EP2867329A1

EP2867329A1 - Polymers containing 2,7-pyrene structure units

Info

Publication number: EP2867329A1
Application number: EP13728120.0A
Authority: EP
Inventors: Anna Hayer; Niels Schulte
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2012-06-29
Filing date: 2013-06-12
Publication date: 2015-05-06
Also published as: WO2014000860A1; US9695274B2; JP2015531002A; JP6422861B2; US20150322198A1

Abstract

The present invention relates to polymers containing 2,7-pyrene structure units, methods for producing thereof, and blends and formulations containing said polymers. The present invention further relates to the use of polymers or blends according to the invention in electronic devices and to electronic devices, particularly OLEDs, containing polymers or blends according to the invention.

Description

Polymers containing 2,7-pyrene structural units

The present invention relates to polymers containing 2,7-pyrene structural units, processes for their preparation and blends and formulations containing these polymers. The present invention further relates to the use of the polymers according to the invention or

Blends in electronic devices and electronic devices, in particular OLEDs, containing the polymers or blends of the invention. Compounds such as the polymers according to the invention are used for a number of different applications, which in the broadest sense of the

Electronics industry can be attributed developed. The construction of organic electroluminescent devices (OLEDs) in which these organic semiconductors as functional materials among others

are preferably used, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136 described.

Various polymeric materials suitable for use in organic electroluminescent devices are known in the art. For example, compounds based on monomer units such as spirobifluorene, fluorene, indenofluorene,

Phenanthrene or dihydrophenanthrene in WO 04/041901, the

WO 04/113412 and WO 05/014689. However, there is a continuing need for new materials for use in organic electronic devices, particularly with a view to improving the devices in the following points: 1. Materials with a larger bandgap are needed so that one gets deeper blue singlet emission for

Achieve display applications with a large color gamut. Greater band gaps in polymers would also allow them to be used as host materials not only for red but also for green triplet Emission to use.

2. The lifetime and efficiency of organic electroluminescent devices should be further increased, especially in blue emitting systems and for high quality applications.

It is therefore an object of the present invention to provide new materials for electronic devices which have a larger band gap or improve the life and efficiency of organic electroluminescent devices.

Surprisingly, it has been found that compounds containing 2,7-pyrene units have been successfully used as materials in electronic

Devices, preferably organic electroluminescent devices, can be used.

The subject of the present application is thus a polymer containing one or more structural units of the following formula (I),

in which

R ¹ in each occurrence, identically or differently H, D, F, Cl, Br, I, OH, N (R ² ) ₂ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, in which also one or more H atoms may be replaced by R ² and in which also one or more non-adjacent CH ₂ groups by O, S, Si (R ² ) ₂ , Ge (R ² ) ₂ , BR ² , NR ² , PR ² , CO, C = S, C = Se, C = ik ² , PO (R ² ), PS (R ² ), R ² C = CR ² , C = C, SO, SO ₂ , COO, O (CO) O or CONR ² may be replaced, or a mono- or polycyclic, aromatic or heteroaromatic ring system;

R ² in each occurrence, identically or differently H, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, in also one or more H atoms may be replaced by F and in which also one or more non-adjacent CH ₂ groups may be replaced by O, CO, COO or O (CO) O, or a mono- or polycyclic, aromatic or heteroaromatic ring system; and

the dashed lines are the bonds to the neighboring ones

Represent structural units in the polymer. The polymers according to the invention preferably contain from 2 to 10 000 repeat units, the term "polymer" being intended to encompass both polymers and dendrimers and oligomers in the present application The oligomeric compounds according to the invention have from 2 to 9 repeat units Preferred polymers and dendrimers according to the invention contain in total 10 to 10,000 repeat units The degree of branching DB of the polymers and dendrimers may be between 0 (linear polymer without branching points) and 1 (fully branched dendrimer).

The polymers according to the invention preferably have a molecular weight M _w in the range from 1000 to 2,000,000 g / mol, more preferably a molecular weight M _w in the range from 10,000 to 1,500,000 g / mol and most preferably a molecular weight M _w in the range of 50,000 up to 1,000,000 g / mol. The determination of the molecular weight M _w is carried out by means of GPC (= gel permeation chromatography) against an internal polystyrene standard.

In the embodiment according to the invention, the proportion of the structural units of the formula (I) in the polymer is from 0.01 to 100 mol%, preferably 1 to 95 mol%, particularly preferably 10 to 80 mol% and very particularly preferably 30 to 60 mol%.

