合体であるテルロフェン重合体および
その製造方法に関する。本発明はまたテルロフェン重合
体を用いた高分子導電体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polymer, a tellurophene polymer, and a method for producing the same. The present invention also relates to polymeric conductors using tellurophene polymers.
最近、複素５員環式化合物の重合体は導電性を有する高
分子化合物として有機高分子導電性材料、あるいは有機
高分子半導体材料として注目されており、ポリピロール
、ポリフラン、ポリチオフェン、ポリセレノフェンが知
られている。Recently, polymers of five-membered heterocyclic compounds have attracted attention as conductive organic polymeric materials or organic polymeric semiconductor materials, such as polypyrrole, polyfuran, polythiophene, and polyselenophene. It is being
従来これら複素５員環式化合物の重合体の製造方法とし
ては、複素５員理式化合物の鉱酸との反応、あるいは電
気化学的酸化重合法で得られていた。Conventionally, polymers of these five-membered heterocyclic compounds have been produced by reacting a five-membered heterocyclic compound with a mineral acid or by electrochemical oxidative polymerization.
しかしながら、ヘテロ原子としてテルルを有する複素５
員環式化合物のテルロフェンは、これらの方法では高分
子量体を生成しないことが報告されており〔例えば、吉
野勝美３．繊維学会誌ｖ０１゜４１、 Ｎｏ、２
Ｐ５９〜６６ （１９８５） 、 ） 、現在までのと
ころポリテルロフェン重合体は得られておらず、その物
性についても不明であった。However, complex 5 with tellurium as a heteroatom
It has been reported that tellurophene, a membered cyclic compound, does not produce a high molecular weight substance by these methods [for example, Katsumi Yoshino 3. Journal of the Textile Science Society v01゜41, No. 2
P59-66 (1985), ), no polytellurophene polymer has been obtained so far, and its physical properties are unknown.
本発明の目的は新規なテルロフェン重合体およびその製
造方法、さらにはテルロフェン重合体を用いた高分子導
電体を提供することにある。An object of the present invention is to provide a novel tellurophene polymer, a method for producing the same, and a polymer conductor using the tellurophene polymer.
本発明者らは前記目的を達成するために鋭意検討した結
果本発明を完成した。即ち本発明は、下記一般式（１）
〔式中ｎは２以上の整数を示す。〕で表わされるテルロ
フェン重合体であり、またテルロフェン重合体にドーパ
ントをドーピングしてなる高分子導電体である。The present inventors completed the present invention as a result of intensive studies to achieve the above object. That is, the present invention is based on the following general formula (1) [wherein n represents an integer of 2 or more]. ] It is a polymeric conductor made by doping a tellurophene polymer with a dopant.
さらに本発明はテルロフェンを酸化剤と接触せしめて重
合させることを特徴とするテルロフェン重合体の製造方
法である。Furthermore, the present invention is a method for producing a tellurophene polymer, which comprises bringing tellurophen into contact with an oxidizing agent and polymerizing it.
本発明のテルロフェン重合体はテルロフェンを酸化剤と
接触させることによって製造される。The tellurophene polymers of the present invention are made by contacting tellurophene with an oxidizing agent.
ここで使用する酸化剤としてはその種類に制限をうけず
、種々の酸化剤が使用可能であるが、中でも鉄、ルテニ
ウム、モリブデンなどのハロゲン化物、特に塩化第二鉄
、塩化ルテニウム、塩化モリブデンなどの遷移金属化合
物が反応性も高く好適である。The oxidizing agent used here is not limited in type and various oxidizing agents can be used, but among them, halides such as iron, ruthenium, and molybdenum, especially ferric chloride, ruthenium chloride, molybdenum chloride, etc. Transition metal compounds having high reactivity are suitable.
上記酸化剤とテルロフェンとの接触方法としては、両者
を単に混合するだけでも良く、また溶媒を使用する方法
も用いられ、通常はこの方が反応を制御する上で好まし
い。この場合溶媒としては、テルロフェンを溶解し、か
つ酸化剤とは実質的に反応せず、しかも酸化剤を比較的
良く熔解する溶媒が好ましく、例えばヘキサン、ヘプタ
ンなどの飽和炭化水素、ジクロロメタン、クロロホルム
。The oxidizing agent and tellurophene may be brought into contact by simply mixing them together, or by using a solvent, which is usually preferable in terms of controlling the reaction. In this case, the solvent is preferably a solvent that dissolves tellurophene, does not substantially react with the oxidizing agent, and dissolves the oxidizing agent relatively well, such as saturated hydrocarbons such as hexane and heptane, dichloromethane, and chloroform.
二塩化エチレンなどのハロゲン化炭化水素、あるいはア
セトニトリルなどのニトリル類が挙げられる。Examples include halogenated hydrocarbons such as ethylene dichloride, and nitriles such as acetonitrile.
