WO2002004543A1 - Copolymer semi-conductor materials made of oligo-phenylene units and at least one fluorene unit - Google Patents

Copolymer semi-conductor materials made of oligo-phenylene units and at least one fluorene unit Download PDF

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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
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unit
phenylene
copolymer
fluorene
fluorene unit
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German (de)
French (fr)
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Rene Faber
Oskar Nuyken
Andrej Stasko
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Siemens Aktiengesellschaft
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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
    • C08G61/02—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%

Abstract

The invention relates to copolymers having oligo-phenylene-based semi-conductor properties, and being especially used in organic light diodes (OLEDS). The conjugation length of said semi-conductor materials is independent of the degree of polymerisation.

Description

Beschreibungdescription
COPO YMERE HALBLEITENDE MATERIALIEN AUS OLIGO-PHENYLENEINHEITEN UND ZUMINDEST EINER FLUORENEINHEITCOPO YMERE SEMI-CONDUCTIVE MATERIALS FROM OLIGO-PHENYLENE UNITS AND AT LEAST ONE FLUORINE UNIT
Die Erfindung betrifft Copolymere mit halbleitenden Eigenschaften auf der Basis von Oligo-phenylen, insbesondere für die Anwendung in Organischen Leuchtdioden (OLEDS) .The invention relates to copolymers with semiconducting properties based on oligophenylene, in particular for use in organic light-emitting diodes (OLEDS).
In den letzten Jahren sind viele organische Materialien in Hinblick auf deren elektronische Eigenschaften erforscht worden. Neben Verbindungen mit ausgedehnten π- Elektronensystemen bewähren sich insbesondere Verbindungen, die eine hohe Glasübergangstemperatur haben. Dies ist vorwiegend bei polymeren Verbindungen der Fall. Deshalb sind Polymere mit ausgedehnten π-Elektronensystemen, wie z.B. Poly (p-phenylen) PPP und Poly (p-Phenylenvinylen) PPV als licht-emittierende Polymere vorgestellt worden (vgl. dazu G.Gustafsson et al in „Natureλ Band 357, 1992 S.477 ff). Das starre, konjugierte Grundgerüst dieser Polymere bewirkt die Unlöslichkeit und schlechte Verarbeitbarkeit der Verbindungen.In recent years, many organic materials have been researched for their electronic properties. In addition to connections with extensive π-electron systems, connections with a high glass transition temperature are particularly useful. This is mainly the case with polymeric compounds. Therefore, polymers with extensive π-electron systems, such as poly (p-phenylene) PPP and poly (p-phenylene vinylene) PPV, have been presented as light-emitting polymers (cf. G. Gustafsson et al in “Nature λ Volume 357, 1992 P.477 ff). The rigid, conjugated backbone of these polymers causes the insolubility and poor processability of the compounds.
Aufgabe der Erfindung ist es, neue organische Verbindungen zur Verwendung in organischen Leuchtdioden zu beschreiben, die gute Löslichkeit und gute Verarbeitbarkeit zeigen.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.
Gegenstand der Erfindung ist ein Copolymer aus zumindest einer Oligo-p-phenyleneinheit und einer Fluoreneinheit, wobei die 'Fluoreneinheit die Phenyleneinheiten über den Spiro- Kohlenstoff (C9) verbindet, so daß auf diese Weise die Polymerhauptkette. gebildet wird. Ein polymerer Halbleiter ist Gegenstand der Erfindung, dessen Konjugationslänge unabhängig vom Polymerisationsgrad ist. Weiterhin ist Gegenstand der Erfindung ein Verfahren zur Herstellung eines halbleitenden Copolymers aus monomeren Einheiten. Schließlich ist Gegenstand der Erfindung die Verwendung des Copolymers in organischen Leuchtdioden.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. Finally is The invention relates to the use of the copolymer in organic light-emitting diodes.
