KR20020068526A - Novel Thiophenes and Method for Polymerization of Said Thiophenes - Google Patents
Novel Thiophenes and Method for Polymerization of Said Thiophenes Download PDFInfo
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Abstract
본 발명은 하기 화학식 I의 신규한 티오펜을 제공한다.The present invention provides novel thiophenes of formula (I)
<화학식 I><Formula I>
식 중,In the formula,
R 및 R'은 서로 독립적으로 수소, 알킬 또는 알콕시를 나타내거나, 또는 함께 -O-(CH2)n-O- 브릿지 (여기서, n은 1 내지 5임)를 나타낸다.R and R 'independently of one another represent hydrogen, alkyl or alkoxy, or together represent an -O- (CH 2 ) n -O- bridge, wherein n is 1 to 5.
상기 티오펜은 유기 전도체로서 사용될 수 있는 폴리티오펜의 제조에 적합하다.The thiophenes are suitable for the production of polythiophenes that can be used as organic conductors.
Description
본 발명은 전기 전도성 중합체의 제조에 적합한 신규한 티오펜 및 이들의 중합 방법에 관한 것이다.The present invention relates to novel thiophenes suitable for the production of electrically conductive polymers and methods of polymerization thereof.
폴리티오펜은 문헌 (미국 특허 출원 제4 987 421호)에 소위 유기 전도체 (organic conductors)로 알려져 있다.Polythiophenes are known in the literature (US Patent Application No. 4 987 421) as so-called organic conductors.
그러나, 가공능 또는 장기간 안정성과 같은 이들의 특성은 아직 모든 기술 분야에 있어서 충분한 것은 아니다. 따라서, 개선된 특성을 나타내는 폴리티오펜이 요구된다.However, their properties, such as processability or long term stability, are not yet sufficient in all technical fields. Accordingly, there is a need for polythiophenes that exhibit improved properties.
폴리티오펜은 보통 티오펜 단량체 또는 올리고머의 화학적 또는 전기화학적 중합에 의해 제조된다.Polythiophenes are usually prepared by chemical or electrochemical polymerization of thiophene monomers or oligomers.
따라서, 폴리티오펜의 특성을 개선시키기 위해서는 신규한 티오펜 단량체 또는 올리고머를 합성하는 것이 필요하다.Thus, it is necessary to synthesize novel thiophene monomers or oligomers in order to improve the properties of polythiophenes.
본 발명은 전기 전도성 중합체의 제조에 적합한 하기 화학식 I의 신규한 티오펜을 제공한다.The present invention provides novel thiophenes of the formula (I) which are suitable for the preparation of electrically conductive polymers.
식 중,In the formula,
R 및 R'은 서로 독립적으로 수소, 알킬 또는 알콕시를 나타내거나, 또는 함께 -O-(CH2)n-O- 브릿지 (여기서, n은 1 내지 5임)를 나타낸다.R and R 'independently of one another represent hydrogen, alkyl or alkoxy, or together represent an -O- (CH 2 ) n -O- bridge, wherein n is 1 to 5.
R 및 R'이 서로 독립적으로 수소, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알콕시기를 나타내거나, 또는 함께 -O-(CH2)n-O- 브릿지 (여기서, n은 1 내지 5임)를 나타내는 화학식 I의 화합물이 바람직한 티오펜이다.R and R 'independently of one another represent hydrogen, an alkyl group of 1 to 30 carbon atoms, an alkoxy group of 1 to 30 carbon atoms, or together an -O- (CH 2 ) n -O- bridge, wherein n is 1 to 5 Is a preferred thiophene.
적합한 화학식 I의 화합물의 예가 하기에 주어진다:Examples of suitable compounds of formula I are given below:
I-1 R = R' = 수소I-1 R = R '= hydrogen
I-2= -O-CH2-CH2-O-I-2 = -O-CH 2 -CH 2 -O-
I-3 R = R' = -O-C6H13(n)I-3 R = R '= -OC 6 H 13 (n)
I-4 R = 수소I-4 R = hydrogen
R' = -C6H13(n)R '= -C 6 H 13 (n)
지금까지 알려진 몇몇 티오펜의 중합은 심각한 단점들을 일으켰다:The polymerization of some thiophenes known to date has caused serious drawbacks:
- 단량체 화합물의 물에서의 난용성으로 인해 클로로포름, 메틸렌 클로라이드 또는 아세토니트릴과 같은 환경상 덜 친화적인 유기 용매를 사용하는 것이 종종 필요하다.Due to the poor solubility of the monomer compounds in water, it is often necessary to use less environmentally friendly organic solvents such as chloroform, methylene chloride or acetonitrile.
