# Patent

## Title
Cross-linkable and cross-linked polymers, process for the preparation thereof, and the use thereof

## Abstract

The present invention relates to cross-linkable and cross-linked polymers, methods for the production thereof, the use of said cross-linked polymers in electronic devices, especially in OLEDs (OLED=Organic Light Emitting Diode), and to electronic devices, especially organic electroluminescent devices which contain the cross-linked polymers.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2013/001067, filed Apr. 12, 2013, which claims benefit of European Application No. 12002655.4, filed Apr. 17, 2012, both of which are incorporated herein by reference in their entirety.
The present invention relates to crosslinkable and crosslinked polymers, to a process for the preparation thereof, to the use of these crosslinked polymers in electronic devices, in particular in organic electroluminescent devices, so-called OLEDs (OLED=organic light-emitting diode), and to electronic devices, in particular organic electroluminescent devices, comprising these crosslinked polymers.
In electronic devices, such as OLEDs, components of various functionality are required. In OLEDs, the different functionalities are normally present in different layers. In this case, the term multilayered OLED systems is used. These multilayered OLED systems have, inter alia, charge-transporting layers, such as electron- and hole-conductor layers, and layers which comprise light-emitting components. These multilayered OLED systems are generally produced by the successive layer-by-layer application of the individual layers. The individual layers here can either be applied by vapour deposition in a high vacuum or from solution. Vapour deposition in a high vacuum is only possible for low-molecular-weight compounds, since only they can be evaporated without decomposition. In addition, application in a high vacuum is very expensive. Application from solution is therefore preferred. However, this requires that the individual materials are soluble in the corresponding solvents or solvent mixtures. A further prerequisite for the application of a plurality of layers from solution is that, on application of each individual layer, the layer applied previously is not partially or fully dissolved again by the solution of the subsequent layer. This can be achieved, for example, by each layer applied, which is, for example, a polymer layer, being crosslinked in order to make it insoluble, before the next layer is applied. Such processes for the crosslinking of polymer layers are described, for example, in EP 0 637 899 and WO 96/20253.
Crosslinkable polymers can be prepared by various processes. One possibility consists in bonding the crosslinkable group directly to a monomer, which then becomes a constituent of a crosslinkable polymer through polymerisation, optionally with further monomers. Corresponding preparation processes for crosslinkable polymers are described, for example, in WO 2006/043087, in WO 2005/049689, in WO 2005/052027 and in US 2007/0228364. Under certain circumstances, side reactions may occur in these processes caused by the crosslinkable group already reacting during the polymerisation and thus resulting in direct crosslinking of the polymer during the polymerisation.
Alternatively, it is proposed in WO 2010/097155 to bond an aldehyde group to a monomer, then to polymerise this monomer, optionally together with further monomers, and only subsequently to convert the aldehyde group of the polymer into a crosslinkable group, for example a vinyl group.
However, OLEDs comprising the crosslinkable or crosslinked materials known from the prior art do not have the desired voltages, efficiencies and/or lifetimes.
It was accordingly one of the objects of the present invention to provide crosslinkable polymers which on the one hand crosslink to an adequate extent, but on the other hand also result in an improvement in the voltage, efficiency and/or lifetime in OLEDs.
This object is achieved by the provision of a polymer which contains both triarylamine units and also aromatic or heteroaromatic diamine units, where at least one of these units contains at least one crosslinkable group.
The present invention thus relates to a polymer which contains at least one structural unit of the following formula (I):




and at least one structural unit of the following formula (II):





where

Ar1 to Ar8 is on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;

i and j is each 0 or 1, where the sum (i+j)=1;

R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, S(═O)R1, S(═O)2R1, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C≡C, Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S or CONR1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1; where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another;

R1 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; and the dashed lines represent bonds to adjacent structural units in the polymer and the dashed lines which are located in brackets represent possible bonds to adjacent structural units; which is characterised in that at least one of the structural units of the formula (I) and/or (II) contains at least one crosslinkable group Q.

The structural unit of the formula (II) accordingly has 2 bonds to adjacent structural units in the polymer. It is possible here for i to be 1 and j to be 0, or for i to be 0 and j to be 1. Preferably, i=0 and j=1.
The structural unit of the formula (II) thus corresponds either to the structural unit of the following formula (IIa):




or to the structural unit of the following formula (IIb):





where the structural unit of the formula (IIa) is preferred.

In a first preferred embodiment, the proportion of structural units of the formulae (I) and (II) in the polymer is 100 mol %, i.e. the polymer consists exclusively of structural units of the formulae (I) and (II).
In a second preferred embodiment, the proportion of structural units of the formulae (I) and (II) in the polymer is in the range from 25 to 75 mol %, i.e. the polymer contains at least one further structural unit which is different from the structural units of the formulae (I) and (II).
The polymer preferably contains at least one further structural unit of the following formula (III) which is different from structural units (I) and (II):

—Ar9—  (III)

where Ar9 is a mono- or polycyclic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.