The term "mono- or polycyclic, aromatic ring system" in the present application means an aromatic ring system having 6 to 60, preferably 6 to 30, more preferably 6 to 14 and most preferably 6 to 10 aromatic ring atoms, which is not necessarily only contains aromatic groups but in which also several aromatic units by a short non-aromatic unit (<0% of the atoms other than H, preferably <5% of the atoms other than H), such as sp ³ -hybridized carbon atom or O or N atom, CO group, etc. may be interrupted. for example, systems such as 9,9 ^{'spirobifluorene,} 9,9-diarylfluorene, etc. should be understood as aromatic ring systems. The aromatic ring systems can be mono- or polycyclic, ie they may have one ring (eg phenyl) or several rings which may also be condensed (eg naphthyl) or covalently linked (eg biphenyl), or a Combination of condensed and linked rings included.

Preferred aromatic ring systems are e.g. Phenyl, biphenyl,

Terphenyl, naphthyl, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, fluorene, indene, indenofluorene and

Spirobifluoren.

By the term "mono- or polycyclic, heteroaromatic

Ring system "in the present application is an aromatic

Ring system with 5 to 60, preferably 5 to 30, more preferably 5 to 20 and most preferably 5 to 9 understood aromatic ring atoms, wherein one or more of these atoms is / are a heteroatom.

The "mono- or polycyclic heteroaromatic ring system" does not necessarily contain only aromatic groups but may also be replaced by a short non-aromatic moiety (<10% of that of H

different atoms, preferably <5% of those other than H. Atoms), such as sp ³ -hybridized carbon atom or O or N atom, CO group, etc., be interrupted.

The heteroaromatic ring systems may be mono- or polycyclic, i. they may have one or more rings, which may also be fused or covalently linked (e.g., pyridylphenyl), or a combination of fused and linked rings. Preference is given to fully conjugated heteroaryl groups.

Preferred heteroaromatic ring systems are e.g. 5-membered rings such as pyrrole, pyrazole, imidazole, 1, 2,3-triazole, 1, 2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole , 1, 2,3-oxadiazole, 1, 2,4-oxadiazole, 1, 2,5-oxadiazole,, 3,4-oxadiazole, 1, 2,3-thiadiazole, 1, 2,4-thiadiazole, 1, 2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,3-triazine , 1, 2,4,5-tetrazine, 1, 2,3,4-tetrazine, 1, 2,3,5-tetrazine, or condensed groups such as indole, isoindole, indolizine, indazole,

Benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine imidazole, quinoxaline imidazole, benzoxazole,

Naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,

Benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole,

Benzocarboline, phenanthridine, phenanthroline, thieno [2,3b] thiophene, thieno [3,2b] thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene or combinations of these groups.

The mono- or polycyclic, aromatic or heteroaromatic ring system may be unsubstituted or substituted. Substituted means in the present application that the mono- or polycyclic, aromatic or heteroaromatic ring system has one or more substituents R ¹ . Preferred structural units of the formula (I) are characterized by those described in the

The following formulas (Ia) to represented (Ic), wherein the formula (Ic) is particularly preferred.

The dashed lines in the formulas (Ia), (Ib) and (Ic) represent the bonds to the adjacent structural units in the polymer. R ¹ in the formulas (Ia) and (Ib) can in this case correspond to those described for R ¹ Assume the meanings given for formula (I).

Preferably, R ¹ in the formulas (I), (Ia) and (Ib) at each occurrence, identically or differently, is a straight-chain alkyl or alkoxy group having 1 to 10 C atoms, particularly preferably 1 to 6 C atoms, or a branched alkyl or alkoxy group having 3 to 10 C atoms, particularly preferably having 3 to 6 C atoms, an aromatic ring system having 6 to 30, particularly preferably having 6 to 18 aromatic ring atoms or a heteroaromatic ring system having 5 to 30, especially preferably having 5 to 20 ring atoms, of which at least one ring atom is a heteroatom is. The aromatic or heteroaromatic ring system may either be unsubstituted or substituted by one or more radicals R ³ , where R ^{3 is the} same or different and is a straight-chain alkyl or alkoxy group having 1 to 10 C atoms, particularly preferably having 1 to 6 C atoms, or a branched alkyl or alkoxy group having 3 to 10 C atoms, particularly preferably having 3 to 6 C atoms.

In a preferred embodiment of the present invention, in addition to one or more structural units of the formula (I), the polymer according to the invention also contains at least one further structural unit which is different from the structural unit of the formula (I). These are, inter alia, those as disclosed in WO 02/077060 A1 and in WO 2005/014689 A2 and are listed extensively. These are considered via quotation as part of the present application. The others

For example, structural units can come from the following classes:

Group 1: units containing the hole injection and / or

Affect hole transport properties of the polymers;

Group 2: units containing the electron injection and / or

Influence the electron transport properties of the polymers;

Group 3: Units that are combinations of individual units of the group

1 and group 2 have;

Group 4 units, which the emission characteristics so far

change that electrophosphorescence instead

Electrofluorescence can be obtained;

Group 5 units improving the singlet-triplet state transition;

Group 6 units which determine the emission color of the resulting

Influence polymers; Group 7: units typically used as a backbone;

Group 8: units containing the film morphology and / or the

Influence the rheology of the resulting polymers.

