EP0863931A2 - Poly(9,9'-spirobisfluorenes), production et utilisation de ces composes - Google Patents

Poly(9,9'-spirobisfluorenes), production et utilisation de ces composes

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Publication number
EP0863931A2
EP0863931A2 EP96939844A EP96939844A EP0863931A2 EP 0863931 A2 EP0863931 A2 EP 0863931A2 EP 96939844 A EP96939844 A EP 96939844A EP 96939844 A EP96939844 A EP 96939844A EP 0863931 A2 EP0863931 A2 EP 0863931A2
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European Patent Office
Prior art keywords
alkyl
formula
polymers
polymer
poly
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EP96939844A
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German (de)
English (en)
Inventor
Ralf-Roman Rietz
Wolfgang Wernet
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Huntsman Advanced Materials Switzerland GmbH
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Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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Publication of EP0863931A2 publication Critical patent/EP0863931A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/33—Polycyclic acids
    • C07C63/49—Polycyclic acids containing rings other than six-membered aromatic rings
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/917—Electroluminescent

Definitions

  • the present invention relates to unsubstituted and substituted poly (9,9'-spirobisfluorene); a process for their manufacture; a composition of a carrier material and a layer of an unsubstituted or substituted poly (9,9'-spirobisfluorene), which optionally additionally contains a luminophore; a composition of an unsubstituted or substituted poly (9,9'-spirobisfluorene) which contains a luminophore; and the use of the compositions or the poly (9,9'-spirobisfluorene) as fluorophores, for example in light-emitting diodes or electrodes in display applications, and 2,2'-dihalo-7,7'-disubstituted 9,9'- Bisfluorenes.
  • 9,9'-bisfluorenes can be polymerized and blue fluorescent polymers are obtained which are soluble in many solvents and are therefore also easy to process, for example by means of conventional coating processes.
  • the polymers have excellent thermal and mechanical stabilities and they are excellent matrix systems for the incorporation of molecular fluorophores which can be used in fluorescent displays and in electroluminescent displays.
  • a first subject of the invention are poly (bis-9,9'-fluorenes) with identical or different recurring structural elements of formula 1,
  • the two Ri independently of one another are H, CrC 18 alkyl, C 6 -C 4 aryl, C 7 -C 15 aralkyl, C r C 18 alkoxy, R 2 - (0-C n H 2n ) m -0- , C, -C 8 alkyl thio, -C 8 -C dialkylamino, -C (0) OH, -C (0) 0-C r C 18 -AI- alkyl, -C (O) -N (C 1 - C 18 alkyl) 2 , -SO 3 H, -SO 3 -C, -C 18 alkyl, -SO 2 -N (C, -C 18 alkyl) 2 , d-C ⁇ -alkyl- C (O) -O- or d-Cu-alkyl-C) - represents, R 2 is H or -CC 12 alkyl, n is a number from 2 to 6, and m is a number of
  • the poly (bis-9,9'-fluorenes) according to the invention are soluble in many organic solvents, e.g. B. in THF, CH 2 CI 2 , DMF, DMSO or toluene.
  • alkyl groups in the radical R 1 as alkyl, alkoxy, alkylthio, diaminoalkyl, carboxylic acid ester or sulfonic acid ester, carboxamides or sulfonic acid amides, alkyl-CO 2 - and alkyl-C (O) - can be linear or branched and preferably contain 1 to 12, and particularly preferably 1 to 8 carbon atoms.
  • alkyl examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, do-decyl, tetradecyl, Hexadecyl and octadecyl.
  • R preferably contains 6 to 10 C atoms as aryl. Some examples are naphthyl, biphenylyl and particularly preferably phenyl.
  • Ri preferably contains 7 to 12 carbon atoms as the aralkyl and the alkylene group in the aralkyl preferably contains 1 or 2 carbon atoms.
  • a preferred example is benzyl and also phenylethyl.
  • R 2 as alkyl preferably contains 1 to 8 and particularly preferably 1 to 4 carbon atoms. It can be linear or branched. Some examples are methyl, ethyl, n-propyl and n-butyl.
  • n is preferably a number from 2 to 4, and particularly preferably 2 or 3.
  • m is preferably a number from 1 to 8, and particularly preferably a number from 1 to 6.