In a further embodiment, the polymer may, besides structural units of the formulae (I), (II) and optionally (III), also contain further structural units which are different from the structural units of the formulae (I), (II) and optionally (III).
In the present application, the term polymer is taken to mean both polymeric compounds, oligomeric compounds and dendrimers. The polymeric compounds according to the invention preferably contain 10 to 10000, particularly preferably 20 to 5000 and very particularly preferably 50 to 2000 structural units (i.e. recurring units). The oligomeric compounds according to the invention preferably contain 3 to 9 structural units. The branching factor of the polymers here is between 0 (linear polymer, no branching points) and 1 (fully branched dendrimer).
The polymers according to the invention preferably have a molecular weight Mw in the range from 1,000 to 2,000,000 g/mol, particularly preferably a molecular weight Mw in the range from 10,000 to 1,500,000 g/mol and very particularly preferably a molecular weight Mw in the range from 50,000 to 1,000,000 g/mol. The molecular weight Mw is determined by means of GPC (=gel permeation chromatography) against an internal polystyrene standard.
The polymers according to the invention are either conjugated, partially conjugated or non-conjugated polymers. Preference is given to conjugated or partially conjugated polymers.
The structural units of the formulae (I) and (II) can in accordance with the invention be incorporated into the main chain or into the side chain of the polymer. However, the structural units of the formulae (I) and (II) are preferably incorporated into the main chain of the polymer.
“Conjugated polymers” in the sense of the present application are polymers which contain principally sp2-hybridised (or optionally also sp-hybridised) carbon atoms in the main chain, which may also be replaced by correspondingly hybridised heteroatoms. In the simplest case, this means the alternating presence of double and single bonds in the main chain, but polymers containing units such as, for example, a meta-linked phenylene are also intended to be regarded as conjugated polymers in the sense of this application. “Principally” means that naturally (spontaneously) occurring defects which result in conjugation interruptions do not devalue the term “conjugated polymer”. The term conjugated polymers is likewise applied to polymers having a conjugated main chain and non-conjugated side chains. Furthermore, the term conjugated is likewise used in the present application if the main chain contains, for example, arylamine units, arylphosphine units, certain heterocycles (i.e. conjugation via N, O or S atoms) and/or organometallic complexes (i.e. conjugation via the metal atom). An analogous situation applies to conjugated dendrimers. By contrast, units such as, for example, simple alkyl bridges, (thio)ether, ester, amide or imide links are clearly defined as non-conjugated segments.
A partially conjugated polymer in the present application is intended to be taken to mean a polymer which contains conjugated regions which are separated from one another by non-conjugated sections, specific conjugation interrupters (for example spacer groups) or branches, for example in which relatively long conjugated sections in the main chain are interrupted by non-conjugated sections, or which contains relatively long conjugated sections in the side chains of a polymer which is non-conjugated in the main chain. Conjugated and partially conjugated polymers may also contain conjugated, partially conjugated or other dendrimers.
The term “dendrimer” in the present application is intended to be taken to mean a highly branched compound built up from a multifunctional centre (core), to which branched monomers are bonded in a regular structure, so that a tree-like structure is obtained. Both the core and also the monomers here can adopt any desired branched structures which consist both of purely organic units and also organometallic compounds or coordination compounds. “Dendrimer” here is generally intended to be understood as described, for example, by M. Fischer and F. Vögtle (Angew. Chem., Int. Ed. 1999, 38, 885).
In the present application, the term “structural unit” is taken to mean a unit which, starting from a monomer unit which contains at least two, preferably two, reactive groups, is incorporated into the polymer backbone as a part thereof by reaction with bond formation and is thus present in the polymer prepared as linked recurring unit.
“Crosslinkable group Q” in the sense of the present application denotes a functional group which is capable of undergoing a reaction and thus forming an insoluble compound. The reaction here can take place with a further, identical group Q, a further, different group Q or any desired other part thereof or another polymer chain. The crosslinkable group is thus a reactive group. The result of the reaction of the crosslinkable group is a correspondingly crosslinked compound. The chemical reaction can also be carried out in the layer, where an insoluble layer forms. The crosslinking can usually be supported by heat or by UV, microwave, X-ray or electron radiation, optionally in the presence of an initiator. “Insoluble” in the sense of the present application preferably means that the polymer according to the invention, after the crosslinking reaction, i.e. after the reaction of the crosslinkable groups, has a solubility in an organic solvent at room temperature which is at least a factor of 3, preferably at least a factor of 10, lower than that of the corresponding uncrosslinked polymer according to the invention in the same organic solvent.
The term “mono- or polycyclic, aromatic ring system” in the present application is taken to mean an aromatic ring system having 6 to 60, preferably 6 to 30 and particularly preferably 6 to 24 aromatic ring atoms, which does not necessarily contain only aromatic groups, but instead in which a plurality of aromatic units may also be interrupted by a short non-aromatic unit (<10% of the atoms other than H, preferably <5% of the atoms other than H), such as, for example, sp3-hybridised C atom or O or N atom, CO group, etc. Thus, for example, systems such as, for example, 9,9′-spirobifluorene and 9,9-diarylfluorene are also intended to be taken to be aromatic ring systems.
The aromatic ring systems may be mono- or polycyclic, i.e. they may contain one ring (for example phenyl) or a plurality of rings, which may also be condensed (for example naphthyl) or covalently linked (for example biphenyl), or contain a combination of condensed and linked rings.
Preferred aromatic ring systems are, for example, phenyl, biphenyl, terphenyl, [1,1′:3′,1′′]terphenyl-2′-yl, quaterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydmphenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene and spirobifluorene.
The term “mono- or polycyclic, heteroaromatic ring system” in the present application is taken to mean an aromatic ring system having 5 to 60, preferably 5 to 30 and particularly preferably 5 to 24 aromatic ring atoms, where 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 instead may also be interrupted by a short non-aromatic unit (<10% of the atoms other than H, preferably <5% of the atoms other than H), such as, for example, sp3-hybridised C atom or O or N atom, CO group, etc.
The heteroaromatic ring systems may be mono- or polycyclic, i.e. they may contain one ring or a plurality of rings, which may also be condensed or covalently linked (for example pyridylphenyl), or contain a combination of condensed and linked rings. Preference is given to fully conjugated heteroaryl groups.
Preferred heteroaromatic ring systems are, for example, 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, 1,3,4-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 carbazole, indenocarbazole, indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, 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 in the present application means that the mono- or polycyclic, aromatic or heteroaromatic ring system contains one or more substituents R.
R is on each occurrence preferably, identically or differently, H, D, F, Cl, Br, I N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, S(═O)R1, S(═O)2R1, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C≡C, Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S or CONR1 and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1; two or more radicals R here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another.
R is on each occurrence particularly preferably, identically or differently, H, F, Cl, Br, I, N(R1)2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which may be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C≡C, Si(R1)2, C═O, C═NR1, P(═O)(R1), NR1, O or CONR1 and where one or more H atoms may be replaced by F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to aromatic ring atoms, which may be substituted by one or more radicals R1; two or more radicals R here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another.
R is on each occurrence very particularly preferably, identically or differently, H, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which may be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C≡C, C═O, C═NR1, NR1, O or CONR1, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 20 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 20 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 20 aromatic ring atoms, which may be substituted by one or more radicals R1; two or more radicals R here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another.
R1 is on each occurrence preferably, identically or differently, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; two or more substituents R1 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another.
R1 is on each occurrence particularly preferably, identically or differently, H or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to C atoms; two or more substituents R1 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another.
R1 is on each occurrence very particularly preferably, identically or differently, H or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 10 C atoms.
Preferred mono- or polycyclic, aromatic or heteroaromatic groups Ar1 in formula (I), Ar4 and Ar6 in formula (IIa) and Ar6 and Ar7 in formula (IIb) are the following:







The radicals R in the formulae E1 to E12 can adopt the same meaning as the radicals R in the formulae (I) and (II). X can denote CR2, SiR2, NR, O or S, where here too R can adopt the same meaning as the radicals R in the formulae (I) and (II).
The indices used have the following meaning:

    m=0, 1 or 2;
    n=0, 1, 2 or 3;
    o=0, 1, 2, 3 or 4 and
    p=0, 1, 2, 3, 4 or 5.


Preferred mono- or polycyclic, aromatic or heteroaromatic groups Ar2 and Ar3 in formula (I), Ar5, Ar7 and Ar8 in formula (IIa), Ar4, Ar5 and Ar8 in formula (IIb), and Ar9 in formula (III) are the following:










The radicals R in the formulae M1 to M19 can adopt the same meaning as the radicals R in the formulae (I) and (II). X can denote CR2, SiR2, O or S, where here too R can adopt the same meaning as the radicals R in the formulae (I) and (II). Y can be CR2, SiR2, O, S or a straight-chain or branched alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, each of which may be substituted by one or more radicals R1, and where one or more non-adjacent CH2 groups, CH groups or C atoms of the alkyl, alkenyl or alkynyl groups may be replaced by Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S, CONR1, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1; where here too the radicals R and R1 can adopt the same meanings as the radicals R and R1 in the formulae (I) and (II).
The indices used have the following meaning:

    k=0 or 1;
    m=0, 1 or 2;
    n=0, 1, 2 or 3;
    o=0, 1, 2, 3 or 4; and
    q=0, 1, 2, 3, 4, 5 or 6.


Particularly preferred mono- or polycyclic, aromatic or heteroaromatic groups Ar1 in formula (I), Ar4 and Ar6 in formula (IIa) and Ar6 and Ar7 in formula (IIb) are the following:










The radicals R in the formulae E1a to E12a can adopt the same meaning as the radicals R in the formulae (I) and (II).
The indices used have the following meaning:

    k=0 or 1; and
    n=0, 1, 2 or 3.


Particularly preferred mono- or polycyclic, aromatic or heteroaromatic groups Ar2 and Ar3 in formula (I), Ar5, Ar7 and Ar8 in formula (IIa), Ar4, Ar5 and Ar8 in formula (IIb) and Ar9 in formula (III) are the following:













The radicals R in the formulae M1a to M17a can adopt the same meaning as the radicals R in the formulae (I) and (II). X can denote CR2 or SiR2, where here too R can adopt the same meaning as the radicals R in the formulae (I) and (II).
Y can be CR2, SiR2, O, S or a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R1, and where one or more non-adjacent CH2 groups, CH groups or C atoms of the alkyl, alkenyl or alkynyl groups may be replaced by Si(R1)2, C═O, C═NR1, P(═O)(R1), NR1, O, CONR1, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 20 aromatic ring atoms, which may be substituted by one or more radicals R1; where here too the radicals R and R1 can adopt the same meanings as the radicals R and R1 in the formulae (I) and (II).
The indices used have the following meaning:

    k=0 or 1;
    m=0, 1 or 2;
    n=0, 1, 2 or 3; and
    o=0, 1, 2, 3 or 4.


