JP2003513100A - Novel thiophenes and polymerization method of the thiophenes - Google Patents
Novel thiophenes and polymerization method of the thiophenesInfo
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- JP2003513100A JP2003513100A JP2001535366A JP2001535366A JP2003513100A JP 2003513100 A JP2003513100 A JP 2003513100A JP 2001535366 A JP2001535366 A JP 2001535366A JP 2001535366 A JP2001535366 A JP 2001535366A JP 2003513100 A JP2003513100 A JP 2003513100A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
Abstract
(57)【要約】 本発明は式（Ｉ）の新規なチオフェン類に関し、式中、Ｒ及びＲ’は独立して−水素、アルキル又はアルコキシであるか、あるいは一緒になって−Ｏ−（ＣＨ 2）n−Ｏ−架橋であり、ここでｎ＝１〜５である。該チオフェン類は有機導電体として用いられ得るポリチオフェン類の製造に適している。 【化１】 (57) [Summary] The present invention relates to novel thiophenes of formula (I), wherein R and R 'are independently -hydrogen, alkyl or alkoxy, or taken together -O- (CH Two)n—O-crosslinking, where n = 1 to 5. The thiophenes are suitable for producing polythiophenes that can be used as an organic conductor. Embedded image
Description
【０００１】
本発明は導電性ポリマーの製造に適した新規なチオフェン類及びそれらの重合
法に関する。The present invention relates to novel thiophenes suitable for the production of electrically conductive polymers and a process for their polymerization.
【０００２】
ポリチオフェンはいわゆる有機導電体として文献から既知である（ＵＳ−Ａ
４ ９８７ ０４２）。Polythiophenes are known from the literature as so-called organic conductors (US-A).
4 987 042).
【０００３】
しかしながら、加工性又は長期安定性のようなそれらの性質はまだすべての工
業的用途に関して十分というわけではない。かくして向上した性質を示すポリチ
オフェン類に対する必要性がある。However, their properties such as processability or long-term stability are not yet sufficient for all industrial applications. Thus, there is a need for polythiophenes that exhibit improved properties.
【０００４】
ポリチオフェン類は通常モノマー性もしくはオリゴマー性チオフェン類の化学
的もしくは電気化学的重合により製造される。Polythiophenes are usually produced by the chemical or electrochemical polymerization of monomeric or oligomeric thiophenes.
【０００５】
ポリチオフェン類の性質を向上させるために、かくして新規なチオフェンモノ
マーもしくはオリゴマーを合成することが必要である。In order to improve the properties of polythiophenes, it is thus necessary to synthesize new thiophene monomers or oligomers.
【０００６】 本発明は、導電性ポリマーの製造に適しており、且つ式Ｉ[0006] The present invention is suitable for the production of conductive polymers and has the formula I
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】
［式中、
Ｒ及びＲ’は互いに独立して水素、アルキル又はアルコキシを示すか、あるいは
一緒になって−Ｏ−（ＣＨ2）n−Ｏ−架橋を示し、ここでｎ＝１〜５である］
を有する新規なチオフェン類を提供する。[0008] In the formula, R and R 'independently of one another are hydrogen, an alkyl or alkoxy, or indicates it by -O- (CH 2) n -O- bridge together, wherein n = 1 The present invention provides a novel thiophene having the following formula.
【０００９】
好ましいチオフェン類は、Ｒ及びＲ’が互いに独立して水素、１〜３０個の炭
素原子を有するアルキル基、１〜３０個の炭素原子を有するアルコキシ基を示す
か、あるいは一緒になって−Ｏ−（ＣＨ2）n−Ｏ−架橋を示し、ここでｎ＝１〜
５である式Ｉの化合物である。Preferred thiophenes are those in which R and R ′ independently of one another represent hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or taken together. Represents a —O— (CH 2 ) n —O— bridge, where n = 1 to
Is a compound of formula I which is 5.