Eine Gruppe gut definierter Copolymere, die Fluorenyliden- verbrückte konjugierte Oligo- (p-phenylen) -Einheiten umfassen, wurden über eine Palladium katalysierte Kupplungs-Reaktion (Suzuki Kupplung) zwischen 9, 9-Bis (4-bromphenyl) -fluoren und verschiedenen aromatischen Bis-boronsäureestern erhalten. Dabei konnte gezeigt werden, dass dies zu polymeren Verbindungen führt, deren Kojugationslänge infolge der elektronischen Entkoppelung durch die Fluoreneinheit definiert ist und daher vom Polymerisationsgrad unabhängig ist. Die erfindungsge ässen Verbindungen können teilweise in hohen Ausbeuten erhalten werden und sind löslich in herkömmlichen organischen Lösungsmitteln wie beispielsweise Chloroform.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.
Die polymeren Halbleiter sind dadurch gekennzeichnet, daß ihre Konjugationslänge unabhängig vom Polymerisationsgrad ist, was durch die elektronische Isolation des Chromophors (der Oligo-p-phenyleneinheit) erreicht wird.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).
Bevorzugt wird zur elektronischen Entkopplung ein Molekül mit einem zentralen sp3-hybridisierten Kohlenstoff-Atom eingesetzt, das als Konjugations-Unterbrecher in der konjugierten Polymerhauptkette wirkt.For electronic decoupling, 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.
Zur Herstellung des Copolymers werden zwei bifunktionelle Monomere im stöchiometrischen Verhältnis unter Anwendung der Suzuki Polykondensationsmethode, wie bei M.Remmers, M. Schulze und G.Wegner in Makromolekulare Chemie, Rapid Communication (Makromol. Chem., Rapid Commun.) 17, 239, (1996) beschrieben, zur Reaktion gebracht.To produce the copolymer, two bifunctional monomers are used in a stoichiometric ratio using the Suzuki polycondensation method, as described by M.Remmers, M. Schulze and G.Wegner in Macromolecular Chemistry, Rapid Communication (Makromol. Chem., Rapid Commun.) 17, 239, (1996).
Bei den beiden Monomeren handelt es sich zum einen um bifunktionelle Boronsäureester des p-Phenylens II bzw. p- Terphenylens III, für deren Substituenten R und R1 gilt: R und R1 sind unabhängig voneinander Wasserstoff oder eine verzweigte oder unverzweigte Alkoxygruppierung mit bis zu 10 Kohlenstoffatomen; und zum anderen um ein bifunktionelles Molekül mit einem Spirozentru , bevorzugt ein Fluorenderivat, z.B. das 9, 9-Bis- (4-bromphenyl) -fluoren IV.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.
Zur Herstellung des Monomeren Fluorenderivats IV, bevorzugt das Dibromderivat, kann von einem kommerziell erhältlichen Fluorenderivat wie dem bifunktionellen Anilinderivat des Fluorens IVa ausgegangen werden, das über eine klassische Sandmayerreaktion in die entsprechende Dibromverbindung IV umgewandelt wird.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.
Die Darstellung der bifunktionellen p-Phenylendiboronsäure- ester II bzw. p-Terphenylendiboronsäureester III erfolgt nach literaturbekannten Vorschriften, wie z.B. aus L. Tietze, T.Eicher „Reaktionen und Synthesen im organisch-chemischen Praktikum und ForschungslaboratoriumN Georg Thieme Verlag, Stuttgart, 1991, Seite 274ff.The 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.
Die Copolymere sind in organischen Lösungsmitteln löslich und konnten deshalb NMR-spektroskopisch untersucht werden. Charakteristisch ist in allen 13C-NMR-Spektren ein Peak bei 65.5 pp , der dem sp3-hybridisiertem Kohlenstoffato der Fluoreneinheit zugeordnet wurde.The 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.