- 제조된 폴리티오펜은 종종 가공이 가능하지 않다.The polythiophenes produced are often not processable.
- 제조된 유기 전도체를 중성 형태로 전환시키기 위해 환원시키는 것이 종종 어렵다.It is often difficult to reduce the prepared organic conductors in order to convert them into neutral form.
본 발명의 또 다른 측면은 용액 중에서 가공할 수 있으며, 산으로 양성자화한 후 상기한 문제점들 없이 높고 안정한 전기 전도성을 나타내는 폴리티오펜을 제조하는 신규한 중합 방법에 관한 것이다.Another aspect of the present invention relates to a novel polymerization process for preparing polythiophenes that can be processed in solution and protonated with acid and then exhibit high and stable electrical conductivity without the above mentioned problems.
따라서, 본 발명은 또한 하기 화학식 I의 티오펜을 pKA가 3.75 미만이고 상응하는 짝염기가 비친핵성인 산을 사용하여 중합시키는 것을 특징으로 하는, 폴리티오펜의 제조 방법을 제공한다.Accordingly, the present invention also provides a process for the preparation of polythiophenes, characterized in that the thiophenes of the general formula (I) are polymerized with acids having a pK A of less than 3.75 and the corresponding counterbase is nonnucleophilic.
<화학식 I><Formula I>
식 중,In the formula,
R 및 R'은 서로 독립적으로 수소, 알킬 또는 알콕시를 나타내거나, 또는 함께 -O-(CH2)n-O- 브릿지 (여기서, n은 1 내지 5임)를 나타낸다.R and R 'independently of one another represent hydrogen, alkyl or alkoxy, or together represent an -O- (CH 2 ) n -O- bridge, wherein n is 1 to 5.
적합한 산의 예로는 포름산, 디플루오로아세트산, 트리플루오로아세트산 및디클로로아세트산이 있다.Examples of suitable acids are formic acid, difluoroacetic acid, trifluoroacetic acid and dichloroacetic acid.
본 발명의 방법은 포름산을 사용하여 수행하는 것이 바람직하다.The process of the invention is preferably carried out using formic acid.
본 발명의 방법은 10 내지 60 ℃의 반응 온도에서 수행하는 것이 바람직하다.The process of the invention is preferably carried out at a reaction temperature of 10 to 60 ℃.
제조된 중합체는 이전에 알려지지 않은 화합물이기 때문에, 본 발명은 또한 하기 화학식 II의 폴리티오펜을 제공한다.Since the polymers produced are previously unknown compounds, the present invention also provides polythiophenes of the formula II.
식 중,In the formula,
R 및 R'은 서로 독립적으로 수소, 알킬 또는 알콕시를 나타내거나, 또는 함께 -O-(CH2)n-O- 브릿지 (여기서, n은 1 내지 5임)를 나타내고, q는 2 내지 10,000일 수 있으며, R과 R'이 모두 수소인 화합물은 제외된다.R and R 'independently of one another represent hydrogen, alkyl or alkoxy, or together represent an -O- (CH 2 ) n -O- bridge, wherein n is 1 to 5, q is 2 to 10,000 days And compounds wherein both R and R 'are hydrogen.
R 및 R'이 모두 수소이고, 화학식 I-1의 티오펜으로부터 제조되는 화학식 II-1의 폴리티오펜은 이미 문헌 [Karikomi 외, J. Am. Chem. Soc.1995, 117, 6791-6792]에 공지되어 있다. 이는 4,8-비스(2-티에닐)벤조[1,2-c:4,5-c']-비스 [1,2,5]티아디아졸의 전기화학적 중합에 의해 제조되었다.Polythiophenes of formula (II-1), wherein R and R 'are both hydrogen and are prepared from thiophenes of formula (I-1), have already been described by Karikomi et al., J. Am. Chem. Soc. 1995 , 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.
벤조-비스[1,2,5]티아디아졸 잔기의 양성자화로 인해, 화학식 II의 폴리티오펜은 양이온 형태이다. 양전하가 분자 전체에 편재되어 있기 때문에 화학식에는 나타나지 않는다.Due to the protonation of the benzo-bis [1,2,5] thiadiazole moiety, the polythiophene of formula (II) is in cationic form. Because positive charges are localized throughout the molecule, they do not appear in the formula.