【００１０】 適した式Ｉの化合物の例を以下に示す：[0010] Examples of suitable compounds of formula I are shown below:
【００１１】[0011]
【化５】 [Chemical 5]
【００１２】
今日までに既知のチオフェンの重合はいくつかの重大な欠点を負っている：
−水中におけるモノマー化合物の低い溶解度のために、あまり環境に優しくない
有機溶媒、例えばクロロホルム、塩化メチレン又はアセトニトリルの使用が多く
の場合に必要である。
−得られるポリチオフェン類は多くの場合に加工不可能である。
−得られる有機導電体を還元して、それらの中性の形態にそれらを変換すること
が多くの場合に困難である。The polymerization of thiophenes known to date suffers from several serious drawbacks: -Because of the low solubility of the monomeric compounds in water, less environmentally friendly organic solvents such as chloroform, methylene chloride or acetonitrile. The use of is often necessary. The resulting polythiophenes are often unprocessable. It is often difficult to reduce the resulting organic conductors and convert them to their neutral form.
【００１３】
本発明の他の部分は、上記の問題がなく、溶液中において加工可能であり、且
つ酸を用いるプロトン化の後に高くて安定な導電性を示すポリチオフェン類を与
える新規な重合法に関する。Another part of the present invention relates to a novel polymerization process, which is free from the above-mentioned problems, is processable in solution, and gives polythiophenes which are highly stable and conductive after protonation with an acid. .
【００１４】 従って本発明は、式Ｉ[0014] Accordingly, the present invention provides formula I
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】
［式中、
Ｒ及びＲ’は互いに独立して水素、アルキル又はアルコキシを示すか、あるいは
一緒になって−Ｏ−（ＣＨ2）n−Ｏ−架橋を示し、ここでｎ＝１〜５である］
のチオフェン類を、≦３．７５のｐＫAを有し且つその対応する共役塩基が非−
求核性である酸を用いて重合させることを特徴とするポリチオフェン類の製造法
をさらに提供する。Wherein R and R ′ independently of one another represent hydrogen, alkyl or alkoxy, or taken together represent a —O— (CH 2 ) n —O— bridge, where n = 1. ~ 5] of thiophenes having a pK A of ≤ 3.75 and the corresponding conjugate base is non-
Further provided is a method for producing polythiophenes, which comprises polymerizing with a nucleophilic acid.
【００１７】
適した酸の例はギ酸、ジフルオロ酢酸、トリフルオロ酢酸及びジクロロ酢酸で
ある。Examples of suitable acids are formic acid, difluoroacetic acid, trifluoroacetic acid and dichloroacetic acid.
【００１８】 本発明の方法は好ましくはギ酸を用いて行われる。[0018] The method of the invention is preferably carried out with formic acid.
【００１９】 該方法は好ましくは１０〜６０℃の反応温度で行われる。[0019] The process is preferably carried out at a reaction temperature of 10-60 ° C.
【００２０】 得られるポリマーは以前には未知の化合物であるので、本発明はさらに式ＩＩ[0020] Since the polymer obtained is a previously unknown compound, the present invention further provides a compound of formula II
【００２１】[0021]
【化７】 [Chemical 7]
【００２２】
［式中、
Ｒ及びＲ’は互いに独立して水素、アルキル又はアルコキシを示すか、あるいは
一緒になって−Ｏ−（ＣＨ2）n−Ｏ−架橋を示し、ここでｎ＝１〜５であり、ｑ
は２〜１０，０００であることができ、Ｒ＝Ｒ’＝水素である化合物を除く］
のポリチオフェン類を提供する。[0022] In the formula, R and R 'independently of one another are hydrogen, an alkyl or alkoxy, or indicates it by -O- (CH 2) n -O- bridge together, wherein n = 1 ~ 5 and q
Can be from 2 to 10,000, except for compounds where R = R '= hydrogen].
【００２３】
Ｒ＝Ｒ’＝水素であり、チオフェンＩ−１から製造されるポリチオフェンＩＩ
−１はＫａｒｉｋｏｍｉ ｅｔ ａｌ．，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９９ ５
，１１７，６７９１−６７９２から既知である。それは４，８−ビス（２−チ
エニル）ベンゾ［１，２−ｃ：４，５−ｃ’］−ビス［１，２，５］チアジアゾ
ールの電気化学的重合により製造された。Polythiophene II prepared from thiophene I-1 with R = R ′ = hydrogen
-1 is based on Karikomi et al. J. Am. Chem. Soc. 199 5, is known from 117,6791-6792. It was prepared by electrochemical polymerization of 4,8-bis (2-thienyl) benzo [1,2-c: 4,5-c ']-bis [1,2,5] thiadiazole.