Die Molekulargewichte, die Absorptionscharakteristiken und die Glasübergangstemperatur der Copolymere sind in Tabelle 1 zusammengefasst. Die gute Löslichkeit der Copolymeren erlaubt auch deren Charakterisierung durch Gel-Permeations- chromatographie in Chloroform unter Benutzung eines Polystyrol Standards. Eine Polydispersität {Mw/Mn) von ca. 2 wurde berechnet, wodurch die Polykondensationsreaktion bestätigt wurde. Die Suzuki-Polykondensationmethode führte zu Copolymeren mit einem Polymerisationsgrad zwischen 26 und 41, wie aus Tabelle 1 ersichtlich. Tabelle 1: Eigenschaften der CopolymereThe molecular weights, the absorption characteristics and the glass transition temperature of the copolymers are summarized in Table 1. The good solubility of the copolymers also allows them to be characterized by gel permeation chromatography in chloroform using a polystyrene standard. A polydispersity {M w / M n ) of about 2 was calculated, whereby the polycondensation reaction was confirmed. The Suzuki polycondensation method resulted in copolymers with a degree of polymerization between 26 and 41, as can be seen in Table 1. Table 1: Properties of the copolymers
oiy er Λusteiu.t-e-6 mn Vlw ru± ur Λmax lg / .-•oiy er Λusteiu.te-6 m n Vl w ru ± ur Λ max lg / .- •
Va 76 7900 12400 1.57 40 297 289Va 76 7900 12400 1.57 40 297 289
Vb 85 11200 22000 1.96 41 325 210Vb 85 11200 22000 1.96 41 325 210
Vc 95 10900 21500 1.97 36 325 150Vc 95 10900 21500 1.97 36 325 150
Vd 84 10200 24500 2.39 26 332 184Vd 84 10200 24500 2.39 26 332 184
a angegeben in g*mol_1; bestimmt über Gel Permeations a given in g * mol _1 ; determined via gel permeations
Chromatographie in Chloroform mit einem UV/VIS Detektor (254 n ) gegen einen Polystyrol Standard. b Grad an Polymerisation, berechnet von Mn der entsprechendenChromatography in chloroform with a UV / VIS detector (254 n) against a polystyrene standard. b Degree of polymerization, calculated from M n of the corresponding
Comono eren Verbindung c Absorptionsmaxima die in verdünnten Dichloro ethan Lösungen gemessen wurden d Glasübergangstemperatur, die über DSC (2OK/min) gemessen wurde .Comono eren compound c absorption maxima which were measured in dilute dichloroethane solutions d glass transition temperature which was measured via DSC (2OK / min).
Unter Verwendung von UV/VIS-Spektroskopie konnten die optischen Eigenschaften der neuen Verbindungen in einer verdünnten Dichloro ethanlösung untersucht werden. Abhängig vom Typ der Oligo (p-phenylen) -Einheit und deren Sequenzlänge können die Absorptionseigenschaften des resultierenden Copolymers praktisch massgeschneidert werden. Die erhaltenen Spektren geben folgende Trends wieder: i) die Absorptionsmaxima sind unabhängig von der Länge der Polymerkette ii) im Vergleich zu dem unsubstituierten Copolymer Va zeigen die Alkoxy-substituierten Copolymere eine bathochro e Verschiebung