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WO2002004543A1 - Materiaux copolymeres semi-conducteurs a base d'unites oligo-phenylene et d'au moins une unite fluorene - Google Patents

Materiaux copolymeres semi-conducteurs a base d'unites oligo-phenylene et d'au moins une unite fluorene Download PDF

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Publication number
WO2002004543A1
WO2002004543A1 PCT/DE2001/002444 DE0102444W WO0204543A1 WO 2002004543 A1 WO2002004543 A1 WO 2002004543A1 DE 0102444 W DE0102444 W DE 0102444W WO 0204543 A1 WO0204543 A1 WO 0204543A1
Authority
WO
WIPO (PCT)
Prior art keywords
unit
phenylene
copolymer
fluorene
fluorene unit
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.)
Ceased
Application number
PCT/DE2001/002444
Other languages
German (de)
English (en)
Inventor
Rene Faber
Oskar Nuyken
Andrej Stasko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of WO2002004543A1 publication Critical patent/WO2002004543A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers

Definitions

  • the invention relates to copolymers with semiconducting properties based on oligophenylene, in particular for use in organic light-emitting diodes (OLEDS).
  • OLEDS organic light-emitting diodes
  • the object of the invention is to describe new organic compounds for use in organic light-emitting diodes which show good solubility and good processability.
  • the invention relates to a copolymer of at least one oligo-p-phenylene unit and a fluorene unit, the fluorene unit connecting the phenylene units via the spirocarbon (C9), so that in this way the main polymer chain. is formed.
  • the invention relates to a polymeric semiconductor whose conjugation length is independent of the degree of polymerization.
  • the invention furthermore relates to a method for producing a semiconducting copolymer from monomeric units.
  • the invention relates to the use of the copolymer in organic light-emitting diodes.
  • a group of well-defined copolymers comprising fluorenylidene-bridged conjugated oligo- (p-phenylene) units have been synthesized between 9, 9-bis (4-bromophenyl) fluorene and various aromatic compounds via a palladium-catalyzed coupling reaction (Suzuki coupling) Get bis boronic esters. It could be shown that this leads to polymeric compounds whose conjugation length is defined by the fluorine unit due to the electronic decoupling and is therefore independent of the degree of polymerization.
  • Some of the compounds according to the invention can be obtained in high yields and are soluble in conventional organic solvents such as chloroform.
  • the polymeric semiconductors are characterized in that their conjugation length is independent of the degree of polymerization, which is achieved by the electronic isolation of the chromophore (the oligo-p-phenylene unit).
  • a molecule with a central sp 3 -hybridized carbon atom is preferably used, which acts as a conjugation interrupter in the conjugated main polymer chain.
  • the two monomers are bifunctional boronic esters of p-phenylene II and p-terphenylene III, for the substituents R and R 1 :
  • R and R 1 are independently hydrogen or a branched or unbranched alkoxy group having up to 10 carbon atoms; and on the other hand a bifunctional molecule with a spirozentru, preferably a fluorene derivative, for example 9, 9-bis (4-bromophenyl) fluorene IV.
  • a commercially available fluorine derivative such as the bifunctional aniline derivative of fluorene IVa, which is converted into the corresponding dibromo compound IV via a conventional Sandmayer reaction, can be used to prepare the monomer fluorene derivative IV, preferably the dibromo derivative.
  • bifunctional p-phenylenediboronic acid esters II and p-terphenylenediboronic acid esters III are represented in accordance with regulations known from the literature, for example from L. Tietze, T.Eicher “Reactions and syntheses in an organic-chemical internship and research laboratory N Georg Thieme Verlag, Stuttgart, 1991, 1991 , Page 274ff.
  • copolymers are soluble in organic solvents and could therefore be examined by NMR spectroscopy.
  • a peak at 65.5 pp is characteristic in all 13 C-NMR spectra, which was assigned to the sp 3 -hybridized carbon atom of the fluorene unit.
  • the optical properties of the new compounds in a dilute dichloroethane solution could be investigated using UV / VIS spectroscopy.
  • the absorption properties of the resulting copolymer can be practically tailored.
  • the spectra obtained reflect the following trends: i) the absorption maxima are independent of the length of the polymer chain ii) compared to the unsubstituted copolymer Va, the alkoxy-substituted copolymers show a bathochro e shift in the absorption maximum. iii) with increasing length of the chromophore unit in the polymer backbone, a bathochromic shift in the absorption maximum is also observed.
  • the polymer is dissolved in hot toluene, the solution is concentrated and filtered. The filtrate is precipitated by dropping it in methanol. The precipitate is isolated and washed with dilute HCl solution. The polymer is then washed in a Soxhlet apparatus with acetone and dried in vacuo. Yield: 85%

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (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