【００２４】
ベンゾ−ビス［１，２，５］チアジアゾール部分のプロトン化のために、式Ｉ
Ｉのポリチオフェンはカチオン性の形態にある。正の電荷は分子全体上に非局在
化しているので、式においてはそれらを示していない。For protonation of the benzo-bis [1,2,5] thiadiazole moiety, the formula I
The polythiophene of I is in the cationic form. Since the positive charges are delocalized on the whole molecule, they are not shown in the equation.
【００２５】
≦３．７５のｐＫAを有し且つその対応する共役塩基が非−求核性である酸の
添加又は除去により、式ＩＩのポリチオフェン類を正に帯電した状態と中性の状
態の間で可逆的に切り替えることができる。The polythiophenes of formula II are brought to the positively charged and neutral states by addition or removal of an acid having a pK A of ≦ 3.75 and whose corresponding conjugate base is non-nucleophilic. Can be reversibly switched between.
【００２６】
式ＩＩのポリチオフェン類の特に重要な用途分野には：
−データ保存、
−光信号の処理、
−電磁干渉（ｅｌｅｃｔｒｏｍａｇｎｅｔｉｃ ｉｎｔｅｒｆｅｒｅｎｃｅ）（
ＥＭＩ）の抑制、
−太陽エネルギー変換、
−再充電可能なバッテリー、
−電極、
−発光ダイオード、
−電界効果型トランジスター、
−コンデンサー、
−センサー、
−エレクトロクロミックパネル、
−特に電子部品用の包装フィルム及び写真フィルム用の基質フィルムのための帯
電防止材料、
−コピー機ドラムのためのコーティングならびに
−印刷回路板及び多層製品（ｍｕｌｔｉｌａｙｅｒｓ）の直通接続
が含まれる。Particularly important fields of application of the polythiophenes of the formula II are: data storage, optical signal processing, electromagnetic interference (electromagnetic interference)
EMI) suppression, solar energy conversion, rechargeable batteries, electrodes, light emitting diodes, field effect transistors, capacitors, sensors, electrochromic panels, packaging films especially for electronic components and Includes antistatic materials for substrate films for photographic films, coatings for copier drums, and direct connection of printed circuit boards and multilayers.
【００２７】
プロトン化された状態における式ＩＩのポリチオフェン類の導電率は１０-8〜
１０3Ｓ／ｃｍ、好ましくは１０-4〜１０2Ｓ／ｃｍの範囲である。The conductivity of polythiophenes of formula II in the protonated state is from 10 −8 to
The range is 10 3 S / cm, preferably 10 −4 to 10 2 S / cm.
【００２８】
式ＩＩのポリチオフェン類を種々の方法、例えばＵＶ−Ｖｉｓ−ＮＩＲ分光分
析、ＦＴ−ＩＲ分光分析、粘度分析、ＧＰＣ、導電率分析、ＭＡＬＤＩ−ＴＯＦ
ＭＳ、ＮＭＲ分光分析、サイクリックボルタムメトリー及び微量分析（Ｃ、Ｈ
、Ｎなど）によって同定した。The polythiophenes of formula II can be prepared by various methods, for example UV-Vis-NIR spectroscopy, FT-IR spectroscopy, viscosity analysis, GPC, conductivity analysis, MALDI-TOF.
MS, NMR spectroscopy, cyclic voltammetry and microanalysis (C, H
, N, etc.).
【００２９】
モノマーＩ−２から製造されたポリチオフェンＩＩ−２に関し、ＵＶ−Ｖｉｓ
−ＮＩＲ分光分析によって０．３ｅＶのバンドギャップが決定された。これは溶
液中で加工可能なポリマーに関して今日までに測定された最も低い値の１つであ
る。Regarding the polythiophene II-2 produced from the monomer I-2, UV-Vis
A band gap of 0.3 eV was determined by NIR spectroscopy. This is one of the lowest values measured to date for polymers processable in solution.