des Absorptionsmaximums . iii) bei steigender Länge der Chromophor-Einheit im Polymer- Grundgerüst wird ebenfalls eine bathochrome Verschiebung des Absorptionsmaximums beobachtet. Schema 1The optical properties of the new compounds in a dilute dichloroethane solution could be investigated using UV / VIS spectroscopy. Depending on the type of oligo (p-phenylene) unit and its sequence length, 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. Scheme 1
Darstellung der Copolymere VRepresentation of the copolymers V
d(PPh3)4d (PPh3) 4
Figure imgf000006_0001
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000006_0002
Figure imgf000006_0003
Beispiele für V sind:
Figure imgf000006_0003
Examples of V are:
Figure imgf000007_0001
Im folgenden wird die Erfindung anhand von Beispielen näher erläutert:
Figure imgf000007_0001
The invention is explained in more detail below with the aid of examples:
Copolymer Va In einen Kolben werden unter Stickstoffatmosphäre 1,90g (4,0 mmol) IV, 0,98g (4,0 mmol) II (R = H) , 20 ml 2-molarer Kaliumcarbonat-Lösung sowie 19 ml THF gegeben. Die Mischung wird mehrmals entgast. 0,14g (0,12 mmol), 3 mol-% in Bezug auf die Monomere) Pd(PPh3)4 in 1 ml THF werden zugegeben. Das Reaktionsgemisch wird erneut entgast und vier Tage lang unter starkem Rühren auf 80 °C erwärmt. Das entstehende Polymer fällt aus der Reaktionsmischung aus. Nach dem Abkühlen wird das Polymer abgetrennt und in Chloroform gelöst. Das Polymer wird durch Eintropfen in Methanol gefällt, abgetrennt und mit verdünnter HCl-Lösung gewaschen. Das Polymer wird dann in einer Soxhlet-Apparatur mit Aceton gewaschen und im Vakuum getrocknet. Ausbeute: 76 % (lösliche Fraktion). IR (KBr) : 3023, 1600, 1487, 1446, 1020, 914, 808, 734 cm"1. XH NMR (CDC13) : δ = 7,71 =CH- fluorene (d, J = 7,3, 2 H) , 7,55-7,10 =CH- ( , 18 H) .Copolymer Va 1.90 g (4.0 mmol) IV, 0.98 g (4.0 mmol) II (R = H), 20 ml 2-molar potassium carbonate solution and 19 ml THF are placed in a flask under a nitrogen atmosphere. The mixture is degassed several times. 0.14 g (0.12 mmol), 3 mol% based on the monomers) Pd (PPh 3 ) 4 in 1 ml THF are added. The reaction mixture is degassed again and heated to 80 ° C. for four days with vigorous stirring. The resulting polymer precipitates out of the reaction mixture. After cooling, the polymer is separated off and dissolved in chloroform. The polymer is precipitated by dropping in methanol, separated off and washed with dilute HCl solution. The polymer is then washed in a Soxhlet with acetone and dried in vacuo. Yield: 76% (soluble fraction). IR (KBr): 3023, 1600, 1487, 1446, 1020, 914, 808, 734 cm "1. X H NMR (CDC1 3 ): δ = 7.71 = CH-fluorene (d, J = 7.3, 2 H), 7.55-7.10 = CH- (, 18 H).