L'invention concerne des copolymères aux propriétés semi-conductrices à base d'oligo-phénylène, s'utilisant notamment dans des diodes électroluminescentes organiques (OLEDS). A cet effet, la longueur de conjugaison de ces matériaux semi-conducteurs est indépendante du degré de polymérisation.
PCT/DE2001/002444 2000-07-07 2001-07-02 Materiaux copolymeres semi-conducteurs a base d'unites oligo-phenylene et d'au moins une unite fluorene Ceased WO2002004543A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10033111A DE10033111A1 (de) 2000-07-07 2000-07-07 Copolymere halbleitende Materialien auf der Basis von Oligo-Phenylen
DE10033111.4 2000-07-07

Publications (1)

Publication Number Publication Date
WO2002004543A1 true WO2002004543A1 (fr) 2002-01-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2001/002444 Ceased WO2002004543A1 (fr) 2000-07-07 2001-07-02 Materiaux copolymeres semi-conducteurs a base d'unites oligo-phenylene et d'au moins une unite fluorene

Country Status (2)

Country Link
DE (1) DE10033111A1 (fr)
WO (1) WO2002004543A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010136110A2 (fr) 2009-05-29 2010-12-02 Merck Patent Gmbh Polymères contenant des dérivés indénofluorène substitués en tant qu'unités structurales, procédés de préparation de ces polymères et leur utilisation
US9099655B2 (en) 2009-05-29 2015-08-04 Merck Patent Gmbh Composition comprising at least one emitter compound and at least one polymer having conjugation-interrupting units

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0755957A1 (fr) * 1995-07-13 1997-01-29 Air Products And Chemicals, Inc. Poly(éthers d'arylène) non halogénées
WO1997010193A1 (fr) * 1995-09-12 1997-03-20 The Dow Chemical Company Composes aromatiques a substitution ethynyl, leurs syntheses, polymeres et utilisations
US5621131A (en) * 1994-10-14 1997-04-15 Hoechst Aktiengesellschaft Conjugated polymers having spiro centers and their use as electroluminescence materials
WO1998033836A1 (fr) * 1997-01-30 1998-08-06 Jsr Corporation Procede de production de polymere contenant du phenylene et de materiau filmogene
EP0922998A1 (fr) * 1997-06-30 1999-06-16 Clariant International Ltd. Composition de reserve sensible au rayonnement et a haute tenue a la chaleur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5621131A (en) * 1994-10-14 1997-04-15 Hoechst Aktiengesellschaft Conjugated polymers having spiro centers and their use as electroluminescence materials
EP0755957A1 (fr) * 1995-07-13 1997-01-29 Air Products And Chemicals, Inc. Poly(éthers d'arylène) non halogénées
WO1997010193A1 (fr) * 1995-09-12 1997-03-20 The Dow Chemical Company Composes aromatiques a substitution ethynyl, leurs syntheses, polymeres et utilisations
WO1998033836A1 (fr) * 1997-01-30 1998-08-06 Jsr Corporation Procede de production de polymere contenant du phenylene et de materiau filmogene
EP0922998A1 (fr) * 1997-06-30 1999-06-16 Clariant International Ltd. Composition de reserve sensible au rayonnement et a haute tenue a la chaleur

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FÀBER, R. ET AL.: "Synthesis and characterization of new copolymers based on fluorenylidene-linked conjugated oligo(phenylene)s", MACROMOL. CHEM. PHYS., vol. 201, no. 17, November 2000 (2000-11-01), pages 2257 - 2266, XP002180805 *
KREYENSCHMIDT, G. ET AL.: "Thermally Stable Blue-Light-Emitting Copolymers of Poly(alkylfluorene)", MACROMOLECULES, vol. 31, no. 4, 1998 - 2 July 1998 (1998-07-02), pages 1099 - 1103, XP002180804 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010136110A2 (fr) 2009-05-29 2010-12-02 Merck Patent Gmbh Polymères contenant des dérivés indénofluorène substitués en tant qu'unités structurales, procédés de préparation de ces polymères et leur utilisation
DE102009023156A1 (de) 2009-05-29 2010-12-02 Merck Patent Gmbh Polymere, die substituierte Indenofluorenderivate als Struktureinheit enthalten, Verfahren zu deren Herstellung sowie deren Verwendung
JP2012528208A (ja) * 2009-05-29 2012-11-12 メルク パテント ゲーエムベーハー 置換インデノフルオレン誘導体を構造単位として含むポリマー、その調製方法およびその使用
US9099655B2 (en) 2009-05-29 2015-08-04 Merck Patent Gmbh Composition comprising at least one emitter compound and at least one polymer having conjugation-interrupting units
US9349960B2 (en) 2009-05-29 2016-05-24 Merck Patent Gmbh Compounds and polymers which contain substituted indenofluorene derivatives as structural unit, process for the preparation thereof, and the use thereof as electronic devices and mixtures and solutions

Also Published As

Publication number Publication date
DE10033111A1 (de) 2002-01-24

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