【００３０】[0030]
式Ｉのチオフェン類及び式ＩＩのポリチオフェン類の製造の１つの方法を以下
の反応経路により記述する：One method for the preparation of thiophenes of formula I and polythiophenes of formula II is described by the following reaction routes:
【００３１】[0031]
【化８】 [Chemical 8]
【００３２】
テトラアミノベンゾキノン及びＳＯＣｌ2から容易に得ることができるベンゾ
ビス［１，２，５］−チアジアゾールジオンを、対応するチオフェン誘導体及び
ｎ−ブチルリチウムから容易に得ることができる対応する２−チエニルリチウム
誘導体と、あるいは２−チエニルブロモマグネシウム誘導体と反応させることに
よりチオフェンを製造する。ギ酸を用いて重合を行う。実施例１
４，８−ジヒドロキシ−４，８−ビス（２−チエニル）ベンゾ［１，２−ｃ：４
，５−ｃ’］−ビス［１，２，５］チアジアゾール（Ｉ−１）の合成
無水ＴＨＦ（７５ｍｌ）中のチオフェン（０．３９４ｇ、４．６８ミリモル）
の溶液をアルゴン雰囲気下で−７８℃に冷却した。ヘキサン（３．０ｍｌ）中の
ｎ−ブチルリチウムの１．６モル溶液をこの溶液に１０分かけて加えた。得られ
る混合物を−７８℃で１５分間撹拌し、室温に温め、この温度で３０分間撹拌し
、再び−７８℃に冷却した。固体のベンゾ［１，２−ｃ：４，５−ｃ’］−ビス
［１，２，５］チアジアゾール−４，８−ジオン（０．５０ｇ、２．２３ミリモ
ル）を、内部温度が−６０℃未満に留まるような速度で量り込んだ。添加の完了
後、紫色の反応混合物を−４０℃に温め、この温度で１５分間撹拌し、再び−７
８℃に冷却した。この温度で無水ＴＨＦ中の酢酸の溶液（５０重量％、２ｍｌ）
を加え、次いで溶液を室温に温めた。酢酸エチル（１５０ｍｌ）及び水（１００
ｍｌ）を加え、相を分離し、有機層を水で十分に洗浄し、次いでＭｇＳＯ4上で
乾燥した。溶媒を蒸発させて粗Ｉ−１を残し、それを酢酸／水から再結晶してＩ
−１の無色のプリズムを得た（０．５２ｇ、１．３２ミリモル、５９．２モル−
％）。融点：２２８℃。実施例２
４，８−ジヒドロキシ−４，８−ビス（２−チエニル）ベンゾ［１，２−ｃ：４
，５−ｃ’］−ビス［１，２，５］チアジアゾール（Ｉ−１）の重合
微粉末状にされた４，８−ジヒドロキシ−４，８−ビス（２−チエニル）ベン
ゾ［１，２−ｃ：４，５−ｃ’］−ビス［１，２，５］チアジアゾール（２５ｍ
ｇ）にギ酸（１０ｍｌ）を加え、混合物を室温で１２時間撹拌した。得られるギ
酸中のポリマーの溶液を続いて直接、例えば加圧空気回転注型法において用いる
ことができる。Benzobis [1,2,5] -thiadiazoledione, which is easily obtained from tetraaminobenzoquinone and SOCl 2, is the corresponding 2-thienyl, which is easily obtained from the corresponding thiophene derivative and n-butyllithium. Thiophene is produced by reacting with a lithium derivative or a 2-thienyl bromomagnesium derivative. Polymerization is carried out using formic acid. Example 1 4,8-Dihydroxy-4,8-bis (2-thienyl) benzo [1,2-c: 4
, 5-c ']-Bis [1,2,5] thiadiazole (I-1) Synthesis of thiophene (0.394 g, 4.68 mmol) in anhydrous THF (75 ml)
Solution was cooled to -78 ° C under an argon atmosphere. A 1.6 molar solution of n-butyllithium in hexane (3.0 ml) was added to this solution over 10 minutes. The resulting mixture was stirred at -78 ° C for 15 minutes, warmed to room temperature, stirred at this temperature for 30 minutes and cooled again to -78 ° C. Solid benzo [1,2-c: 4,5-c ']-bis [1,2,5] thiadiazole-4,8-dione (0.50 g, 2.23 mmol) was added at an internal temperature of -60. It was weighed in at such a rate that it remained below ℃. After the addition was complete, the purple reaction mixture was warmed to -40 ° C and stirred at this temperature for 15 minutes, again at -7
Cooled to 8 ° C. A solution of acetic acid in anhydrous THF at this temperature (50% by weight, 2 ml)
Was added and then the solution was warmed to room temperature. Ethyl acetate (150 ml) and water (100
ml) was added, the phases were separated and the organic layer was washed well with water and then dried over MgSO 4 . Evaporation of the solvent left crude I-1, which was recrystallized from acetic acid / water to give I
-1 colorless prism was obtained (0.52 g, 1.32 mmol, 59.2 mol-).