13C NMR (CDCI3) δ = 151,47, 145,38, 140,59, 139,86, 139,34 aro . Cq, 129,01, 128,23, 128,01, 127,63, 127,18, 126,60, 120,66 arom. CH, 65,44 aliph. Cq. Elementaranalyse: (C3ιH2o)n (392, 50) n ber. C 94,86 H 5,14 gef. C 93,07 H 4,67 13 C NMR (CDCI3) δ = 151.47, 145.38, 140.59, 139.86, 139.34 aro. C q , 129.01, 128.23, 128.01, 127.63, 127.18, 126.60, 120.66 aromatic CH, 65.44 aliph. C q . Elemental analysis: (C 3 ιH 2 o) n (392, 50) n calc. C 94.86 H 5.14 found C 93.07 H 4.67
Copolymer (Vb)Copolymer (Vb)
Unter Stickstoffatmosphäre wird ein Kolben mit 1,43 g (3,0 mmol) des Monomers IV, 1,17g (3,0 mmol) des Monomers II (R= - 0-C4H9) , 20 ml 2-molarer Kaliumcarbonat-Lösung und 19 ml THF befüllt. Der Ansatz wird mehrmals entgast und anschließend mit Stickstoff begast. Dann werden 0,1g (0,09 mmol, 3 mol-% in Bezug auf die Monomere) Pd(PPh3)4 in 1 ml THF zugegeben und der Ansatz nochmals entgast. Das Reaktionsgemisch wird vier Tage lang bei 80 °C kräftig gerührt. Nach dem Abkühlen des Ansatzes wird die organische Phase abgetrennt und das Lösemittel am Rotationsverdampfer entfernt. Das Polymer wird in heißem Toluol gelöst, die Lösung eingeengt und filtriert. Das Filtrat wird durch Eintropfen in Methanol gefällt. Der Niederschlag wird isoliert und mit verdünnter HCl-Lösung gewaschen. Das Polymer wird anschließend in einer Soxhlet- Apparatur mit Aceton gewaschen und im Vakuum getrocknet. Ausbeute: 85%Under a nitrogen atmosphere, a flask containing 1.43 g (3.0 mmol) of monomer IV, 1.17 g (3.0 mmol) of monomer II (R = - 0-C 4 H 9 ), 20 ml of 2 molar potassium carbonate Solution and 19 ml THF filled. The batch is degassed several times and then gassed with nitrogen. Then 0.1 g (0.09 mmol, 3 mol% in relation to the monomers) Pd (PPh 3 ) 4 in 1 ml THF and the mixture degassed again. The reaction mixture is stirred vigorously at 80 ° C for four days. After the mixture has cooled, the organic phase is separated off and the solvent is removed on a rotary evaporator. 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%
IR (KBr) : 2955, 2868, 1487, 1375, 1203, 1017, 825, 739 cm"1. λE NMR (CDC13) : δ = 7,71 =CH- fluorene (d, J = 7,4, 2 H) , 7,43-7,17 =CH- (m, 14 H) , 6,84 -CH=C-0- (s, 2 H) , 3,77 -O-CHz- (t, J = 6,5, 4 H) , 1,54 -CH2- (q, J= 6,9, 4 H) , 1,24 (sext., J = 7,6, 4 H) , 0,77 -CH3 (t, J= 7,44, 6 H) .IR (KBr): 2955, 2868, 1487, 1375, 1203, 1017, 825, 739 cm "1. λ E NMR (CDC1 3 ): δ = 7.71 = CH-fluorene (d, J = 7.4, 2 H), 7.43-7.17 = CH- (m, 14 H), 6.84 -CH = C-0- (s, 2 H), 3.77 -O-CHz- (t, J = 6.5, 4 H), 1.54 -CH 2 - (q, J = 6.9, 4 H), 1.24 (sext., J = 7.6, 4 H), 0.77 - CH 3 (t, J = 7.44.6 H).
13C NMR (CDCI3) δ = 151,73, 150,66, 144,88, 140,62, 137,02, 130,76 arom. Cq, 129,65, 128,16, 127,83, 126,77, 120,54, 116,67 arom. CH, 69,80 -0-CH2-, 65,62 aliph. Cq, 31,78, 19,63 -CH2-, 14,19 -CH3. 13 C NMR (CDCI3) δ = 151.73, 150.66, 144.88, 140.62, 137.02, 130.76 aroma. C q , 129.65, 128.16, 127.83, 126, 77, 120.54, 116.67 aromatic CH, 69.80 -0-CH 2 -, 65.62 aliph. C q , 31.78, 19.63 -CH 2 -, 14.19 -CH 3 .