Very particularly preferred mono- or polycyclic, aromatic or heteroaromatic groups Ar1 in formula (I), Ar4 and Ar6 in formula (IIa) and Ar6 and Ar7 in formula (IIb) are the following:













The radicals R3 in the formulae E1b to E1f, E8g to E8i, E8m, E9c and E9d are on each occurrence, identically or differently, H or a straight-chain or branched alkyl group having 1 to 12 C atoms, preferably 1 to 10 C atoms. The radicals R3 are particularly preferably methyl, n-butyl, sec-butyl, tert-butyl, n-hexyl or n-octyl.
The radicals R4 in the formulae E2d to E2f, E3b and E4b to E4e are on each occurrence, identically or differently, H or a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radicals R4 are particularly preferably methyl, n-butyl, sec-butyl or tert-butyl.
The radicals R in the formulae E8k and E12b are identical or different on each occurrence and can adopt the same meaning as the radicals R in the formulae (I) and (II).
Very particularly preferred mono- or polycyclic, aromatic or heteroaromatic groups Ar2 and Ar3 in formula (I), Ar5, Ar7 and Ar8 in formula (IIa), Ar4, Ar5 and Ar8 in formula (IIb) and Ar9 in formula (III) are the following:
















The radicals R3 in the formulae M7b, M10d, M12b, M13b, M14b, M14c, M17b, M20d, M20e, M20g, M20h, M20j, M21c, M22c, M22d and M23c are on each occurrence, identically or differently, H or a straight-chain or branched alkyl group having 1 to 12 C atoms, preferably 1 to 10 C atoms. The radicals R3 are particularly preferably methyl, n-butyl, sec-butyl, tert-butyl, n-hexyl and n-octyl.
The radicals R4 in the formulae M1c, M1d, M14c, M20d, M20e, M20f, M20g, M20i, M20j, M21c, M22c, M22d, M23c and M23d are on each occurrence, identically or differently, H or a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radicals R4 are particularly preferably methyl, n-butyl, sec-butyl or tert-butyl.
Preferred structural units of the following formula (I)




are structural units in which Ar1 is selected from the groups of the formulae E1 to E12 and Ar2 and Ar3 are selected from the groups of the formulae M1 to M19, where it is particularly preferred for Ar2 and Ar3 to be identical.

A selection of preferred structural units of the formula (I) is shown in the following Table 1.












TABLE 1







Formula (I)
Ar1
Ar2
Ar3









I1
E1
M1
M1



I2
E1
M2
M2



I3
E1
M10
M10



I4
E1
M12
M12



I5
E1
M14
M14



I6
E1
M19
M19



I7
E2
M1
M1



I8
E2
M2
M1



I9
E2
M7
M7



I10
E2
M12
M12



I11
E2
M13
M13



I12
E3
M1
M1



I13
E3
M13
M13



I14
E4
M1
M1



I15
E4
M2
M2



I16
E4
M14
M14



I17
E5
M3
M3



I18
E5
M12
M12



I19
E6
M6
M6



I20
E6
M10
M10



I21
E6
M16
M16



I22
E7
M2
M2



I23
E7
M15
M15



I24
E8
M1
M1



I25
E8
M2
M2



I26
E8
M4
M4



I27
E8
M5
M5



I28
E8
M10
M10



I29
E8
M12
M12



I30
E8
M14
M14



I31
E9
M1
M1



I32
E9
M8
M8



I33
E9
M13
M13



I34
E10
M10
M10



I35
E11
M9
M9



I36
E11
M17
M17



I37
E12
M7
M7



I38
E12
M18
M18



I39
E1
M23
M23



I40
E2
M21
M1



I41
E8
M20
M20



I41
E9
M22
M22










Particularly preferred structural units of the formula (I) are structural units in which Ar1 is selected from the groups of the formulae E1a to E12a and Ar2 and Ar3 are selected from the groups of the formulae M1a to M17a, where it is particularly preferred for Ar2 and Ar3 to be identical.
A selection of particularly preferred structural units of the formula (I) is shown in the following Table 2.












TABLE 2







Formula (I)
Ar1
Ar2
Ar3









I1a
E1a
M1a
M1a



I2a
E1a
M2a
M2a



I2b
E1a
M2c
M2c



I3a
E1a
M10a
M10a



I4a
E1a
M12a
M12a



I5a
E1a
M14a
M14a



I7a
E2a
M1b
M1b



I7b
E2c
M1a
M1a



I8a
E2c
M2c
M1a



I9a
E2b
M7a
M7a



I10a
E2a
M12a
M12a



I11a
E2a
M13a
M13a



I12a
E3a
M1b
M1b



I13a
E3a
M13a
M13a



I14a
E4a
M1a
M1a



I15a
E4a
M2a
M2a



I15b
E4a
M2b
M2b



I16a
E4a
M14a
M14a



I17a
E5a
M3a
M3a



I18a
E5a
M12a
M12a



I19a
E6a
M6a
M6a



I20a
E6b
M10b
M10b



I22a
E7a
M2a
M2a



I24a
E8a
M1a
M1a



I24b
E8b
M1b
M1b



I24c
E8e
M1a
M1a



I24d
E8f
M1b
M1b



I25a
E8a
M2c
M2c



I25b
E8b
M2b
M2b



I25c
E8f
M2c
M2c



I26a
E8c
M4a
M4a



I27a
E8d
M5a
M5a



I28a
E8c
M10a
M10a



I29a
E8b
M12a
M12a



I30a
E8e
M14a
M14a



I31a
E9b
M1a
M1a



I32a
E9a
M8a
M8a



I33a
E9a
M13a
M13a



I34a
E10a
M10c
M10c



I36a
E11a
M17a
M17a



I37a
E12a
M7a
M7a



I39a
E1a
M23a
M23a



I39b
E1a
M23b
M23b



I40a
E2c
M21a
M1a



I40b
E2a
M21a
M1b



I41a
E8b
M20a
M20a



I41b
E8c
M20b
M20b










Very particularly preferred structural units of the formula (I) are structural units in which Ar1 is selected from the groups of the formulae E1b to E12b and Ar2 and Ar3 are selected from the groups of the formulae M1c to M14c, where it is particularly preferred for Ar2 and Ar3 to be identical.
A selection of very particularly preferred structural units of the formula (I) is shown in the following Table 3.