Structural units from group 1, the hole injection and / or

Have hole transport properties are, for example, triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine,

Phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiin, carbazole, azulene, thiophene, pyrrole and

Furan derivatives and other O-, S- or N-containing heterocycles with high-lying HOMO (HOMO = highest occupied molecular orbital).

Preferably, these arylamines and heterocycles result in a HOMO in the polymer of greater than -5.8 eV (at vacuum level), more preferably greater than -5.5 eV.

Group 2 structural units which have electron injection and / or electron transport properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline,

Anthracene, benzanthracene, pyrene, benzimidazole, triazine, ketone, phosphine oxide and phenazine derivatives, but also triarylboranes and other O-, S- or N-containing heterozygoses with low-lying LUMO (LUMO = lowest unoccupied molecular orbital). Preferably, these units in the polymer result in a LUMO of less than -1.5 eV (vs. vacuum level), more preferably less than -2.0 eV.

It may be preferred if the polymers according to the invention contain units from group 3 in which structures which influence the hole mobility and which electron mobility are involved (ie units from groups 1 and 2) are bonded directly to one another or structures are contained both the hole mobility and the

Influence electron mobility. Some of these units can serve as emitters and shift the emission color to green, yellow or blue Roie. Their use is thus suitable, for example, for the production of other emission colors from originally blue-emitting polymers.

Structural units from group 4, so-called triplet emitter units, are those which can emit light at room temperature with high efficiency from the triplet state, ie

Electrophorescence rather than electrofluorescence show what often results in an increase in energy efficiency. A triplet emitter unit is understood in the present application to mean a compound which comprises a triplet emitter. In the present application, triplet emitters are understood as meaning all compounds which are capable of emitting light in the visible or NIR range by transition from a triplet state into an energetically lower state. This is also called phosphorescence. Compounds which contain heavy atoms with an atomic number of more than 36 are suitable for this purpose. Preference is given to compounds containing d- or f-transition metals, which are the above-mentioned. Fulfill condition. Particular preference is given here to corresponding structural units which contain elements of group 8 to 10 of the periodic table (Ru, Os, Rh, Ir, Pd, Pt). When

Structural units for the polymers according to the invention can be found here e.g. various complexes, such as e.g. in WO 02/068435 A1, in WO 02/081488 A1 and in EP 1239526 A2. Corresponding monomers are described in WO 02/068435 A1 and in WO 2005/042548 A1. According to the invention, it is preferred to use triplet emitters which emit in the visible spectral range (red, green or blue). The triplet emitter may be part of the backbone of the polymer (i.e., in the backbone of the polymer) or it may be located in a side chain of the polymer.

Group 5 structural units are those which improve the transition from the singlet to the triplet state and which, in support of the abovementioned triplet emitter units, use the

Improve phosphorescence properties of these structural elements.

In particular, carbazole and bridged carbazole dimer units are suitable for this purpose, as described, for example, in WO 2004/070772 A2 and in WO 2004/1 3468 A1. Furthermore come for this ketones, Phosphine oxides, sulfoxides, sulfones, silane derivatives and the like

Compounds in question, as e.g. in WO 2005/040302 A1

to be discribed.

Group 6 structural units are, in addition to the above, those having at least one more aromatic or other conjugated structure other than those mentioned above. Groups fall, i. which only slightly affect the charge carrier mobilities, which are not organometallic complexes or which do not affect the

Have singlet-triplet transition. Such structural elements can influence the emission color of the resulting polymers. Depending on the unit, they can therefore also be used as emitters. Preference is given to aromatic structures having 6 to 40 carbon atoms or else toluenes, stilbene or bisstyrylarylene derivatives which may each be substituted by one or more radicals R ¹ . Particularly preferred is the incorporation of 1, 4 phenylene, 1, 4-naphthylene, 1, 4 or 9,10-anthrylene, 1, 6, 2,7- or 4,9-pyrenylene, 4th , 4'-biphenylylene, 4.4 "terphenylylene, 4,4'-bi-1, 1'-naphthylylene, 4,4'-tolanylene, 4,4'-stilbenylene, 4,4" bisstyryl arylene, benzothiadiazole and corresponding oxygen derivatives, quinoxaline, phenothiazine, phenoxazine, dihydrophenazine,

Bis (thiophenyl) arylene, oligo (thiophenylene), phenazine, rubrene,

Pentacene or perylene derivatives, which are preferably substituted, or preferably conjugated push-pull systems (systems substituted with donor and acceptor substituents) or systems such as squarins or quinacridones, which are preferably substituted.