テルロフェンと酸化剤またはその溶液との接触温度およ
び接触時間については格別制限はなく必要に応じて定め
れば良い。接触温度としては常温でも良く、時間として
は数分ないし数十時間接触させるのが一般的である。There are no particular restrictions on the contact temperature and contact time between tellurophene and the oxidizing agent or its solution, and they may be determined as necessary. The contact temperature may be room temperature, and the contact time is generally several minutes to several tens of hours.
本発明の方法で得られた重合体は、ろ過など、および必
要によっては前記の溶媒を用いた洗浄により未反応のテ
ルロフェンおよび余分の酸化剤を除去し、乾燥すること
で分離される。The polymer obtained by the method of the present invention is separated by removing unreacted tellurophene and excess oxidizing agent by filtration or the like and, if necessary, washing with the above-mentioned solvent, and then drying.
こうして得られたテルロフェン重合体は酸化剤化合物が
ドーパントとしてドーピングされた状態の重合体であり
、これをさらにメタノール、アセトン、水、アンモニア
水などの極性溶媒で十分に洗浄処理することによってド
ーパントを含まないテルロフェン重合体を得ることがで
きる。The tellurophene polymer obtained in this way is a polymer doped with an oxidizing agent compound as a dopant, and is further washed thoroughly with a polar solvent such as methanol, acetone, water, or aqueous ammonia to remove the dopant. tellurophene polymer can be obtained.
本発明の方法で得られたテルロフェン重合体は種々の溶
剤に不溶で、通常の分子量測定方法では分子量を特定す
ることはできないが、元素分析の結果水素と炭素の重量
比率がテルロフェン単量体では０．０８４に対して、得
られたテルロフェン重合体では０．０５１〜０．０４４
であって、約４量体から２０量体のテルロフェン重合体
に相当する。The tellurophene polymer obtained by the method of the present invention is insoluble in various solvents, and the molecular weight cannot be determined by ordinary molecular weight measurement methods, but elemental analysis shows that the weight ratio of hydrogen and carbon is different from that of the tellurophen monomer. 0.084, whereas the obtained tellurophene polymer had a concentration of 0.051 to 0.044.
and corresponds to about a tetramer to 20mer tellurophene polymer.
後に述べる実施例−１で得られたテルロフェンの重合体
の赤外吸収スペクトルを第１図に示す。FIG. 1 shows the infrared absorption spectrum of the tellurophene polymer obtained in Example 1, which will be described later.
本発明のテルロフェン重合体にドーパントがドーピング
されてなる高分子導電体は、テルロフェン重合体製造の
さいに得られた酸化剤がドーピングされたテルロフェン
重合体そのま＼でも良く、また上述のようにドーピング
された酸化剤を実質的に除去した後、例えばヨウ素、臭
素など゛のハロゲン、三フッ化アンチモン、五フッ化ヒ
素などのルイス酸、あるいはアルカリ金属などをドーピ
ングして得ることもでき、さらにはドーピングされた酸
化剤を除去することなくさらに別のドーパントをドーピ
ングして得ることもできる。The polymeric conductor of the present invention, which is made by doping the tellurophene polymer with a dopant, may be the tellurophene polymer itself doped with the oxidizing agent obtained during the production of the tellurophene polymer, or it may be doped as described above. After substantially removing the oxidizing agent, it can be doped with a halogen such as iodine or bromine, a Lewis acid such as antimony trifluoride or arsenic pentafluoride, or an alkali metal. It can also be obtained by further doping with another dopant without removing the doped oxidizing agent.
本発明を実施例によりさらに具体的に説明する。 The present invention will be explained in more detail with reference to Examples.
実施例−１
アルゴンガス雰囲気下で、精製したテルロフェン１０ｇ
をクロロホルム１０ ｍｌに溶解した溶液を塩化第二鉄
２０ｇをクロロホルム５０ｍ７！中に懸濁した溶液中に
滴下した。室温で３時間かきまぜて反応させたのち、生
成したテルロフェン重合体をろ別してクロロホルムおよ
びエチルアルコールで洗浄した。さらにソックスレー抽
出器を用いてエタノ−ル、アセトニトリル、クロロホル
ムで可溶物を抽出して取り除いた。テルロフェン重合体
の収量は３．５ｇであった。得られた生成物は、螢光Ｘ
線分析により、テルルの存在が確認された。また、元素
分析による水素と炭素の重量比率よりテルロフェン重合
体であることが確認された。この重合体の赤外吸収スペ
クトルは第１図に示されている。Example-1 10g of purified tellurophene under argon gas atmosphere
A solution of 20 g of ferric chloride dissolved in 10 ml of chloroform was added to 50 m7 of chloroform! into the suspended solution. After stirring and reacting at room temperature for 3 hours, the produced tellurophene polymer was filtered off and washed with chloroform and ethyl alcohol. Furthermore, soluble materials were extracted and removed using ethanol, acetonitrile, and chloroform using a Soxhlet extractor. The yield of tellurophene polymer was 3.5 g. The product obtained is fluorescent
Line analysis confirmed the presence of tellurium. In addition, it was confirmed that it was a tellurophene polymer based on the weight ratio of hydrogen and carbon by elemental analysis. The infrared absorption spectrum of this polymer is shown in FIG.