Elementaranalyse: (C39H36θ2)n (536,71)n ber. C 87,28 H 6,76 gef. C 87,23 H 6,44Elemental analysis: (C 3 9H 3 6θ 2 ) n (536.71) n calc. C 87.28 H 6.76 found C 87.23 H 6.44
Copolymer VcCopolymer Vc
In einen Kolben werden unter Stickstoffatmosphäre 1,90g (4,0 mmol) IV, 1,78g (4,0 mmol) II (R= -0-C6Hι3) , 20 ml 2-molarer Kaliumcarbonat-Lösung sowie 19 ml THF gegeben. Die Reaktionsmischung wird mehrmals entgast und mit Stickstoff begast. Anschließend werden 0,14g (0,12 mmol, 3 mol-% in Bezug auf die Monomere) Pd(PPh3)4 in 1 ml THF zugegeben. Der Ansatz wird nochmals entgast und vier Tage lang bei 80 °C kräftig gerührt. Nach dem Abkühlen des Ansatzes wird die organische Phase abgetrennt und das Lösemittel am Rotationsverdampfer entfernt. Das Polymer wird in heißem Toluol gelöst, die Lösung eingeengt und filtriert. Das Filtrat wird durch Eintropfen in Methanol gefällt. Der Niederschlag wird isoliert und mit verdünnter HCl-Lösung gewaschen. Das Polymer wird dann in einer Soxhlet-Apparatur mit Aceton gewaschen und im Vakuum getrocknet. Ausbeute: 95% IR (KBr) : 2927, 2856, 1488, 1378, 1206, 1017, 823, 741 cm"1. 1H NMR (CDC13) : δ = 7,71 =CH- fluorene (d, J = 7,4, 2 H) , 7,42-7,15 =CH- (m, 14 H) , 6,83 -CH=C-0- (s, 2 H) , 3,78 -O-CH2- (t, J = 6, 3, 4 H) , 1,56 -CH2- (q, J = 6, 5, 4 H) , 1,25- 1,14 -CH2- (m, 12 H) , 0,75 -CH3 (t, J= 6,7, 6 H) . 13C NMR (CDCI3) δ = 151,74, 150,59, 144,83, 140,61, 137,01, 130,57 arom. Cq, 129,66, 128,15, 128,04, 127,81, 126,74, 120,53, 116,44 arom. CH, 69,94 -0-CH2-, 65,60 aliph. Cq, 31,82, 29,63, 26,05, 22,89 -CH2-, 14,39 -CH3.1.90 g (4.0 mmol) IV, 1.78 g (4.0 mmol) II (R = -0-C 6 Hι 3 ), 20 ml 2-molar potassium carbonate solution and 19 ml are placed in a flask under a nitrogen atmosphere Given THF. The reaction mixture is degassed several times and gassed with nitrogen. Then 0.14 g (0.12 mmol, 3 mol% based on the monomers) of Pd (PPh 3 ) 4 in 1 ml of THF are added. The mixture is degassed again and stirred vigorously at 80 ° C. for four days. After the batch has cooled, the organic phase separated and the solvent removed on a rotary evaporator. 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 with acetone and dried in vacuo. Yield: 95% IR (KBr): 2927, 2856, 1488, 1378, 1206, 1017, 823, 741 cm "1. 1 H NMR (CDC1 3 ): δ = 7.71 = CH-fluorene (d, J = 7.4, 2 H), 7.42-7.15 = CH- (m, 14 H), 6.83 -CH = C-0- (s, 2 H), 3.78 -O-CH 2 - (t, J = 6, 3, 4 H), 1.56 -CH 2 - (q, J = 6, 5, 4 H), 1.25-1.14 -CH 2 - (m, 12 H ), 0.75 -CH 3 (t, J = 6.7, 6 H). 13 C NMR (CDCI3) δ = 151.74, 150.59, 144.83, 140.61, 137.01, 130 , 57 aroma C q , 129.66, 128.15, 128.04, 127.81, 126.74, 120.53, 116.44 aroma CH, 69.94 -0-CH 2 -, 65, 60 aliph. C q , 31.82, 29.63, 26.05, 22.89 -CH 2 -, 14.39 -CH 3 .