  • the two R ⁇ in the polymers of the formula I stand for the same radicals within the scope of the definitions.
  • a preferred embodiment of the subject of the invention is in the polymers of the formula IR, each for H, dC 12 alkyl-C (0) - or C r C ⁇ 2 alkoxy.
  • the polymers according to the invention can be crosslinked, which essentially depends on the production method.
  • the degree of crosslinking can be so high that a practically only crosslinked low molecular polymer is present, but is still soluble.
  • Such polymers contain structural elements of the formula (Ia), Ib or both structural elements,
  • Structural elements of the formula la are formed from monosubstituted and structural elements of the formula Ib from unsubstituted 9,9'-bisfluorenes.
  • the degree of polymerization (number of recurring structural units) can be from 2 to 100, more preferably 3 to 50, more preferably 3 to 40, and particularly preferably 5 to 30.
  • the term polymers thus also includes oligomers.
  • the polymers according to the invention contain polymer chains with different degrees of polymerization (chain lengths).
  • the polymers according to the invention can be prepared by analog processes known per se and described in the literature.
  • Another object of the invention is a process for the preparation of poly (bis-9,9'-fluorenes) with the same or different recurring structural elements of the formula
  • R t has the meaning given above, which is characterized in that a) at least one halogen-free 9,9'-bisfluorene of the formula II,
  • R which has the meaning given above, polymerizes cationically-oxidatively in the presence of an inert solvent.
  • Suitable solvents are, for example, N, N-disubstituted carboxamides and N-substituted lactams (dimethylformamide, N-methylpyrrolidone), esters (butyl acetate), ethers (dibutyl ether), sulfoxides (dimethyl sulfoxide), sulfones (tetramethylene sulfone), aliphatic and aromatic hydrocarbons (Toluene, xylene), halogenated or nitrated aliphatic table and aromatic hydrocarbons (carbon tetrachloride, tetrachloroethane) and carbon disulfide.
  • N, N-disubstituted carboxamides and N-substituted lactams dimethylformamide, N-methylpyrrolidone
  • esters butyl acetate
  • ethers dibutyl ether
  • sulfoxides dimethyl sulfoxide
  • the polymerization is carried out, for example, with oxidizing Lewis acids such as FeCI 3 , or with Lewis acids, mainly metal halides such as AICI 3 , AIBr 3 , BF 3 or BCI 3 , in combination with an oxidizing agent such as metal compounds with a higher valence level.
  • CuCI 2 is frequently used.
  • Oxidizing agents such as KMnO 4 , Fe +3 salts, benzoquinone derivatives such as tetrachlorobenzoquinone can also be used.
  • the electrochemical oxidation can also be used in a suitable organic solvent for the polymerization.
  • the molar ratio of spirobis fluorene to catalyst or Lewis acid can be from 1: 0.2 to 1: 2, preferably 1: 0.4 to 1 '1.5 and particularly preferably 1.0.5 to 1 1, 2.
  • the molar ratio of Lewis acid the oxidizing agent can be, for example, from 1 0.2 to 1 * 1, preferably 1 -0.3 to 1: 0.8 and particularly preferably 1: 0.4 to 1 0.6
  • the reaction temperature is preferably from 20 ° C. to 200 ° C., more preferably 20 ° C. to 150 ° C., particularly preferably 20 ° C. to 100 ° C., and particularly preferably 30 ° C. to 80 ° C.
  • the reaction can be carried out, for example, by adding the catalyst to the dissolved spirobis fluorene, heating if necessary and letting it react for some time (for example up to 24 hours) with stirring.
  • the polymer formed can then be precipitated and filtered off or the solvent removed.