この試料を６００ｋｇ／ｃＩ１１２で加圧成形したのち
電気伝導度を測定したところｌＱ＝′ＬＳ ／ ＣＩＩ
Ｉであった。After this sample was pressure-molded at 600 kg/cI112, the electrical conductivity was measured and found that lQ='LS/CII
It was I.
実施例−２
実施例−１で合成したテルロフェン重合体１ｇをヨウ素
蒸気で満たされたサンプル管中に２４時間放置しておい
たところ０．５４ｇのヨウ素がドーピングされた。Example 2 When 1 g of the tellurophene polymer synthesized in Example 1 was left in a sample tube filled with iodine vapor for 24 hours, it was doped with 0.54 g of iodine.
このテルロフェン重合体のヨウ素混合物を実施例−１と
同様の方法で電気伝導度を測定したところ１０４Ｓ／ｃ
Ｉｎであった。The electrical conductivity of this tellurophene polymer iodine mixture was measured in the same manner as in Example 1, and it was found to be 104 S/c.
It was In.
実施例−３
酸化剤として五塩化モリブデンを用いた外は実施例−１
と同様に反応を行い、ソックスレー抽出器で抽出するこ
となく乾燥秤量したところ収量は９．０ｇであった。ま
た加圧成形して電気伝導度を測定したところ１０ ”Ｓ
／ ｃｍであった。Example-3 Example-1 except that molybdenum pentachloride was used as the oxidizing agent
The reaction was carried out in the same manner as above, and the yield was 9.0 g when dry and weighed without extraction using a Soxhlet extractor. In addition, when the electrical conductivity was measured after pressure molding, it was 10”S.
/ cm.
本発明の重合体は、圧縮成形加工等の成形方法により成
形することが可能でドーパントをドーピング、脱ドーピ
ングすることが可能であり、電池の電極材料、太陽電池
用材料、光電素子材料、半導体材料などの用途に供する
ことができる新らしい重合体である。The polymer of the present invention can be molded by a molding method such as compression molding, and can be doped and undoped with a dopant, and can be used as a battery electrode material, a solar cell material, a photoelectric element material, and a semiconductor material. This is a new polymer that can be used for various purposes.
第１図は実施例−１で得られたテルロフェンの重合体の
赤外吸収スペクトルである。FIG. 1 is an infrared absorption spectrum of the tellurophene polymer obtained in Example-1.
Claims (1)
フェン重合体。 ２）テルロフェン重合体にドーパントをドーピングして
なる高分子導電体。 ３）テルロフェンを酸化剤と接触せしめて重合させるこ
とを特徴とするテルロフェン重合体の製造方法。[Claims] 1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n represents an integer of 2 or more. ] A tellurophene polymer represented by 2) A polymer conductor made by doping a tellurophene polymer with a dopant. 3) A method for producing a tellurophene polymer, which comprises bringing tellurophen into contact with an oxidizing agent and polymerizing it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60118745A JPS61276818A (en) | 1985-06-03 | 1985-06-03 | Tellurophene polymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60118745A JPS61276818A (en) | 1985-06-03 | 1985-06-03 | Tellurophene polymer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61276818A true JPS61276818A (en) | 1986-12-06 |
Family
ID=14744005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60118745A Pending JPS61276818A (en) | 1985-06-03 | 1985-06-03 | Tellurophene polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61276818A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0399299A2 (en) * | 1989-05-26 | 1990-11-28 | International Business Machines Corporation | Electrically conductive polymeric materials and uses thereof |
| JP2009533530A (en) * | 2006-04-13 | 2009-09-17 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conductive polymer composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58196233A (en) * | 1982-05-13 | 1983-11-15 | Matsushita Electric Ind Co Ltd | Production of electrically conductive or semiconductive polymer composition |
| JPS5912933A (en) * | 1982-06-29 | 1984-01-23 | バイエル・アクチエンゲゼルシヤフト | Oxidation polymerization using no+ or no2+ |
-
1985
- 1985-06-03 JP JP60118745A patent/JPS61276818A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58196233A (en) * | 1982-05-13 | 1983-11-15 | Matsushita Electric Ind Co Ltd | Production of electrically conductive or semiconductive polymer composition |
| JPS5912933A (en) * | 1982-06-29 | 1984-01-23 | バイエル・アクチエンゲゼルシヤフト | Oxidation polymerization using no+ or no2+ |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0399299A2 (en) * | 1989-05-26 | 1990-11-28 | International Business Machines Corporation | Electrically conductive polymeric materials and uses thereof |
| JP2009533530A (en) * | 2006-04-13 | 2009-09-17 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Conductive polymer composition |
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