TABLE 3







Formula (I)
Ar1
Ar2
Ar3









I1b
E1b
M1c
M1c



I1c
E1e
M1c
M1c



I2c
E1c
M2d
M2d



I2d
E1e
M2f
M2f



I2e
E1f
M2f
M2f



I3b
E1d
M10d
M10d



I4b
E1f
M12b
M12b



I5b
E1c
M14b
M14b



I5c
E1d
M14b
M14c



I7c
E2d
M1d
M1d



I7d
E2f
M1c
M1c



I8b
E2f
M2f
M1c



I9b
E2e
M7b
M7b



I10b
E2e
M12b
M12b



I11b
E2d
M13b
M13b



I12b
E3b
M1d
M1d



I13b
E3b
M13b
M13b



I14b
E4c
M1c
M1c



I14c
E4d
M1c
M1c



I15c
E4b
M2e
M2e



I15d
E4e
M2d
M2d



I16b
E4b
M14c
M14c



I18b
E5b
M12b
M12b



I24e
E8g
M1c
M1c



I24f
E8j
M1c
M1c



I24g
E8k
M1d
M1d



I24h
E8l
M1d
M1d



I25d
E8g
M2f
M2f



I25e
E8h
M2e
M2e



I25f
E8k
M2f
M2f



I28b
E8i
M10d
M10d



I29b
E8m
M12b
M12b



I30b
E8j
M14b
M14b



I31b
E9d
M1c
M1c



I33b
E9c
M13b
M13b



I37b
E12b
M7b
M7b



I39c
E1b
M23c
M23c



I40c
E2f
M21c
M1c



I40d
E2d
M21c
M1d



I41c
E8h
M20d
M20d



I41d
E8h
M20g
M20g



I41e
E8h
M20i
M20i



I41f
E8i
M20h
M20h










Preferred structural units of the following formula (IIa)




are structural units in which Ar4 and Ar6, independently of one another, identically or differently, are selected from the groups of the formulae E1 to E12 and Ar5, Ar7 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1 to M19, where it is particularly preferred for Ar4 and Ar6 or Ar5 and Ar7 to be identical.

Preferred structural units of the following formula (IIb)




are structural units in which Ar6 and Ar7, independently of one another, identically or differently, are selected from the groups of the formulae E1 to E12 and Ar4, Ar5 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1 to M19, where it is particularly preferred for Ar4 and Ar5 or Ar6 and Ar7 to be identical.

A selection of preferred structural units of the formula (IIa) or (IIb) is shown in the following Table 4.










TABLE 4









Formula (IIa)














Ar4
Ar6
Ar5
Ar7
Ar8










Formula (IIb)














Ar7
Ar6
Ar5
Ar4
Ar8


















II1
E1
E1
M1
M1
M1



II2
E1
E1
M1
M1
M2



II3
E1
E1
M1
M1
M10



II4
E1
E1
M1
M1
M13



II5
E1
E1
M1
M1
M14



II6
E1
E1
M14
M14
M12



II7
E2
E2
M1
M1
M2



II8
E2
E2
M2
M2
M12



II9
E3
E3
M7
M7
M1



II10
E3
E3
M10
M10
M16



II11
E4
E4
M1
M1
M7



II12
E4
E4
M1
M1
M12



II13
E4
E4
M2
M2
M14



II14
E4
E4
M10
M10
M13



II15
E4
E8
M1
M1
M7



II16
E5
E5
M2
M13
M13



II17
E6
E6
M3
M3
M6



II18
E6
E6
M17
M17
M10



II19
E7
E7
M5
M5
M4



II20
E8
E8
M1
M1
M1



II21
E8
E8
M1
M1
M2



II22
E8
E8
M1
M1
M12



II23
E8
E8
M2
M2
M10



II24
E8
E8
M6
M6
M8



II25
E8
E8
M10
M10
M7



II26
E8
E8
M13
M13
M2



II27
E8
E8
M14
M14
M12



II28
E9
E9
M1
M1
M2



II29
E9
E9
M9
M9
M11



II30
E9
E9
M19
M19
M18



II31
E10
E10
M1
M1
M4



II32
E11
E11
M2
M2
M10



II33
E11
E11
M13
M13
M15



II34
E12
E12
M7
M7
M14



II35
E2
E2
M1
M1
M14



II36
E2
E2
M1
M1
M12



II37
E8
E8
M1
M1
M20



II38
E9
E9
M1
M1
M23










Particularly preferred structural units of the formula (IIa) are structural units in which Ar4 and Ar6, independently of one another, identically or differently, are selected from the groups of the formulae E1a to E12a and Ar5, Ar7 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1a to M17a, where it is particularly preferred for Ar4 and Ar6 or Ar5 and Ar7 to be identical.
Particularly preferred structural units of the formula (IIb) are structural units in which Ar6 and Ar7, independently of one another, identically or differently, are selected from the groups of the formulae E1a to E12a and Ar4, Ar5 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1a to M17a, where it is particularly preferred for Ar4 and Ar5 or Ar6 and Ar7 to be identical.
A selection of particularly preferred structural units of the formula (IIa) or (IIb) is shown in the following Table 5.










