EP1294791A1 - FUNKTIONALISIERTE &pgr;-KONJUGIERTE POLYMERE AUF 3,4-ALKYLENDIOXYTHIOPHEN-BASIS - Google Patents
FUNKTIONALISIERTE &pgr;-KONJUGIERTE POLYMERE AUF 3,4-ALKYLENDIOXYTHIOPHEN-BASISInfo
- Publication number
- EP1294791A1 EP1294791A1 EP01943342A EP01943342A EP1294791A1 EP 1294791 A1 EP1294791 A1 EP 1294791A1 EP 01943342 A EP01943342 A EP 01943342A EP 01943342 A EP01943342 A EP 01943342A EP 1294791 A1 EP1294791 A1 EP 1294791A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- branched
- independently
- linear
- another
- 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.)
- Withdrawn
Links
Classifications
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
- H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
Definitions
- the invention relates to new, active ester-functionalized ⁇ -conjugated polymers based on 3,4-alkylenedioxythiophene, their preparation from the monomers and their modification via the active ester function.
- these polymers Because of the considerable delocalization of the ⁇ electrons along the main chain, these polymers show interesting (nonlinear) optical properties and after oxidation or reduction they are good electrical conductors. As a result, these compounds are expected to play a leading and active role in various practical fields of application, such as in data storage, optical signal processing, electromagnetic interference suppression (EMI) and solar energy conversion, as well as in rechargeable batteries, light-emitting diodes, field-effect transistors, printed circuit boards, sensors and antistatic materials.
- EMI electromagnetic interference suppression
- Examples of known ⁇ -conjugated polymers are polypyrroles, polythiophenes, polyanilines, polyacetylenes, polyphenylenes and poly (p-phenylene-vinylenes).
- Active ester-functionalized ⁇ -conjugated polymers are known. Bäuerle et al. (Adv. Mater. 1996, 8, 214-218) produced active ester-functionalized polythiophenes.
- Active ester-functionalized ⁇ -conjugated polymers based on 3,4-alkylenedioxythiophene are not yet known.
- the conversion of these active ester-functionalized ⁇ -conjugated polymers into new functionalized ⁇ -conjugated polymers based on 3,4-alkylenedioxythiophene and the underlying monomers are also new.
- the invention relates to terthiophenes of the formula I which are suitable for the preparation of functionalized ⁇ -conjugated polymers based on 3,4-alkylenedioxythiophene:
- R, R ' independently of one another, are the same or different H, a linear or branched Cl to C18 alkyl or alkoxy radical or a linear or branched Cl to C18 alkyl or alkoxysulfonate radical.
- Scheme 1 shows the synthesis starting from N- ⁇ 6- [2,5-bis (3,4-ethylenedioxythien-2-yl) thien-3-yl] hexanoyl-oxy ⁇ pyrrolidin-2,5-dione (5) of 6- (Thien-3-yl) hexanoic acid (1).
- Compound 1 was described by Bäuerle et al. in Adv. Mater. 1996, 8, 214-218. Examples 1 to 4 describe the synthesis of monomer 5.
- the invention further relates to a process for the electrochemical polymerization of the monomers of the formula I.
- This electropolymerization can be carried out in various solvents (preferably in CH 2 C1 2 or acetonitrile) in the presence of various electrolytes (preferably tetrabutylammonium hexafluorophosphate or tetrabutylammonium perchlorate) ) occur.
- various electrolytes preferably tetrabutylammonium hexafluorophosphate or tetrabutylammonium perchlorate
- the above-mentioned monomers can also be chemically oxidatively polymerized, which is also the subject of the invention.
- Suitable oxidizing agents for the chemical polymerization of the abovementioned monomers are, for example, Fe (III) salts, in particular FeCl3, H2O2, K2S2O8, Na2S2 ⁇ g, KMnO_ ⁇ , alkali perborates and alkali or ammonium persulfates. Further suitable oxidizing agents are described, for example, in the Handbook of Conducting Polymers (Ed. Skotheim, TA), Marcel Dekker: New York, 1986, Vol. 1, 46-57.
- the invention furthermore relates to polythiophenes of the formula II which can be prepared by electrochemical or chemically oxidative polymerization of the monomeric terthiophenes of the formula II:
- R, R ' are, independently of one another, identical or different, H, a linear or branched Cl to C18 alkyl or alkoxy radical or a linear or branched Cl to C18 alkyl or alkoxy sulfonate radical.
- the invention relates to the modification of the polymers or layers of the ⁇ -conjugated polymers of the formula II produced electrochemically or by chemical oxidation by chemical reaction, in particular the reaction of the active ester with amines to form amides corresponding to formula III.
- R independently of one another, identically or differently, H, a linear or branched Cl to C18 alkyl or alkoxy radical or a linear or branched Cl to C18 alkyl or alkoxysulfonate radical and
- R £ is an oligonucleotide residue, such as
- R " is an oligonucleotide residue, such as
- Example 6 is the modification of poly (N- ⁇ 6- [2,5-bis (3,4-ethylenedioxylMen-2-yl) thien-3-yl] hexanoyl-oxy ⁇ pyrrolidin-2,5-dione (5) with an amino-substituted porphyrin derivative (for the preparation of this compound see Meunier et al. Tetrahedron, 1989, 45, 2641-2648).