%). Melting point: 228 ° C. Example 2 4,8-Dihydroxy-4,8-bis (2-thienyl) benzo [1,2-c: 4
, 5-c ']-Bis [1,2,5] thiadiazole (I-1) Polymerization Micronized 4,8-dihydroxy-4,8-bis (2-thienyl) benzo [1,2] -C: 4,5-c ']-bis [1,2,5] thiadiazole (25 m
Formic acid (10 ml) was added to g) and the mixture was stirred at room temperature for 12 hours. The resulting solution of polymer in formic acid can then be used directly, for example in a pressurized air rotary casting process.
───────────────────────────────────────────────────── フロントページの続き (81)指定国 ＥＰ(ＡＴ，ＢＥ，ＣＨ，ＣＹ， ＤＥ，ＤＫ，ＥＳ，ＦＩ，ＦＲ，ＧＢ，ＧＲ，ＩＥ，Ｉ Ｔ，ＬＵ，ＭＣ，ＮＬ，ＰＴ，ＳＥ)，ＯＡ(ＢＦ，ＢＪ ，ＣＦ，ＣＧ，ＣＩ，ＣＭ，ＧＡ，ＧＮ，ＧＷ，ＭＬ， ＭＲ，ＮＥ，ＳＮ，ＴＤ，ＴＧ)，ＡＰ(ＧＨ，ＧＭ，Ｋ Ｅ，ＬＳ，ＭＷ，ＭＺ，ＳＤ，ＳＬ，ＳＺ，ＴＺ，ＵＧ ，ＺＷ)，ＥＡ(ＡＭ，ＡＺ，ＢＹ，ＫＧ，ＫＺ，ＭＤ， ＲＵ，ＴＪ，ＴＭ)，ＡＥ，ＡＧ，ＡＬ，ＡＭ，ＡＴ， ＡＵ，ＡＺ，ＢＡ，ＢＢ，ＢＧ，ＢＲ，ＢＹ，ＢＺ，Ｃ Ａ，ＣＨ，ＣＮ，ＣＲ，ＣＵ，ＣＺ，ＤＥ，ＤＫ，ＤＭ ，ＤＺ，ＥＥ，ＥＳ，ＦＩ，ＧＢ，ＧＤ，ＧＥ，ＧＨ， ＧＭ，ＨＲ，ＨＵ，ＩＤ，ＩＬ，ＩＮ，ＩＳ，ＪＰ，Ｋ Ｅ，ＫＧ，ＫＰ，ＫＲ，ＫＺ，ＬＣ，ＬＫ，ＬＲ，ＬＳ ，ＬＴ，ＬＵ，ＬＶ，ＭＡ，ＭＤ，ＭＧ，ＭＫ，ＭＮ， ＭＷ，ＭＸ，ＭＺ，ＮＯ，ＮＺ，ＰＬ，ＰＴ，ＲＯ，Ｒ Ｕ，ＳＤ，ＳＥ，ＳＧ，ＳＩ，ＳＫ，ＳＬ，ＴＪ，ＴＭ ，ＴＲ，ＴＴ，ＴＺ，ＵＡ，ＵＧ，ＵＳ，ＵＺ，ＶＮ， ＹＵ，ＺＡ，ＺＷ (72)発明者 ベケマンス，ジエフ・エイ・ジエイ・エム オランダ・エヌエル−5283ダブリユーアー ル ボクステル・デハンドボーグ10 (72)発明者 バン・ムレコム，ロバート・エイチ・エ イ・エム オランダ・エヌエル−6029ピーエヌ ステ ルクセル・アルベルトラーン２ Ｆターム(参考） 4C072 AA01 AA07 BB02 BB06 CC04 CC17 EE20 FF13 GG07 HH06 JJ03 UU08 ─────────────────────────────────────────────────── ─── Continued front page (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, C A, CH, CN, CR, CU, CZ, DE, DK, DM , DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Bekemans, JF AJ M Netherlands Nuel-5283 Doubler Le Boxtel Dehandborg 10 (72) Inventors Van Mulecome, Robert H.E. Lee M Netherlands Nuel-6029 P.N. Luxel Albert Lahn 2 F-term (reference) 4C072 AA01 AA07 BB02 BB06 CC04 CC17 EE20 FF13 GG07 HH06 JJ03 UU08
Claims (3)
一緒になって−Ｏ−（ＣＨ2）n−Ｏ−架橋を示し、ここでｎ＝１〜５である］ のチオフェン類。1. Formula I In the formula, R and R 'independently of one another are hydrogen, an alkyl or alkoxy, or indicates it by -O- (CH 2) n -O- bridge together, wherein at n = 1 to 5 Yes] thiophenes.