  • the residues can be washed with water to remove the Lewis acids / oxidizing agents, dried and then treated with solvents such as, for example, methylene chloride or tetrahydrofuran, in order to obtain the desired soluble polymers isolate
  • solvents such as, for example, methylene chloride or tetrahydrofuran
  • Another object of the invention is a process for the preparation of poly (b ⁇ s-9,9'-fluorenes) with the same or different recurring structural elements of the formula
  • R t has the meanings given above, and X represents halogen, in the presence of an inert solvent, an alkali or alkaline earth metal and one
  • Transition metal complex or metal salt of a transition metal react
  • X preferably represents F, Cl or Br, more preferably Cl or Br, and particularly preferably Br
  • Suitable solvents are mainly the solvents used for Gnardard reactions, for example aromatic hydrocarbons such as benzene, toluene, xylene, nitrobenzene, and ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol diethyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether
  • aromatic hydrocarbons such as benzene, toluene, xylene, nitrobenzene
  • ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol diethyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether
  • Li, Na, K, Zn, Cd, Mg and Ca are frequently used as alkali and alkaline earth metals; Li and Mg are particularly preferred
  • the transition metal complexes can be those of metal ions or neutral metals.
  • metals are Fe, Co, Ni, Mo, Cr, W, and noble metals such as Pt, Pd, Ru, lr and Os.
  • the anions can be derived from inorganic or organic acids, for example acetic acid, benzoic acid, toluenesulfonic acid, sulfuric acid and hydrohalic acid.
  • Metal halide complexes are preferred.
  • neutral ligands are open-chain and cyclic 1, 3-dienes (cyclohexadiene, cyclooctadiene), nitriles (aceto- and benzonite), ethers, alcohols, tertiary phosphines (t ⁇ phenyl- and tncyclohexylphosphine), ditertiary diphosphines, tertiary amines and diene amines for example bipyndin.
  • metal complexes are N ⁇ (Cycloocta- d ⁇ en) 2 in a mixture with P (C 6 H 5 ) 3 , N ⁇ [P (C 6 H 5 ) 3 ] 4, N ⁇ CI 2 (B ⁇ pyr ⁇ d ⁇ n) 2 , N ⁇ Br 2 [P (C 6 H 5 ) 3 ] 2 , Pd (Cl) 2 (B ⁇ pyr ⁇ d ⁇ n) 2 , NiCI 2 , CoCI 2 , FeCI 2 and FeCI 3
  • the amount of alkali or alkaline earth metals is preferably aquimolar to the amount of dihalo-9,9'sp ⁇ rob ⁇ sfluoren; however, a slight excess can also be used.
  • the amount of transition metal complexes or transition metal salts is preferably also aquimolar, although a slight excess or deficit can be used.
  • the reaction can take place under mild conditions at room temperature. A higher temperature, for example up to 150 ° C, preferably up to 100 ° C accelerates the reaction
  • the polymerization can be carried out by combining the reaction components and the solvent, then heating and letting them react completely. To avoid excessively long incubation times, for example, less elemental iodine can be added.
  • the reaction can also be carried out in such a way that firstly the dihalo-9,9'-spioblefluorene and an alkali metal or alkaline earth metal or a corresponding one Metallalkyl produces the corresponding organometallic compound (Gngnard compound) and only then adds a transition metal complex
  • the polymers can be isolated in the customary manner, for example by filtration of insoluble constituents of the reaction mixture, washing to remove salts, precipitation or removal of the solvent.
  • the polymers can be purified by falling over and, if appropriate, washing
  • 2,2'-D ⁇ bromo-9,9'-sp ⁇ rob ⁇ sfluoren can be prepared by direct bromination of 9,9'Sp ⁇ rob ⁇ sfluoren in the presence of Lewis acids such as FeBr 3 (V Prelog et al., Helvetica Chimica Acta 52 (5), page 4253 (1969).
  • Lewis acids such as FeBr 3 (V Prelog et al., Helvetica Chimica Acta 52 (5), page 4253 (1969).
  • the product mixtures obtained from compounds with different degrees of bromination and positional isomers can be purified by recrystallization and chromatographic methods (1950) and purified from the product mixture by recrystallization and chromatographic processes.
  • the dinitro compound can, for example, be reduced to diamine using iron in ethanol, then diazotized and reacted with CuBr to form 2,2'-dibromo-9,9'-spinfluorene become
  • 2,2'-D ⁇ am ⁇ no-9,9'-sp ⁇ rob ⁇ sfluoren can be converted with alkylating agents into the corresponding N, N, N ', N'-tetraalkyl compounds.
  • the reaction of the dibromo compounds with organometallic hydrocarbon compounds (conventional compounds) leads to the dialkyl or diaryl derivatives.