Group 7 structural units are units having aromatic structures of 6 to 40 carbon atoms, which are typically used as a backbone

preferably 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9'-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzooxepine derivatives and cis- and trans -Indenofluorenderivate, but

in principle, all similar structures that would lead to a conjugated, bridged or unbridged polyphenylene or poly-phenylene-vinylene homopolymer after the polymerization. Again, you can said aromatic structure heteroatoms such as O, S or N im

Backbone or a side chain included.

Group 8 structural units are those which influence the film morphology and / or the rheology of the polymers, e.g. Siloxanes, long alkyl chains or fluorinated groups, but also particularly rigid or flexible units, such as e.g. liquid crystal forming units or

crosslinkable groups.

Preferred polymers according to the invention are those in which

at least one structural unit has charge transport properties, i. Polymers which contain inter alia at least one unit selected from groups 1 and 2.

Preferred compounds of the invention are polymers which

in addition to structural units of the formula (I) additionally contain one or more units selected from groups 1 to 8. It may also be preferred that at the same time more than one structural unit is present in a group. It is likewise preferred if the polymers according to the invention

Contain units that improve the charge transport and / or the charge injection, ie units from the group 1 and / or 2;

particularly preferred is a proportion of 0.5 to 50 mol% of these units; very particular preference is given to a proportion of from 1 to 30 mol% of these

Units.

It is furthermore particularly preferred if the polymers according to the invention contain structural units from group 7 and units from group 1 and / or 2. It is particularly preferred if the sum of structural units of the formula (I), of units of group 7 and units of group 1 and / or 2 of the polymer is at least 50 mol%, based on all units of the polymer, preferably 0, 5 to 50 mo!% Units from group 1 and / or 2 are. As the above-mentioned copolymers can be obtained and which further structural elements are particularly preferred for it, is

for example, described in detail in WO 2005/014688 A2. This is by quotation part of the disclosure of the present application. It should also be emphasized at this point that the polymer can also have dendritic structures.

The synthesis of the above-described units from groups 1 to 8 and the other emitting units is known to the person skilled in the art and is described in the literature, e.g. in WO 2005/014689 A2, in WO

2005/030827 A1 and in WO 2005/030828 A1. These

Documents and the literature cited therein are incorporated by reference into the technical teaching disclosed in the present application.

For the synthesis of the compounds according to the invention, a polymerization reaction is generally carried out with one or more different monomer units, wherein at least one monomer incorporated in the polymer leads to structural units of the formula (I).

Suitable polymerization reactions are known in the art and described in the literature. Particularly suitable and preferred

Polymerization reactions leading to C-C or C-N linkages are as follows: SUZUKI, YAMAMOTO, SILENCE, HECK,

NEGISHI, SONOGASHIRA, HIYAMA, ULLMANN, WITTIG, or HARTWIG BUCHWALD polymerisation. How the polymerization can be carried out by these methods and how the polymers can then be separated off from the reaction medium and purified is known to the person skilled in the art and described in the literature, for example in WO 03/048225 A2, in WO 2004/037887 A2 and in US Pat WO 2004/037887 A2 described in detail. The subject matter of the present application is thus also a process for the preparation of the polymers according to the invention, which is characterized

are characterized by being prepared by SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, HIYAMA, ULLMANN, WITTIG, or HARTWIG-BUCHWALD polymerization. The dendrimers according to the invention can be prepared according to methods known to the person skilled in the art or in analogy thereto. Suitable methods are described in the literature, eg in Frechet, Jean MJ; Hawker, Craig J., "Hyperbranched polyphenylenes and hyperbranched polyesters: new soluble, three-dimensional, reactive polymers", Reactive & Functional Polymers (1995), 26 (1-3), 127-36; Janssen, HM; Meijer, EW, "The synthesis and characterization of dendritic molecules", Materials Science and Technology (999), 20 (Synthesis of Polymers), 403-458; Tomalia, Donald A., "Dendrimer molecules", Scientific American (1995), 272 (5), 62-6, WO 02/067343 A1 and WO 2005/026144 A1.

For the synthesis of the polymers according to the invention, the

corresponding monomers of the formula (II) are required.