- Particularly important areas of application for the prepared ⁇ -conjugated polymers based on 3,4-alkylenedioxythiophene include:
- the reaction is controlled by HPLC. After 8 hours the halogen component has been consumed and the reaction mixture is slowly warmed to room temperature. The solution is poured onto ice and extracted several times with dichloromethane. The organic phases are combined, washed several times with water and dried over sodium sulfate. After removal of the solvent, the crude product is chromatographed on silica gel with ethyl acetate / V ⁇ -hexane (2: 1) as the eluent. 0.63 g (55%) of 5 are obtained as yellow
- poly N- ⁇ 6- [2,5-bis (3,4-ethylenedioxythien-2-yl) thien-3-yl] hexanoyl-oxy ⁇ pyrrolidin-2,5-dione
- substitution of poly is carried out by immersion the polymer layer in a THF solution of the amino-substituted porphyrin A. After 20-30 min at room temperature, the polymer layer was removed and washed with absolute THF.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10025309 | 2000-05-23 | ||
DE10025309A DE10025309A1 (de) | 2000-05-23 | 2000-05-23 | Funktionalisierte PI-konjugierte Copolymere auf 3,4-Alkylendioxythiophen-Basis |
PCT/EP2001/005362 WO2001090212A1 (de) | 2000-05-23 | 2001-05-10 | FUNKTIONALISIERTE π-KONJUGIERTE POLYMERE AUF 3,4-ALKYLENDIOXYTHIOPHEN-BASIS |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1294791A1 true EP1294791A1 (de) | 2003-03-26 |
Family
ID=7643123
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01943342A Withdrawn EP1294791A1 (de) | 2000-05-23 | 2001-05-10 | FUNKTIONALISIERTE &pgr;-KONJUGIERTE POLYMERE AUF 3,4-ALKYLENDIOXYTHIOPHEN-BASIS |
Country Status (6)
Country | Link |
---|---|
US (1) | US20030195330A1 (de) |
EP (1) | EP1294791A1 (de) |
JP (1) | JP2003534418A (de) |
AU (1) | AU2001265942A1 (de) |
DE (1) | DE10025309A1 (de) |
WO (1) | WO2001090212A1 (de) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10302086A1 (de) * | 2003-01-21 | 2004-07-29 | Bayer Ag | Alkylendioxythiophene und Poly(alkylendioxythiophene) mit mesogenen Gruppen |
FR2852320B1 (fr) * | 2003-03-14 | 2005-05-20 | Nouveaux polymeres a base de nouveaux monomeres de types bithiophene, leur procede de preparation, et leurs applications | |
GB0319900D0 (en) * | 2003-08-23 | 2003-09-24 | Secr Defence | Polythiophene-based sensors |
JP2005255591A (ja) * | 2004-03-10 | 2005-09-22 | Kyoto Univ | 長鎖アルキル基を有するターチオフェン−フラーレン連結化合物及びその重合体 |
CN100372006C (zh) * | 2004-04-19 | 2008-02-27 | 财团法人工业技术研究院 | 具有三维数据图形的光学记录媒体及其制造方法 |
ITBO20040697A1 (it) * | 2004-11-11 | 2005-02-11 | Consiglio Nazionale Ricerche | Sonde oligonucleotidiche |
WO2009111675A1 (en) | 2008-03-06 | 2009-09-11 | Plextronics, Inc. | Modified planarizing agents and devices |
EP2509972B1 (de) * | 2009-12-11 | 2015-07-08 | Imec | Polymere mit 3-substituierten thiophenteilen als aktive schichten für solarzellen |
EP3234017A4 (de) | 2014-12-15 | 2018-05-30 | Nissan Chemical Industries, Ltd. | Zusammensetzungen mit lochträgermaterialien und fluorpolymeren sowie verwendungen davon |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3843412A1 (de) * | 1988-04-22 | 1990-06-28 | Bayer Ag | Neue polythiophene, verfahren zu ihrer herstellung und ihre verwendung |
-
2000
- 2000-05-23 DE DE10025309A patent/DE10025309A1/de not_active Withdrawn
-
2001
- 2001-05-10 EP EP01943342A patent/EP1294791A1/de not_active Withdrawn
- 2001-05-10 WO PCT/EP2001/005362 patent/WO2001090212A1/de not_active Application Discontinuation
- 2001-05-10 AU AU2001265942A patent/AU2001265942A1/en not_active Abandoned
- 2001-05-10 US US10/296,570 patent/US20030195330A1/en not_active Abandoned
- 2001-05-10 JP JP2001587021A patent/JP2003534418A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO0190212A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2001090212A1 (de) | 2001-11-29 |
JP2003534418A (ja) | 2003-11-18 |
US20030195330A1 (en) | 2003-10-16 |
AU2001265942A1 (en) | 2001-12-03 |
DE10025309A1 (de) | 2001-11-29 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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Extension state: AL LT LV MK RO SI |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: MEYER, ALEXANDER Inventor name: BAEUERLE, PETER Inventor name: REUTER, KNUD Inventor name: GROENENDAAL, LAMBERTUS |
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RBV | Designated contracting states (corrected) |
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