  • Substitution with alcohols, thiols or polyoxaalkylene diol monoethers gives the derivatives substituted with alkoxy, alkylthio and polyoxaalkyleneoxy.
  • Diazotized 2,2'-dinitro-9,9'-spirobisfluorene can be converted with concentrated sulfuric acid into 2,2'-dihydroxy-9,9'-spirobis fluorene, which can be esterified in a manner known per se.
  • 2,2'-dimethyl-9,9'-spirobisfluorene can be oxidized to the carboxylic acid in a conventional manner and then esterified or amidated.
  • 9,9'-spirobisfluorene-2,2'-sulfonic acid can be obtained in a known manner by oxidation of 9,9'-spirobisfluorene-2,2'-dithiol, the ditiol being replaced by nucleophilic substitution of 2,2'-dibromo -9,9'-spirobisfluorene is accessible.
  • 2,2'-diacyl-9,9'-spirobisfluorenes are simple and high yields through Frie ⁇ del-Crafts acylation with carboxylic acid halides in the presence of Lewis acids such as AICI 3 .
  • the invention furthermore relates to compounds of the formula IV,
  • X represents halogen, and R 3 d-dg-alkyl, C 6 -C 4 aryl, C 7 -C 15 aralkyl, dC 18 alkoxy, R 2 - (OC n H 2n ) m -O-, C r C 8 alkyl thio , d-ds-dialkylamino, -C (0) OH, -C (0) 0-C ⁇ -C ⁇ e- alkyl, -C (0) -N (dC 18 -alkyl) 2 , -SO 3 H, -SO 3 -d-C ⁇ - 8 alkyl, -S0 2 -N (dC 18 -alkyl) 2 , dC 17 -alkyl-C (0) -O- or C, -C 17 -alkyl-C (0) - dar ⁇ represents, R 2 is H or -CC 12 alkyl, n is a number from 2 to 6, and m is a
  • X preferably represents Cl, Br or I, more preferably Cl or Br, and particularly preferably Br.
  • Another object of the invention is a process for the preparation of the compounds of formula IV, which is characterized in that a compound of formula V,
  • R 3 has the meaning given above, in an inert solvent with elemental halogen in the presence of an excess of a Lewis acid.
  • the reaction temperature can be from room temperature to 200 ° C., preferably from 20 to 100 ° C. and particularly preferably 20 to 50 ° C.
  • the reaction is particularly preferably carried out at room temperature, which may require cooling at the start of the reaction.
  • the halogen is preferably used in equimolar amounts.
  • Suitable solvents are polar aprotic solvents, which can be used alone or in mixtures. Some examples are open chain or cyclic ethers, Carbon disulfide and halogenated aliphatic or cycloaliphatic hydrocarbons
  • Suitable Lewis acids are, for example, BF 3 , BCI 3 , AIBr 3 , AICI 3 , ZnCI 2 , ZnBr 2 , FeCI 2l FeCI 3 , FeBr 2 , FeBr 3 , T ⁇ CI 4 , T ⁇ Br 4 , SnCI 2 , SnBr 2 , SnCI 4 and SnBr 4th AICI 3 or AIBr 3 is preferably used
  • Lewis acids otherwise used in halogenation reactions of aromatics in catalytic amounts are present in an amount of at least 1 mol, preferably at least 2 mol, more preferably at least 4 mol and particularly preferably at least 10 mol, based on 1 mol of the compound of Formula V
  • the isolation of the desired compounds and their purification can be carried out in a customary manner, the purification itself often not being necessary since by-products are formed only in small amounts.
  • the compounds according to the invention are crystalline or amorphous solids which are soluble in polar aprotic solvents and are therefore easy to process.
  • the monomers already have structural fluorescence radiation and they are outstandingly suitable for producing defined and generally uncrosslinked polymers
  • the polymers according to the invention are still soluble in conventional organic solvents and can therefore be used in solution as coating agents and easily processed. They have very high thermostabilities, glass transition temperatures and excellent mechanical properties. Furthermore, the poly (b ⁇ s-9,9'-fluorenes) according to the invention have absorption bands in the wavelength range below approximately 400 nm, and fluorescence emission maxima at wavelengths of approximately 420 to 460 nm. They are therefore blue fluorescent materials which are first are sometimes provided as processable polymers
  • Another object of the invention is a composition of (a) a solvent, such as THF, CH 2 Cl 2 , DMF, DMSO or toluene, and (b) a poly (b ⁇ s-9,9'-fluorene) with identical or different recurring structural elements of the formula I.