Monomers which lead to structural units of the formula (I) in the polymers according to the invention are compounds which are correspondingly substituted and have at two positions suitable functionalities which make it possible to incorporate this monomer unit in the polymer. These

Monomers of the formula (II) are therefore likewise the subject of

present application. The symbols R used in formula (II) are defined as described with respect to formula (I). The group X represents, identically or differently, a leaving group suitable for a polymerization reaction, so that the incorporation of the monomer building blocks into polymeric compounds is made possible. Preferably, X represents a chemical functionality which is identically or differently selected from the class of halogens, O-tosylates, O-triflates, O-sulfonates, boric acid esters, partially fluorinated silyl groups, diazonium groups and organotin compounds. The backbone of the monomer compounds can be functionalized by standard methods, for example by Friedel-Crafts alkylation or acylation. Furthermore, the skeleton can be halogenated according to standard methods of organic chemistry. The halo- genated compounds can optionally be further implemented in additional functionalization steps. For example, the halogenated compounds can be used either directly or after conversion to a boronic acid derivative or organotin derivative as starting materials for the reaction to polymers, oligomers or dendrimers.

The methods mentioned are merely a selection of the reactions known to the person skilled in the art which, without being inventive, can be used for the synthesis of the compounds according to the invention.

It may be preferred not to use the polymers according to the invention as a pure substance but as a mixture (blend) together with further any desired polymeric, oligomeric, dendritic or low molecular weight substances. These may e.g. the electronic

Improve properties or self-emit. A mixture is understood above and below to mean a composition which contains at least one polymeric component. Another object of the present application is thus a mixture (blend) containing one or more polymers of the invention, and one or more other polymeric, oligomeric, dendritic or low molecular weight substances. In a further embodiment of the present application, it is preferred that a mixture contains a polymer according to the invention comprising structural units of the formula (I) and a low molecular weight substance. In a further embodiment of the invention it is preferred that a mixture contains a polymer according to the invention, an emitter which is either present in the polymer according to the invention or, as in the abovementioned embodiments, mixed as low molecular weight substance, and other low molecular weight substances. These low molecular weight substances can have the same functionalities as have been mentioned for possible monomer units in groups 1 to 8.

The present application furthermore relates to formulations comprising one or more polymers according to the invention and

at least one solvent. How such solutions can be prepared is known to the person skilled in the art and, for example, in WO

02/072714 A1, in WO 03/019694 A2 and in the literature cited therein.

Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, tetrahydrofuran (THF), methyl THF, tetrahydropyran (THP), chlorobenzene, dioxane, phenoxytoluene, in particular 3 Phenoxytoluene, (-) - fenchone, 1,2,3,5-tetramethylbenzene, 1, 2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4 Methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecyibenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, Phenol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene,

Heptylbenzene, octylbenzene, 1, 1-bis (3,4-dimethylphenyl) ethane or

Mixtures of these solvents.

These solutions can be used to prepare thin polymer layers, for example, by area coating methods (eg, spin-coating) or by printing methods (eg, ink-jet printing). The polymers, mixtures and formulations according to the invention can be used in electronic or optoelectronic devices or for their production. The present application relates to the use of the polymers, mixtures and formulations according to the invention in electronic or optoelectronic devices, preferably in organic electroluminescent devices (OLED), organic light-emitting electrochemical cells (OLEC), organic field-effect transistors (OFETs), organic integrated circuits ( O-ICs), organic thin-film transistors (TFTs), organic solar cells (O-SCs), organic laser diodes (O-lasers), organic photovoltaic elements or devices (OPV) or organic photoreceptors (OPCs), particularly preferably in organic electroluminescent devices ( OLED).

The present application is focused on the use of the compounds of the invention in organic electroluminescent devices (OLEDs). However, it is possible for the skilled person without further inventive step to use the compounds of the invention for other uses in other electronic devices.

For the purposes of the present invention, it is preferred that the

Polymer, oligomer or dendrimer according to the invention as a layer (or in a layer) in the electronic device is present.

The present application thus also relates to a layer, in particular an organic layer, comprising one or more polymers according to the invention.

Preferably, the compounds are used in organic electronic devices containing at least one layer containing one or more of the polymers of the invention. Preferably, the use is particularly in organic electroluminescent devices containing anode, cathode and at least one

emitting layer, characterized in that at least one layer contains at least one inventive polymer having structural units of the formula (I). In a further embodiment, it is preferred that the polymer containing structural units of the formula (I) together with a

emitting compound is used in an emitting layer. The mixture of the polymer containing structural units of the formula (I) and the emitting compound then contains between 99 and 1% by weight, preferably between 98 and 60% by weight, particularly preferably between 97 and 70% by weight, in particular between 95 and 75 wt .-% of the polymer based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 1 and 99 wt .-%, preferably between 2 and 40 wt .-%, particularly preferably between 3 and 30 wt .-%, in particular between 5 and 25 wt .-% of the emitter based on the total mixture of Emitter and matrix material.

In yet a further embodiment of the present invention, the polymers according to the invention are used as hole transport material or as hole injection material. The polymer is preferably used in a hole transport or in a hole injection layer.