TABLE 5









Formula (IIa)














Ar4
Ar6
Ar5
Ar7
Ar8










Formula (IIb)














Ar7
Ar6
Ar5
Ar4
Ar8


















II1a
E1a
E1a
M1a
M1a
M1a



II1b
E1a
E1a
M1b
M1b
M1b



II2a
E1a
E1a
M1a
M1a
M2a



II3a
E1a
E1a
M1a
M1a
M10a



II4a
E1a
E1a
M1a
M1a
M13a



II4b
E1a
E1a
M1b
M1b
M13a



II5a
E1a
E1a
M1a
M1a
M14a



II6a
E1a
E1a
M14a
M14a
M12a



II7a
E2a
E2a
M1a
M1a
M2a



II7b
E2c
E2c
M1a
M1a
M2a



II8a
E2b
E2b
M2b
M2b
M12a



II9a
E3a
E3a
M7a
M7a
M1b



II11a
E4a
E4a
M1b
M1b
M7a



II12a
E4a
E4a
M1b
M1b
M12a



II13a
E4a
E4a
M2b
M2b
M14a



II14a
E4a
E4a
M10a
M10a
M13a



II15a
E4a
E8a
M1b
M1b
M7a



II16a
E5a
E5a
M2c
M13a
M13a



II17a
E6a
E6a
M3a
M3a
M6a



II18a
E6b
E6b
M17a
M17a
M10b



II19a
E7a
E7a
M5a
M5a
M4a



II20a
E8f
E8f
M1a
M1a
M1a



II21a
E8b
E8b
M1a
M1a
M2a



II21b
E8e
E8e
M1a
M1a
M2a



II22a
E8b
E8b
M1b
M1b
M12a



II23a
E8d
E8d
M2b
M2b
M10c



II24a
E8f
E8f
M6a
M6a
M8a



II25a
E8a
E8a
M10a
M10a
M7a



II26a
E8c
E8c
M13a
M13a
M2c



II27a
E8b
E8b
M14a
M14a
M12a



II28a
E9a
E9a
M1a
M1a
M2a



II28b
E9b
E9b
M1a
M1a
M2a



II31a
E10a
E10a
M1b
M1b
M4a



II32a
E11a
E11a
M2c
M2c
M10c



II34a
E12a
E12a
M7a
M7a
M14a



II35a
E2a
E2a
M1a
M1a
M14a



II35b
E2c
E2c
M1a
M1a
M14a



II36a
E2c
E2c
M1a
M1a
M12a



II37a
E8b
E8b
M1a
M1a
M20a



II37b
E8e
E8e
M1a
M1a
M20b



II38a
E9a
E9a
M1b
M1b
M23a



II38b
E9b
E9b
M1b
M1b
M23b










Very particularly preferred structural units of the formula (IIa) are structural units in which Ar4 and Ar6, independently of one another, identically or differently, are selected from the groups of the formulae E1b to E12b and Ar5, Ar7 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1c to M14c, where it is particularly preferred for Ar4 and Ar6 or Ar5 and Ar7 to be identical.
Very particularly preferred structural units of the formula (IIb) are structural units in which Ar6 and Ar7, independently of one another, identically or differently, are selected from the groups of the formulae E1b to E12b and Ar4, Ar5 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1c to M14c, where it is particularly preferred for Ar4 and Ar5 or Ar6 and Ar7 to be identical.
A selection of very particularly preferred structural units of the formula (IIa) or (IIb) is shown in the following Table 6.










TABLE 6









Formula (IIa)














Ar4
Ar6
Ar5
Ar7
Ar8










Formula (IIb)