  • the amount of dissolved poly (bis-9,9'-fluorene) essentially depends on the solvent, degree of polymerization and crosslinking and the substitution.
  • the solutions according to the invention can contain 0.01 to 80, preferably 0.01 to 60, more preferably 0.01 to 50, particularly preferably 0.1 to 30 and particularly preferably 0.1 to 20% by weight of poly (to-9.9 '-fluorene) contain, based on the total amount of the composition.
  • composition according to the invention can contain further additives, for example processing aids, agents for improving the mechanical and thermal properties, agents for improving the appearance, or agents for improving the adhesive properties.
  • processing aids agents for improving the mechanical and thermal properties, agents for improving the appearance, or agents for improving the adhesive properties.
  • Some examples are flow agents or adhesion promoters, dyes, pigments, heat stabilizers and light stabilizers, antistatic agents, antioxidants, lubricants, mold release agents, fillers, reinforcing fillers and viscosity-increasing agents.
  • the composition (solution) according to the invention additionally contains at least one fluorescent dye (fluorophore).
  • fluorescent dyes are preferred whose absorption band overlaps the emission band (fluorescence emission) of the polymer according to the invention.
  • the amount of additional fluorescent dye can be, for example, 0.000001 to 10, preferably 0.00001 to 5, more preferably 0.0001 to 3, particularly preferably 0.001 to 2, and particularly preferably 0.001 to 2% by weight on the amount of polymer. A large number of such dyes are known.
  • Fluorescent latent pigments (solubilized pigments with solubilizing substituents such as cleavable protective groups) from the series of diketopyrrolopyrroles or quinacridones, fluorescent perylene derivatives or fluorescent perinones can also be used.
  • Commercial products such as Lumogen L Yellow ® , Brilliant Yellow “, Yellow Orange ® or Red Orange ® (BASF) and also 2,2'-dihydroxybipyridiles and related compounds can also be used.
  • compositions can be obtained by dissolving pigments solubilized with protective groups in the polymer according to the invention and then removing the protective group, for example by heating.
  • the composition (solution) according to the invention can be processed in molds with removal of the solvent, if appropriate using a vacuum, to form unsupported moldings and films.
  • the polymers obtained can be doped with, for example, iodine or salts such as, for example, alkali metal hexafluorometalates and used as electrical conductors, for example as electrodes.
  • the solutions are of particular importance for the coating of carrier materials.
  • Another object of the invention is a carrier material which is coated on at least one side with a polymer according to the invention.
  • the polymer layer in homogeneous distribution contains at least one further fluorophore in homogeneous distribution, the emission band of the polymer preferably overlapping the absorption band of the fluorophore. Due to the content of additional fluorophores, by choosing different emissions in the visible range, all colors of the visible spectrum can be generated, the polymer itself having the blue fluorescent radiation. This blue fluorescent background radiation can be amplified or modified by blue-emitting fluorophores. The preferred amounts and a few selected fluorophores have been stated beforehand
  • the carrier material can be inorganic or organic carrier materials.
  • the carrier material can be opaque, translucent or transparent.
  • Transparent carrier materials are preferred. Suitable carrier materials are, for example, plastics, glass, ceramics, minerals, rocks, metal oxides and mixed oxides, metal nitrides, metal carbides, semiconductors, transparent electrical conductors (for example ITO glass, glass carriers with SnO 2 / ln 2 O) 3 coated), metals and metal alloys.
  • a particularly advantageous embodiment of the invention is therefore electroluminescent compositions which consist of an electrical conductor as the carrier material, which on at least one side with a polymer according to the invention, alone or in a mixture with other at least one additional fluorophore is coated.
  • the coating is preferably connected to a counter electrode, which is particularly preferably transparent
  • the electrical conductors can be opaque, translucent or transparent and semiconductors or metallic conductors.
  • Transparent conductors are preferably glasses coated with semiconducting metal oxides or mixtures of metal oxides.