For example, these hole injection layers according to the invention are triarylamines, carbazoles, silanes or phosphanes. A hole injection layer in the sense of the present application is a layer which directly adjoins the anode. A hole transport layer in the sense of the present application is a layer that lies between a hole injection layer and an emission layer. When polymers according to the invention are used as hole-transporting or hole-injecting material, it may be preferred if they are doped with electron-accepting compounds, for example with F ₄ -tetracyanoquinodimethane (TCNQ) or with compounds as described in EP 1476881 and in EP 596445 described. In addition, the polymers of the invention can be used in charge blocking layers. These charge blocking layers may consist of various suitable materials,

including alumina, polyvinyl butyral, silane, and mixtures thereof. This layer, which is generally applied by known coating techniques, may be of any effective thickness, preferably in the range of 0.05 to 0.5 μm.

The present application furthermore relates to electronic or optoelectronic components, preferably organic electroluminescent devices (OLED), organic light-emitting electrochemical cells (OLEC), organic field-effect transistors (OFETs), organic integrated circuits (O-ICs), organic thin film transistors (TFTs), organic solar cells (O-SCs), organic laser diodes (O-lasers), organic photovoltaic elements or devices (OPV) or organic photoreceptors (OPCs), more preferably organic electroluminescent devices with one or more active ones

Layers, wherein at least one of these active layers contains one or more polymers according to the invention. The active layer may be, for example, a light-emitting layer, a charge-transport layer and / or a charge-injection layer.

How OLEDs can be produced is known to the person skilled in the art and is described in detail, for example, as a general method in WO 2004/070772 A2, which is to be adapted accordingly for the individual case.

Preferably, an organic electroluminescent device, characterized in that one or more layers of solution, such as by spin coating, or with any printing method, such as roll to roll, screen printing, Fiexodruck or offset printing, more preferably, however, LITI (Light Induced Thermal Imaging, Thermal transfer printing), ink-jet printing (ink-jet printing), dipping method or spraying method. For this purpose, soluble compounds are needed. In addition to the cathode, anode and the emitting layer, the organic electroluminescent device may contain further layers. These may be selected, for example, from charge carrier injection, charge carrier transport or carrier blocking layer (T. Matsumoto et al., Multiphoton Organic EL Device Having Charge Generation Layer, IDMC 2003, Taiwan, Session 21 OLED (5)). But be it

It should be noted that not necessarily each of these layers must be present and also several layers with the same function may be present. In a further preferred embodiment of the present invention

Invention, the organic electroluminescent device comprises a plurality of emitting layers, wherein at least one layer contains at least one inventive polymer. The emission layers preferably have a plurality of emission maxima between 380 nm and 750 nm, so that overall white emission results in this case.

Particularly preferred are three-layer systems, wherein at least one of these layers contains at least one polymer according to the invention and wherein the three layers show blue, green and orange or red emission (for the basic structure see for example WO 05/01 1013).

The subject of the present application are thus both the

Devices themselves as well as the use of the polymers of the invention in the corresponding devices. All preferred and not explicitly preferred features of the abovementioned polymers according to the invention, their use in

electronic devices and the electronic devices themselves can be combined with each other as desired. All resulting combinations are also part of the present application.

When used in organic electroluminescent devices, the compounds according to the invention preferably have one or more of the following advantageous properties: 1. The polymers of the present invention have a large bandgap to achieve a deep blue singlet emission for large color gamut display applications, and the larger band gaps in the polymers of this invention also allow their use as host materials not only for red but also for green triplet emission.

2. The compounds according to the invention increase the lifetime and the efficiency of, in particular, blue-emitting organic compounds

Electroluminescent devices for high-quality applications.

The following examples are intended to illustrate the present invention without limiting it. In particular, the features, characteristics and advantages of the defined compounds underlying the example in question are also applicable to other compounds not mentioned in detail but falling within the scope of the claims, unless otherwise stated elsewhere.

embodiments

A) Preparation of the monomers Example 1

Bis-2,7- [1,2,2] dioxaborolanpy

M1

20 g (99 mmol) of pyrene, 55 g (217 mmol) of bisborolane and 400 mg (mmol) of di-tert-butylbipyridine are suspended in 300 ml of cyclohexane and carefully degassed. The reaction mixture is treated with 500 mg dimethoxy biscyclooctadiendiiridium and heated to 80 ° C overnight. The solution is cooled to room temperature, treated with 100 ml of water and 100 ml of dichloromethane. The phases are separated and the aqueous phase extracted twice with dichloromethane. The combined organic phases are dried over magnesium sulfate, filtered and the

Solvent removed in vacuo. The brown residue is washed several times with ethanol. This gives 38.9 g (85.6 mmol) (86%) of a white solid having a purity of 99.9%.