Elementaranalyse: (C43H44θ2)n (592, 82) n ber. C 87,12 H 7,48 gef. C 85,76 H 7,25Elemental analysis: (C 4 3H 44 θ 2 ) n (592, 82) n calc. C 87.12 H 7.48 found. C 85.76 H 7.25
Copolymer (Vd)Copolymer (Vd)
Unter Stickstoffatmosphäre wird ein Kolben mit 0,71g (1,5 mmol) des Monomers IV, 0,90g (1,5 mmol) des Monomers III (R= -O-C6H13, R1 = H) , 15 ml 2-molarer Kaliumcarbonat-Lösung sowie 14,5 ml THF gegeben. Die Reaktionsmischung wird mehrmals entgast und mit Stickstoff begast. Anschließend werden 0,05 g (0,045 mmol, 3 mol-% in Bezug auf die Monomere) Pd(PPh3)4 in 0,5 ml THF zugegeben. Der Ansatz wird nochmals entgast und vier Tage lang bei 80 °C kräftig gerührt. Das Polymer fällt aus dem Raktionsgemisch aus. Nach dem Abkühlen des Ansatzes wird das Polymer abgetrennt und in Chloroform gelöst. Nach dem Einengen wird die Lösung filtriert. Das Filtrat wird durch Eintropfen in Methanol gefällt. Der Niederschlag wird isoliert, mit verdünnter HCl-Lösung gewaschen. Das Polymer wird dann in einer Soxhlet-Apparatur mit Aceton gewaschen und im Vakuum getrocknet . Ausbeute: 84% IR (KBr): 2926, 2855, 1601, 1485, 1376, 1205, 1004, 815 cm"1. 1H NMR (CDC1 ) : δ = 7,74 =CH- fluorene (d, J = 7,7, 2 H) , 7,61-7,25 =CH- (m, 22 H) , 6,95 -CH=C-0- (s, 2 H) , 3,86 -O-CH2- (t, J= 6,3, 4 H), 1,62 -CH2- (q, J= 6,7, 4 H) , 1,32- 1,15 -CH2- (m, 12 H) , 0,77 -CH3 (t, J= 6,7, 6 H) . 13C NMR (CDCI3) δ = 151,56, 150,78, 145,30, 140,63, 139,69, 139,60, 137,71, 130,74 arom. Cq, 130,26, 129,00, 128,23, 127,27, 126,87, 126,64, 120,68, 116,53 arom. CH, 70,04 -O-CH2-, 65,49 aliph. Cq, 31,83, 29,70, 26,14, 22,95 -CH2-, 14,37 -CH3. Elementaranalyse: (C55H52θ2)n (745,01)n ber. C 88,67 H 7,03 gef . C 86,78 H 6, 91 Under a nitrogen atmosphere, a flask containing 0.71 g (1.5 mmol) of monomer IV, 0.90 g (1.5 mmol) of monomer III (R = -O-C6H 1 3, R 1 = H), 15 ml 2 -molar potassium carbonate solution and 14.5 ml of THF. The reaction mixture is degassed several times and gassed with nitrogen. Then 0.05 g (0.045 mmol, 3 mol% based on the monomers) of Pd (PPh 3 ) 4 in 0.5 ml of THF are added. The mixture is degassed again and stirred vigorously at 80 ° C. for four days. The polymer precipitates out of the reaction mixture. After the mixture has cooled, the polymer is separated off and dissolved in chloroform. After concentration, the solution is filtered. The filtrate is precipitated by dropping it in methanol. The precipitation will isolated, washed with dilute HCl solution. The polymer is then washed in a Soxhlet with acetone and dried in vacuo. Yield: 84% IR (KBr): 2926, 2855, 1601, 1485, 1376, 1205, 1004, 815 cm "1. 1 H NMR (CDC1): δ = 7.74 = CH-fluorene (d, J = 7 , 7.2 H), 7.61-7.25 = CH- (m, 22 H), 6.95 -CH = C-0- (s, 2 H), 3.86 -O-CH2- ( t, J = 6.3, 4 H), 1.62 -CH 2 - (q, J = 6.7, 4 H), 1.32- 1.15 -CH 2 - (m, 12 H), 0.77 -CH 3 (t, J = 6.7, 6 H). 13 C NMR (CDCI3) δ = 151.56, 150.78, 145.30, 140.63, 139.69, 139.60 , 137.71, 130.74 aroma. C q , 130.26, 129.00, 128.23, 127.27, 126.87, 126.64, 120.68, 116.53 aroma. CH, 70, 04 -O-CH 2 -, 65.49 aliphatic. C q , 31.83, 29.70, 26.14, 22.95 -CH 2 -, 14.37 -CH 3. Elemental analysis: (C 5 5H 5 2θ 2 ) n (745.01) n calc. C 88.67 H 7.03 found C 86.78 H 6, 91

Claims

Patentansprüche claims
1. Copolymer aus zumindest einer Oligo-phenyleneinheit und zumindest einer Fluoreneinheit, wobei die Fluoreneinheit die Phenyleneinheiten über den Spiro-Kohlenstoff (C9) verbindet, so dass auf diese Weise die Polymerhauptkette gebildet wird.1. Copolymer of at least one oligophenylene unit and at least one fluorene unit, the fluorene unit connecting the phenylene units via the spirocarbon (C9), so that the main polymer chain is formed in this way.