  • the layer thickness of the polymer layer can be, for example, 0.1 to 1000, preferably 1 to 500 and particularly preferably 10 to 200 ⁇ m.
  • the coated carrier material can be produced in a manner known per se by immersion, brushing or casting processes, in particular centrifugal casting, the layer thickness being able to be determined via the content of polymer and, if appropriate, fluorophore in the solution and the choice of process conditions.
  • the polymers and coated carrier materials according to the invention can be used wherever markings are to be detected using fluorophores or decorative effects are to be achieved.
  • the coated electrical conductors can be used particularly advantageously as light-emitting diodes for the entire visible spectrum.
  • Transparent coated electrodes are also suitable for screens or display elements of electronic image display systems.
  • Another object of the invention is the use of the polymers according to the invention, optionally additionally doped with at least one further fluorophore, as the active radiation layer for light-emitting diodes, screens and display elements.
  • Example A1 Preparation of 2,2'-d ⁇ bromo-9,9'-sp ⁇ rob ⁇ sfluoren.
  • Example A2 Preparation of 2,2'-dihydroxy-9,9'-spirobisfluorene.
  • a solution of 0.7 g of 2,2'-diamino-9,9'-spirobisfluorene in 70 ml of semi-concentrated sulfuric acid is mixed at 0 to 5 ° C with a solution of 0.337 NaN0 2 in 20 ml of water and stirred for one hour .
  • the reaction solution is added to 40 ml of concentrated sulfuric acid and stirred at reflux for one hour.
  • the precipitate is filtered off, washed with water and the title compound is obtained in 74% yield.
  • Example A3 Preparation of 2,2'-dihexanoyl-9,9'-spirobisfluorene.
  • a solution of 31.6 9,9'-spirobisfluorene is added to a suspension of 79.1 mmol of finely divided AICI 3 and 69.9 mmol of hexanoyl chloride in 100 ml of CS 2 .
  • the mixture is stirred for one hour at room temperature and then poured into 40 ml of ice-cold water.
  • the mixture is acidified with hydrochloric acid and the two phases are separated.
  • the aqueous phase is extracted once with methylene chloride.
  • the combined organic phases are washed with water and dried over anhydrous potassium carbonate.
  • Example A4 Preparation of 2,2'-dibromo-7,7'-dihexanoyl-9.9'-spirobisfluorene.
  • a solution of 28.5 mmol of 2,2'-dihexanoyl-9,9'-spirobisfluorene in 50 ml of CS 2 is slowly added to a stirred suspension of 0.171 mmol of finely divided AICI 3 in 100 ml of CS 2 and then heated under reflux for one hour .
  • the reaction solution is cooled and then 57 mmol bromine in 50 ml CS 2 are added.
  • the mixture is stirred at room temperature overnight with the exclusion of light.
  • the reaction mixture is then made up of a mixture of 300 Poured ml of ice and 30 ml of hydrochloric acid and separated the phases.
  • the aqueous phase is washed twice with 200 ml of CS 2.
  • the combined organic phases are washed with 300 ml of five percent aqueous sodium bicarbonate solution and then dried with Na 2 SO 4 . After evaporation of the solvent, the title compound is obtained in 95% yield. Elemental analysis [(found) (theoretical)]: C 64.98% (66.28); H 4.87% (5.11); Br 25.33% (23.83) O 4.48% (4.77).
  • Examples B1 -B4 Direct polymerization of 9,9'-spirobisfluorene (SBF). 1 mole of 9,9'-spirobisfluorene is polymerized in CS 2 with AICI3 / CUCI at 30 ° C. Further information can be found in Table 1.
  • PSBF means poly (9,9'-spirobisfluorene). The polymers are amorphous and light brown, blue fluorescent solids.
  • the polymer of Example B2 gives a M n of 2684 and an M w of 16516 in the GPC analysis with polystyrene as standard. In the analysis with MALDI-MS, a degree of polymerization of up to 31 can be detected.
  • the polymer B1 softens at 349 ° C and decomposes at 434 ° C.
  • Table 2 The other data determined by differential thermal analysis are given in Table 2.
  • the resulting polymer is precipitated in HCl acidic methanol (100-150 ml), filtered, washed with methanol, dilute hydrochloric acid and water and then dried at 50 9 C in vacuo.