Ar7
Ar6
Ar5
Ar4
Ar8


















II1c
E1b
E1b
M1c
M1c
M1c



II1d
E1e
E1e
M1d
M1d
M1d



II2b
E1b
E1b
M1c
M1c
M2d



II3b
E1b
E1b
M1c
M1c
M10d



II4c
E1b
E1b
M1c
M1c
M13b



II4d
E1d
E1d
M1d
M1d
M13b



II5b
E1c
E1c
M1c
M1c
M14b



II6b
E1f
E1f
M14b
M14b
M12b



II7c
E2d
E2d
M1c
M1c
M2d



II7d
E2f
E2f
M1c
M1c
M2d



II8b
E2e
E2e
M2e
M2e
M12b



II9b
E3b
E3b
M7b
M7b
M1d



II11b
E4d
E4d
M1d
M1d
M7b



II12b
E4c
E4c
M1d
M1d
M12b



II13b
E4b
E4b
M2e
M2e
M14c



II14b
E4e
E4e
M10d
M10d
M13b



II15b
E4d
E8g
M1d
M1d
M7b



II16b
E5b
E5b
M2f
M13b
M13b



II20b
E8k
E8k
M1c
M1c
M1c



II21c
E8h
E8h
M1c
M1c
M2d



II21d
E8j
E8j
M1c
M1c
M2d



II22b
E8m
E8m
M1d
M1d
M12b



II25b
E8g
E8g
M10d
M10d
M7b



II26b
E8i
E8i
M13b
M13b
M2f



II27b
E8l
E8l
M14c
M14c
M12b



II28c
E9c
E9c
M1c
M1c
M2d



II28d
E9d
E9d
M1c
M1c
M2d



II34b
E12b
E12b
M7b
M7b
M14c



II35c
E2d
E2d
M1c
M1c
M14b



II35d
E2f
E2f
M1c
M1c
M14b



II36b
E2f
E2f
M1c
M1c
M12b



II37c
E8h
E8h
M1c
M1c
M20g



II37d
E8j
E8j
M1c
M1c
M20e



II38c
E9c
E9c
M1d
M1d
M23c










Preferred structural units of the following formula (III)

—Ar9—  (III)

are structural units in which Ar9 is selected from the groups of the formulae M1 to M19, as shown in the following Table 7.











TABLE 7







Formula (III)
Ar9









III1
M1



III2
M2



III3
M3



III4
M4



III5
M5



III6
M6



III7
M7



III8
M8



III9
M9



III10
M10



III11
M11



III12
M12



III13
M13



III14
M14



III15
M15



III16
M16



III17
M17



III18
M18



III19
M19



III20
M20



III21
M21



III22
M22



III23
M23










Particularly preferred structural units of the formula (III) are structural units in which Ar9 is selected from the groups of the formulae M1a to M17a, as shown in the following Table 8.










TABLE 8







Formula (III)
Ar9









III1a
M1a



III1b
M1b



III2a
M2a



III2b
M2b



III2c
M2c



III3a
M3a



III4a
M4a



III5a
M5a



III6a
M6a



III7a
M7a



III8a
M8a



III10a
M10a



III10b
M10b



III10c
M10c



III12a
M12a



III13a
M13a



III14a
M14a



III17a
M17a



III20a
M20a



III20b
M20b



III20c
M20c



III21a
M21a



III21b
M21b



III22a
M22a



III22b
M22b



III23a
M23a



III23b
M23b










Very particularly preferred structural units of the formula (III) are structural units in which Ar9 is selected from the groups of the formulae M1c to M14c, as shown in the following Table 9.










TABLE 9







Formula (III)
Ar9









III1c
M1c



III1d
M1d



III2d
M2d



III2e
M2e



III2f
M2f



III7b
M7b



III10d
M10d



III12b
M12b



III13b
M13b



III14b
M14b



III14c
M14c



III17b
M17b



III20d
M20d



III20e
M20e



III20f
M20f



III20g
M20g



III20h
M20h



III20i
M20i



III20j
M20j



III20k
M20k



III21c
M21c



III22c
M22c



III22d
M22d



III23c
M23c



III23d
M23d










In accordance with the invention, at least one of the structural units of the formula (I) and/or (II) contains at least one crosslinkable group Q, i.e.:

    a) at least one of the structural units of the formula (I) contains at least one crosslinkable group, or
    b) at least one of the structural units of the formula (II) or (IIa) or (IIb) contains at least one crosslinkable group, or
    c) at least one of the structural units of the formula (I) and at least one of the structural units of the formula (II) or (IIa) or (IIb) contains at least one crosslinkable group.


Preference is given to alternatives a) and b), where alternative a) is particularly preferred, i.e. at least one of the structural units of the formula (I) contains at least one crosslinkable group.
At least one crosslinkable group in the present application means that a structural unit contains one or more crosslinkable groups. A structural unit preferably contains one crosslinkable group.
If the structural unit of the formula (II) or (IIa) or (IIb) contains the crosslinkable group, this can be bonded to Ar4, Ar5, Ar6, Ar7 or Ar8. The crosslinkable group is preferably bonded to one of the monovalent-bonded, mono- or polycyclic, aromatic or heteroaromatic ring systems, i.e. to Ar4 or Ar6 in the case of the formula (IIa) and to Ar6 or Ar7 in the case of the formula (IIb).
If the structural unit of the formula (I) contains the crosslinkable group, this can be bonded to Ar1, Ar2 or Ar3. The crosslinkable group is preferably bonded to the monovalent-bonded, mono- or polycyclic, aromatic or heteroaromatic ring system Ar1.
As described above, the crosslinkable group Q is a functional group which is capable of undergoing a chemical reaction and thus forming an insoluble polymeric compound. In general, all groups Q which are known to the person skilled in the art for this purpose can be employed. The task of this group is, in particular, to link the polymeric compounds according to the invention to one another, optionally to further reactive polymeric compounds, by a crosslinking reaction. This results in a crosslinked compound, or, if the reaction is carried out in a layer, in a crosslinked layer. A crosslinked layer in the sense of the present application is taken to mean a layer which is obtainable by carrying out the crosslinking reaction from a layer of the crosslinkable, polymeric compound according to the invention. The crosslinking reaction can in general be initiated by heat and/or by UV, microwave, X-ray or electron radiation and/or by the use of free-radical formers, anions, cations, acids and/or photoacids. The presence of catalysts may likewise be helpful or necessary. The crosslinking reaction is preferably a reaction for which no initiator and no catalyst has to be added.
Crosslinkable groups Q which are preferred in accordance with the invention are the groups mentioned below:

    a) Terminal or cyclic alkenyl or terminal dienyl and alkynyl groups:
    