Comparative Example 2

Bis-1, 6- [1,2,2] -dioxaborolanpyrene

1st step: Preparation of 1,4- and 1,6-dibromopyrene

202.26

360.05

In a 4 l four-necked flask equipped with reflux condenser,

Gas discharge into a wash bottle with NaOH solution, KPG stirrer and 500 ml dropping funnel, 58 g (288 mmol) of pyrene, dissolved in 1500 ml of dichloromethane, presented. This solution is heated to boiling. To this boiling solution are added within 6 hours (until the

Gas formation is complete) 31, 2 ml (600 mmol) of bromine, dissolved in 240 ml of dichloromethane, added dropwise. It is then boiled under reflux for a further 30 minutes. Thereafter, the solution is allowed to cool and crystallize overnight. The precipitate is filtered off with suction and washed with ethanol and heptane. The yield is 74.8 g (72%).

The two resulting isomers, 1, 6 dibromopyrene and 1, 8 dibromopyrene, in a carrier gas sublimation at 10 ^{~ 2} mbar and 230 to 250 ° C, fractionated sublimated as the carrier gas is argon, the 1, 6

Dibrompyren condensed a little later and accumulates in the front of the sublimation tube. This gives 24.9 g (33.3%) of a white solid having a purity of 99.9%.

2nd step: conversion of bisbromide to bisboronic acid ester

15 g (41.7 mmol) of dibromopyrene are dissolved in 250 ml of dioxane, and 12.7 g (50 mmol) of bis (pinacolato) diborane and 8 g (81.5 mmol) are added.

Potassium acetate added. Subsequently, 163 mg (0.2 mmol) of 1, 1-bis (diphenylphosphino) ferrocene-palladium (II) chloride (complex with

Dichloromethane (1: 1), Pd 13%) was added and the batch to 110 ° C. heated. After TLC monitoring, the batch is cooled to room temperature and treated with 200 ml of water. Subsequently, the phases are separated. The organic phase is washed with water and the aqueous phase extracted with ethyl acetate, then the combined organic phases are dried over magnesium sulfate, filtered and the solvent removed in vacuo. The residue is recrystallized from ethanol. 17.2 g (37.9 mmol) (91%) of a 99.6% pure white solid are obtained.

B) Preparation of the polymers

The inventive polymers P1 to P4 and the comparative polymers V1 to V6 are synthesized using the following monomers (percentages = mol%) by SUZUKI coupling according to WO 03/048225 A2.

The monomers used in addition to the 2,7-pyrenebisboron ester M1 and the 6-pyrenebisboron ester M2 are the following monomers whose preparation has already been disclosed in the prior art:

The monomers are copolymerized in the composition shown in the following Table 1, whereby the polymers P1 to P4 according to the invention and the comparative polymers V1 to V6 are obtained in the stated compositions [in mol%], the sum always equal to 100% and in equal parts Bromides and boronic esters are used. Table 1

C) Production of the OLEDs

The production of an organic light-emitting diode (OLED) has already been described many times in the literature (for example in WO 2004/037887 A2). To illustrate the present invention by way of example, OLEDs are prepared by the inventive polymers P1 to P4 and the comparative polymers V1 to V6 from Table 1 (with different proportions of the monomers) by spin coating.

For this purpose, substrates of the company Technoprint (Sodalimeglas) are used, on which the ITO structure (indium tin oxide, a transparent, conductive anode) is applied.

The substrates are cleaned in the clean room with DI water and a detergent (Deconex 15 PF) and then activated by a UV / ozone plasma treatment. Thereafter, an 80 nm layer of PEDOT (PEDOT is a polythiophene derivative (Baytron P VAI 4083sp.) From HC Starck, Goslar, which is supplied as aqueous dispersion) is also applied by spin coating in the clean room as buffer layer. The required spin rate depends on the degree of dilution and the specific spincoater geometry (typically 80 nm: 4500 rpm). To remove residual water from the layer, the substrates for 10 minutes at 180 ° C on a Heating plate baked out. Thereafter, under an inert gas atmosphere

(Nitrogen or argon) first 20 nm of an interlayer (typically a hole-dominated polymer, here HIL-012 Merck) and then 65 nm of the polymer layers of toluene solutions (concentration interlayer 5 g / l, for the polymers P1 to P4 and each 8th g / l for the comparative polymers V1 to V6). Both layers are baked at 180 ° C for at least 10 minutes. Thereafter, the Ba / Al cathode is vapor deposited (high purity metals from Aldrich, especially barium 99.99% (stock number 474711); vapor deposition units from Lesker et al., More typically

Vapor pressure 5 × 10 ^-6 mbar). To protect especially the cathode from air and humidity, the device is finally encapsulated and then characterized.