2. Copolymer nach Anspruch 1, bei dem die Fluoreneinheit eine 9, 9 ^-bifunktionelle Fluoreneinheit ist.2. A copolymer according to claim 1, wherein the fluorene unit is a 9, 9 ^ -ifunctional fluorene unit.
3. Copolymer nach einem der Ansprüche 1 oder 2, bei dem die Oligo-phenyleneinheit ein Pa-ra-Phenylenderivat ist.3. Copolymer according to one of claims 1 or 2, wherein the oligophenylene unit is a para-phenylene derivative.
4. Copolymer nach einem der vorstehenden Ansprüche, bei dem die inneren Benzolkerne der Oligo-p-phenyleneinheiten unabhängig voneinander 2, 5-Bis-alkoxy-l, 4-phenylenfragmente sind, wobei die Alkoxyreste unabhängig voneinander verzweigt oder unverzweigt sind und bis zu 10 Kohlenstoff-Atome umfassen.4. Copolymer according to one of the preceding claims, in which the inner benzene nuclei of the oligo-p-phenylene units are independently 2, 5-bis-alkoxy-l, 4-phenylene fragments, the alkoxy radicals being independently branched or unbranched and up to 10 Include carbon atoms.
5. Verfahren zur Herstellung eines Copolymers aus zumindest einer Oligo-phenyleneinheit mit zumindest einer Fluoreneinheit, wobei die Phenyleneinheit die Polymerhauptkette bildet und die Fluoreneinheit in regelmässigen Abständen eingebaut ist, das Copolymer aus monomeren Einheiten hergestellt wird und zumindest eine monomere Einheit eine Dibro verbindung eines nicht π- konjugierten Moleküls ist und zumindest eine andere monomere Einheit ein 1, 4-Phenylenboronsäurediester ist, die unter Palladium-Katalyse einer Suzuki-Kondensation unterworfen werden.5. A process for producing a copolymer from at least one oligophenylene unit with at least one fluorene unit, the phenylene unit forming the main polymer chain and the fluorene unit being installed at regular intervals, the copolymer being produced from monomeric units and at least one monomeric unit being a dibro compound is π-conjugated molecule and at least one other monomeric unit is a 1,4-phenylene-boronic diester, which are subjected to Suzuki condensation under palladium catalysis.
6. Verfahren zur Herstellung von polymeren Halbleitern durch den Einbau zumindest eines elektronisch isolierten Chromophors mit definierter Länge und Struktur in ein konjugiertes Polymer-Grundgerüst. 6. Process for the production of polymeric semiconductors by incorporating at least one electronically isolated chromophore with a defined length and structure into a conjugated polymer backbone.
7. Verfahren nach Anspruch 8, bei dem als elektronisch isoliertes Chromophor ein Monomer mit einem sp3- hybridisierten Kohlenstoffatom in die Polymerhauptkette eingebaut ist.7. The method as claimed in claim 8, in which a monomer with an sp 3 -hybridized carbon atom is incorporated into the main polymer chain as the electronically isolated chromophore.
8. Verwendung eines Copolymers nach einem der Ansprüche 1 bis 5 in einer organischen Leuchtdiode.8. Use of a copolymer according to one of claims 1 to 5 in an organic light emitting diode.
9. Polymerer Halbleiter dessen Kon ugationslänge unabhängig vom Polymerisationsgrad ist. 9. Polymer semiconductor whose conjugation length is independent of the degree of polymerization.
PCT/DE2001/002444 2000-07-07 2001-07-02 Copolymer semi-conductor materials made of oligo-phenylene units and at least one fluorene unit WO2002004543A1 (en)

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