  • 0.605 g (91% of theory) of a blue fluorescent polymer which is soluble in tetrahydrofuran, DMF and CH 2 Cl 2 are obtained.
  • the investigation with MALDI-MS shows degrees of polymerization around 12.
  • the GPC analysis with polystyrene as standard gives an M n of 2264 and an M w of 9213.
  • Example B6 Polymerization of 2,2'-dibromo-7,7'-dihexanoyl-9.9-spirobisfluorene. 1 g (1.47 mmol) of 2,2'-dibromo-7,7'-dihexanoyl-9.9'-spirobifluorene together with 274 mg (1.76 mmol) of bipyridil, 158 mg (1.47 mmol) of COD and 293 mg (1.76 mmol) Ni (COD) 2 dispersed in 15 ml DMF. The dispersion is heated to 70 9 C and stirred for 4 days under inert gas (argon) at this temperature. Then proceed as in example B5.
  • inert gas argon
  • Example B2 The polymer of example B2 or example B5 is dissolved in CH 2 CI 2 and a 100 nm thick film is produced on a quartz plate by means of centrifugal casting and the absorption and emission spectrum are measured.
  • the absorption maximum is in both cases at ⁇ max equal to 370 nm and the emission maximum at ⁇ m a x equal to 420 nm.
  • the absorption maximum is irradiated (370 nm) and the emitted radiation is measured with a suitable device (fluorescence spectrometer) depending on the wavelength.
  • Example C2 Example C2:
  • a film according to example C1 is produced from the polymer according to example B6.
  • the absorption spectrum is broadened compared to example C1 and has two absorption maxima at ⁇ max equal to 340 and 355 nm.
  • the emission maximum is ⁇ max equal to 430 nm.
  • a film according to example C1 is produced from the polymer according to example B6, with an additional 0.5% by weight of a fluorophore being dissolved.
  • the results are shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Luminescent Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des poly(bis 9,9'-fluorènes) avec des éléments structuraux récurrents, identiques ou différents, de la formule (I) où les deux radicaux R1 représentent, indépendamment l'un de l'autre, H, alkyle C1-C18, aryle C6-C14, aralkyle C7-C15, alcoxy C1-C18, R2-(O-CnH2n)m-O-, alkylthio C1-C18, dialkylamino C1-C18, -C(O)OH, -C(O)O-alkyle C1-C18, -C(O)-N(alkyle C1-C18)2, -SO3H, -SO3-alkyle C1-C18, -SO2-N(alkyle C1-C18)2, alkyle C1-C17-C(O)-O- ou alkyle C1-C17-C(O), R2 représente H ou alkyle C1-C12, n vaut un nombre compris entre 2 et 6 et m vaut un nombre compris entre 1 et 12. Les polymères peuvent être utilisés seuls ou en mélange avec au moins un fluorophore dont la bande d'absorption recouvre la bande d'émission (émission fluorescente) du polymère de la formule (I), sous forme de couche de rayonnement active pour les diodes électroluminescentes, les écrans et les afficheurs.
EP96939844A 1995-12-01 1996-11-19 Poly(9,9'-spirobisfluorenes), production et utilisation de ces composes Withdrawn EP0863931A2 (fr)

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CH341195 1995-12-01
CH3411/95 1995-12-01
PCT/EP1996/005091 WO1997020877A2 (fr) 1995-12-01 1996-11-19 Poly(9,9'-spirobisfluorenes), production et utilisation de ces composes

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WO1997020877A2 (fr) 1997-06-12
CA2237461A1 (fr) 1997-06-12
JP2000502128A (ja) 2000-02-22
US6132641A (en) 2000-10-17
WO1997020877A3 (fr) 1997-09-12
KR19990071499A (ko) 1999-09-27
US20020132911A1 (en) 2002-09-19
AU7693396A (en) 1997-06-27
US6380445B1 (en) 2002-04-30
US6559277B2 (en) 2003-05-06
CN1203609A (zh) 1998-12-30
BR9612111A (pt) 1999-02-17
EA001312B1 (ru) 2001-02-26
PL326841A1 (en) 1998-10-26
EA199800496A1 (ru) 1998-12-24

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