一緒になって−Ｏ−（ＣＨ2）n−Ｏ−架橋を示し、ここでｎ＝１〜５である］ のチオフェン類を、≦３．７５のｐＫAを有し且つその対応する共役塩基が非−
求核性である酸を用いて重合させることを特徴とするポリチオフェン類の製造法
。2. Formula I In the formula, R and R 'independently of one another are hydrogen, an alkyl or alkoxy, or indicates it by -O- (CH 2) n -O- bridge together, wherein at n = 1 to 5 A] of thiophenes having a pK A of ≦ 3.75 and the corresponding conjugate base is non-
A method for producing polythiophenes, which comprises polymerizing using a nucleophilic acid.
一緒になって−Ｏ−（ＣＨ2）n−Ｏ−架橋を示し、ここでｎ＝１〜５であり、ｑ
は２〜１０，０００であることができ、Ｒ＝Ｒ’＝水素である化合物を除く］ のポリチオフェン類。3. Formula II: In the formula, R and R 'independently of one another are hydrogen, an alkyl or alkoxy, or indicates it by -O- (CH 2) n -O- bridge together, wherein at n = 1 to 5 Yes, q
Can be from 2 to 10,000, except for compounds where R = R '= hydrogen].
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19953454A DE19953454A1 (en) | 1999-11-05 | 1999-11-05 | New thiophenes and processes for their polymerization |
| DE19953454.3 | 1999-11-05 | ||
| PCT/EP2000/010471 WO2001032664A2 (en) | 1999-11-05 | 2000-10-24 | Novel thiophenes and method for polymerization of said thiophenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003513100A true JP2003513100A (en) | 2003-04-08 |
Family
ID=7928137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001535366A Pending JP2003513100A (en) | 1999-11-05 | 2000-10-24 | Novel thiophenes and polymerization method of the thiophenes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1230246A2 (en) |
| JP (1) | JP2003513100A (en) |
| KR (1) | KR20020068526A (en) |
| AU (1) | AU7922200A (en) |
| DE (1) | DE19953454A1 (en) |
| WO (1) | WO2001032664A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188899A (en) * | 2017-05-23 | 2017-09-22 | 苏州赛乐生物科技有限公司 | 4,8 disubstituted benzenes and double thiadiazole compound, derivative and synthetic methods |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5021586A (en) * | 1989-03-31 | 1991-06-04 | Miles, Inc. | Dithiophenylpyrrole derivative monomers for preparing semi-conducting polymers |
-
1999
- 1999-11-05 DE DE19953454A patent/DE19953454A1/en not_active Withdrawn
-
2000
- 2000-10-24 JP JP2001535366A patent/JP2003513100A/en active Pending
- 2000-10-24 EP EP00969542A patent/EP1230246A2/en not_active Withdrawn
- 2000-10-24 KR KR1020027005608A patent/KR20020068526A/en not_active Application Discontinuation
- 2000-10-24 WO PCT/EP2000/010471 patent/WO2001032664A2/en not_active Application Discontinuation
- 2000-10-24 AU AU79222/00A patent/AU7922200A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188899A (en) * | 2017-05-23 | 2017-09-22 | 苏州赛乐生物科技有限公司 | 4,8 disubstituted benzenes and double thiadiazole compound, derivative and synthetic methods |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001032664A3 (en) | 2002-05-10 |
| WO2001032664A2 (en) | 2001-05-10 |
| EP1230246A2 (en) | 2002-08-14 |
| AU7922200A (en) | 2001-05-14 |
| KR20020068526A (en) | 2002-08-27 |
| DE19953454A1 (en) | 2001-05-17 |
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