For this purpose, the devices are clamped in holder specially made for the substrate size and contacted by means of spring contacts. A

Photodiode with eye-tracking filter can be placed directly on the measuring holder to exclude the influence of extraneous light.

Typically, the voltages are from 0 to max. 20 V in 0.2 V increments and lowered again. For each measuring point, the current through the device and the photocurrent obtained by the

Photodiode measured. In this way one obtains the IVL data of the test devices. Important parameters are the measured maximum efficiency ("Eff." In cd / A) and that required for 000 cd / m ²

Tension.

In addition, in order to know the color and the exact electroluminescence spectrum of the test devices, the voltage required for 1000 cd / m ^{2 is} again applied after the first measurement and the photodiode is replaced by a spectrum measuring head. This is connected by an optical fiber with a spectrometer (Ocean Optics). The color coordinates from the measured spectrum (CIE: Commission International de ^l'eclairage, standard observer from 1931) can be derived. The results obtained when using the polymers P1 to P4 according to the invention and the comparative polymers V1 to V6 in OLEDs are summarized in the following Table 2.

Table 2

As can be seen from the results in Table 2, the polymers according to the invention have a deeper blue emission than

Comparable prior art polymers. Table 2 also shows that polymer blends also show a deep blue emission, even if only one component, namely the component containing the emitter, has the structural unit of the formula (I) according to the invention.

In addition, the polymers according to the invention lead to longer lifetimes.

Claims

claims

Polymer comprising one or more structural units of the formula (I),

in which

R ¹ in each occurrence, identically or differently H, D, F, Cl, Br, I, OH, N (R ² ) 2, a straight-chain alkyl, alkoxy or thio alkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, in which also one or more H atoms may be replaced by R ² and in which also one or more non-adjacent CH ₂ groups by O, S , Si (R ² ) ₂ , Ge (R ² ) ₂ , BR ² , NR ² , PR ² , CO, C = S, C = Se, C = NR ² , PO (R ² ), PS (R ² ) , R ² C = CR ² , CsC, SO, SO ₂ , COO, O (CO) O or CONR ² may be replaced, or a mono- or polycyclic, aromatic or heteroaromatic ring system;

R ² at each occurrence, the same or different H, F, a

straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, in which also one or more H atoms may be replaced by F, and in which also one or more non-adjacent CH ₂ groups may be replaced by O, CO, COO or O (CO) O, or a mono- or polycyclic, aromatic or heteroaromatic ring system; and the dashed lines are the bonds to the neighboring ones

Represent structural units.

Polymer according to claim 1, characterized in that the

Structural unit of the formula (I) is selected from the

Structural units of the formulas (Ia) to (Ic)

wherein the dashed lines in formulas (la), (lb) and (lc) represent the bonds to the adjacent structural units in the polymer and R ¹ in formulas (la) and (lb) are the same for R ¹ with respect to formula (i ) may assume meanings given in claim 1.

3. Polymer according to claim 1 or 2, characterized in that it has a molecular weight M _w in the range of 1,000 to 2,000,000 g / mol. Polymer according to one or more of claims 1 to 3, characterized in that the proportion of the structural units of the formula (I) in the polymer is 1 to 95 mol%. 5. Polymer according to one or more of claims 1 to 4, characterized in that the polymer also contains at least one further structural unit which is different from the structural unit of the formula (I). 6. Compound of the formula (II)

where the symbols R used can assume the meanings given for R in relation to formula (I) in claim 1 and additionally that X represents a leaving group suitable for the polymerization reaction.

Compound according to claim 6, characterized in that X 7

independently of one another, the same or different selected from halogen, O-tosylate, O-triflate, O-sulfonate, boric acid esters, partially fluorinated silyl groups, diazonium groups and organotin compounds. Mixtures containing at least one polymer according to one or more of claims 1 to 5 and additionally one or more compounds selected from the classes of polymeric, oligomeric, dendritic and low molecular weight substances. Formulations containing at least one polymer according to one or more of claims 1 to 5 and at least one

Solvent.

Use of a polymer according to one or more of claims 1 to 5 or a mixture according to claim 8 in

organic electronic devices.

Organic electronic device having one or more active layers, characterized in that at least one of these active layers contains one or more polymers according to one or more of claims 1 to 5 or a mixture according to claim 8.

Organic electronic device according to claim 11, characterized in that it is an organic

Electroluminescent device (OLED), an organic light emitting electrochemical cell (OLEC), an organic integrated circuit (O-IC), an organic field effect transistor (OFET), organic thin film transistor (OTFT), an organic solar cell (O-SC), an organic laser diode (O-laser), an organic photovoltaic element or device (OPV) or an organic photoreceptor (OPC), preferably an organic electroluminescent device (OLED).