화학식 II의 폴리티오펜은 pKA가 3.75 이하이며 상응하는 짝염기가 비친핵성인 산의 첨가 또는 제거에 의해 양으로 하전된 상태와 중성 상태를 가역적으로 바꿀 수 있다.Polythiophenes of formula (II) can reversibly change the positively charged and neutral states by the addition or removal of acids having a pK A of 3.75 or less and the corresponding counterbase is nonnucleophilic.
화학식 II의 폴리티오펜의 특히 중요한 적용 분야에는 데이타 저장, 광학 시그날 프로세싱, 전자파 장애(EMI) 억제, 태양 에너지 전환, 재충전식 배터리, 전극, 발광 다이오드, 전계 효과 트랜지스터, 축전지, 센서, 전기채색 패널, 정전기 방지 재료, 특히 전기 부품용 포장 필름 및 사진 필름용 기재 필름, 복사기 드럼용 코팅, 및 인쇄 회로판 및 멀티층의 접속이 포함된다.Particularly important applications of the polythiophene of formula II include data storage, optical signal processing, electromagnetic interference (EMI) suppression, solar energy conversion, rechargeable batteries, electrodes, light emitting diodes, field effect transistors, batteries, sensors, electrochromic panels , Antistatic materials, in particular substrate films for packaging and photo films for electrical components, coatings for copier drums, and connections of printed circuit boards and multi-layers.
양성자화된 상태에 있어서의 화학식 II의 폴리티오펜의 전도성은 10-8내지 103S/cm, 바람직하게는 10-4내지 102S/cm의 범위이다.The conductivity of the polythiophene of formula (II) in the protonated state is in the range of 10 −8 to 10 3 S / cm, preferably 10 −4 to 10 2 S / cm.
화학식 II의 폴리티오펜은 각종 기술, 예컨대 UV-Vis-NIR 분광법, FT-IR 분광법, 점도 분석, GPC, 전도도 분석, MALDI-TOF MS, NMR 분광법, 순환 전압전류법 및 미량분석 (C, H, N 등)에 의해 특성화 하였다.Polythiophenes of formula (II) can be prepared by various techniques such as 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.).
화학식 I-2의 단량체로부터 제조된 화학식 II-2의 폴리티오펜의 경우, UV-Vis-NIR 분광법에 의해 밴드 간격이 0.3 eV인 것으로 측정되었다. 이는 용액 중에서 가공될 수 있는 중합체에 대해 지금까지 측정된 것 중 가능 낮은 값이다.For polythiophenes of formula II-2 prepared from monomers of formula I-2, the band spacing was determined to be 0.3 eV by UV-Vis-NIR spectroscopy. This is the lowest possible value measured so far for polymers that can be processed in solution.
화학식 I의 티오펜과 화학식 II의 폴리티오펜을 제조하는 한 방법이 하기 반응식에 의해 설명된다.One method of preparing thiophene of formula (I) and polythiophene of formula (II) is illustrated by the following scheme.
티오펜은 테트라아미노벤조퀴논과 SOCl2로부터 용이하게 얻어질 수 있는 벤조비스[1,2,5]-티아디아졸디온을, 상응하는 티오펜 유도체와 n-부틸리튬으로부터 용이하게 얻어질 수 있는 상응하는 2-티에닐리튬 유도체, 또는 2-티에닐브로모마그네슘 유도체와 반응시켜 제조한다. 중합은 포름산을 사용하여 수행한다.Thiophene is a benzobis [1,2,5] -thiadiazoledione, which can be easily obtained from tetraaminobenzoquinone and SOCl 2, and can be easily obtained from the corresponding thiophene derivative and n-butyllithium. Prepared by reaction with the corresponding 2-thienyllithium derivative, or 2-thienylbromo magnesium derivative. The polymerization is carried out using formic acid.
<실시예 1><Example 1>
4,8-디히드록시-4,8-비스(2-티에닐)벤조[1,2-c:4,5-c']-비스[1,2,5]티아디아졸 (I-1)의 합성4,8-dihydroxy-4,8-bis (2-thienyl) benzo [1,2-c: 4,5-c ']-bis [1,2,5] thiadiazole (I-1 ) Synthesis
무수 THF (75 ml) 중의 티오펜 (0.394 g, 4.68 mmol)의 용액을 아르곤 분위기하에서 -78 ℃로 냉각시켰다. 헥산 (3.0 ml) 중의 n-부틸리튬의 1.6 몰 용액을 10분에 걸쳐 이 용액에 첨가하였다. 얻어진 혼합물을 -78 ℃에서 15분간 교반시키고, 실온으로 가온하고, 이 온도에서 30분간 교반시키고, 다시 -78 ℃로 냉각시켰다. 내부 온도가 -60 ℃ 미만으로 유지되는 속도로 고형 벤조[1,2-c:4,5-c']-비스[1,2,5]티아디아졸-4,8-디온 (0.50 g, 2.23 mmol)을 칭량 투입하였다. 첨가가 완료된 후, 보라색 반응 혼합물을 -40 ℃로 가온하고, 이 온도에서 15분간 교반시키고, 다시 - 78℃로 냉각시켰다. 이 온도에서 무수 THF 중의 아세트산 용액 (50 중량%, 2 ml)을 첨가한 후, 이 용액을 실온으로 가온하였다. 아세트산에틸 (150 ml) 및 물 (100 ml)을 첨가하고, 상들을 분리하고, 유기층을 물로 잘 세척한 후, MgSO4에서 건조시켰다. 용매를 증발시켜 조질의 I-1이 남았고, 이를 아세트산/물로 재결정하여 화학식 I-1의 무색 프리즘 (0.52 g, 1.32 mmol, 59.2 몰%)을 얻었다. 융점: 228 ℃.A solution of thiophene (0.394 g, 4.68 mmol) in anhydrous THF (75 ml) was cooled to -78 ° C under 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 to −78 ° C. again. Solid benzo [1,2-c: 4,5-c ']-bis [1,2,5] thiadiazole-4,8-dione (0.50 g, 2.23 mmol) was weighed in. After the addition was complete, the purple reaction mixture was warmed to −40 ° C., stirred at this temperature for 15 minutes, and cooled to −78 ° C. again. At this temperature, an acetic acid solution (50% by weight, 2 ml) in dry THF was added and then the solution was allowed to warm to room temperature. Ethyl acetate (150 ml) and water (100 ml) were added, the phases were separated and the organic layer washed well with water and then dried over MgSO 4 . The solvent was evaporated to leave crude I-1, which was recrystallized from acetic acid / water to give a colorless prism of formula I-1 (0.52 g, 1.32 mmol, 59.2 mol%). Melting point: 228 ° C.
<실시예 2><Example 2>
4,8-디히드록시-4,8-비스(2-티에닐)벤조[1,2-c:4,5-c']-비스[1,2,5]-티아디아졸 (I-1)의 중합4,8-dihydroxy-4,8-bis (2-thienyl) benzo [1,2-c: 4,5-c ']-bis [1,2,5] -thiadiazole (I- 1) polymerization
포름산 (10 ml)을 미세하게 분쇄된 4,8-디히드록시-4,8-비스(2-티에닐) 벤조[1,2-c:4,5-c']-비스[1,2,5]티아디아졸 (25 mg)에 첨가하고, 이 혼합물을 실온에서 12 시간 동안 교반시켰다. 포름산 중의 얻어진 중합체 용액을 후속적으로 예를 들어 가압 공기 회전 주형 공정에 직접 사용할 수 있다.Formic acid (10 ml) was finely ground 4,8-dihydroxy-4,8-bis (2-thienyl) benzo [1,2-c: 4,5-c ']-bis [1,2 , 5] thiadiazole (25 mg) and the mixture was stirred at rt for 12 h. The resulting polymer solution in formic acid can subsequently be used directly, for example in a pressurized air rotary mold process.
Claims (3)
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 |
|---|---|
| KR20020068526A true KR20020068526A (en) | 2002-08-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020027005608A KR20020068526A (en) | 1999-11-05 | 2000-10-24 | Novel Thiophenes and Method for Polymerization of Said 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) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 EP EP00969542A patent/EP1230246A2/en not_active Withdrawn
- 2000-10-24 WO PCT/EP2000/010471 patent/WO2001032664A2/en not_active Application Discontinuation
- 2000-10-24 KR KR1020027005608A patent/KR20020068526A/en not_active Application Discontinuation
- 2000-10-24 AU AU79222/00A patent/AU7922200A/en not_active Abandoned
- 2000-10-24 JP JP2001535366A patent/JP2003513100A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001032664A3 (en) | 2002-05-10 |
| WO2001032664A2 (en) | 2001-05-10 |
| DE19953454A1 (en) | 2001-05-17 |
| EP1230246A2 (en) | 2002-08-14 |
| JP2003513100A (en) | 2003-04-08 |
| AU7922200A (en) | 2001-05-14 |
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