        Suitable units are those which contain a terminal or cyclic double bond, a terminal dienyl group or a terminal triple bond, in particular terminal or cyclic alkenyl, terminal dienyl or terminal alkynyl groups having 2 to 40 C atoms, preferably having 2 to 10 C atoms, where individual CH2 groups and/or individual H atoms may also be replaced by the above-mentioned groups R. Furthermore suitable are also groups which are to be regarded as precursors and are capable of the in-situ formation of a double or triple bond.
    
    
    b) Alkenyloxy, dienyloxy or alkynyloxy groups:
    
        Furthermore suitable are alkenyloxy, dienyloxy or alkynyloxy groups, preferably alkenyloxy groups.
    
    
    c) Acrylic acid groups:
    
        Furthermore suitable are acrylic acid units in the broadest sense, preferably acrylates, acrylamides, methacrylates and methacrylamides. C1-10-alkyl acrylate and C1-10-alkyl methacrylate are particularly preferred.
        The crosslinking reaction of the groups mentioned above under a) to c) can take place via a free-radical, cationic or anionic mechanism, but also via cycloaddition.
        It may be helpful to add a corresponding initiator for the crosslinking reaction. Suitable initiators for free-radical crosslinking are, for example, dibenzoyl peroxide. AIBN or TEMPO. Suitable initiators for cationic crosslinking are, for example, AlCl3, BF3, triphenylmethyl perchlorate or tropylium hexachloroantimonate. Suitable initiators for anionic crosslinking are bases, in particular butyllithium.
        In a preferred embodiment of the present invention, however, the crosslinking is carried out without the addition of an initiator and is initiated exclusively thermally. This preference is due to the fact that the absence of the initiator prevents contamination of the layer, which could result in impairment of the device properties.
    
    
    d) Oxetanes and oxiranes:
    
        A further suitable class of crosslinkable groups Q are oxetanes and oxiranes, which crosslink cationically by ring opening.
        It may be helpful to add a corresponding initiator for the crosslinking reaction. Suitable initiators are, for example, AlCl3, BF3, triphenylmethyl perchlorate or tropylium hexachloroantimonate. Photoacids can likewise be added as initiators.
    
    
    e) Silanes:
    
        Furthermore suitable as a class of crosslinkable groups are silane groups SiR3, where at least two groups R, preferably all three groups R, stand for Cl or an alkoxy group having 1 to 20 C atoms. This group reacts in the presence of water to give an oligo- or polysiloxane.
    
    
    f) Cyclobutane groups
    
        The above-mentioned crosslinkable groups Q are generally known to the person skilled in the art, as are the suitable reaction conditions which are used for the reaction of these groups.
    
    


Preferred crosslinkable groups Q include alkenyl groups of the following formula Q1, dienyl groups of the following formula Q2, alkynyl groups of the following formula Q3, alkenyloxy groups of the following formula Q4, dienyloxy groups of the following formulae Q5, alkynyloxy groups of the following formula Q6, acrylic acid groups of the following formulae Q7 and Q8, oxetane groups of the following formulae Q9 and Q10, oxirane groups of the following formula Q11 and cyclobutane groups of the following formula Q12:







The radicals R11, R12 and R13 in the formulae Q1 to Q8 and Q11 are on each occurrence, identically or differently, H, a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radicals R11, R12 and R13 are particularly preferably H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl and very particularly preferably H or methyl. The indices used have the following meaning: s=0 to 8; and t=1 to 8.
The dashed bond in the formulae Q1 to Q11 and the dashed bonds in the formula Q12 represent the linking of the crosslinkable group to one of the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar1 to Ar8.
The crosslinkable groups of the formulae Q1 to Q12 may be linked directly to one of the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar1 to Ar8, or else indirectly, via a further mono- or polycyclic, aromatic or heteroaromatic ring system Ar10, as depicted in the following formulae Q13 to Q24:







where Ar10 in the formulae Q13 to Q24 can adopt the same meanings as Ar9, in particular the preferred, particularly preferred and very particularly preferred meanings of Ar9.

Particularly preferred crosslinkable groups Q are the following:







The radicals R11 and R12 in the formulae Q7a and Q13a to Q19a are on each occurrence, identically or differently, H or a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radicals R11 and R12 are particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl and very particularly preferably methyl.
The radical R13 in the formulae Q7b and Q19b is on each occurrence a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radical R13 is particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl and very particularly preferably methyl.
The indices used have the following meaning: s=0 to 8 and t=1 to 8.
Very particularly preferred crosslinkable groups Q are the following:










In the preferred groups Q1 to Q24, in the particularly preferred groups Q1a to Q24a and in the very particularly preferred groups Q1b to Q24c, the dashed lines represent the bonds to the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar1 to Ar8. It should be noted in this connection that the groups Q12 and Q24 each have two bonds to two adjacent ring carbon atoms of a mono- or polycyclic, aromatic or heteroaromatic ring system. All other crosslinkable groups have only one bond to the mono- or polycyclic, aromatic or heteroaromatic ring system.
As explained above, the crosslinkable group Q can be bonded to each of the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar1 to Ar8.
If the structural unit of the formula (I) contains the crosslinkable group Q, this can be bonded to Ar1, Ar2 or Ar3. The crosslinkable group is preferably bonded to the monovalent-bonded, mono- or polycyclic, aromatic or heteroaromatic ring system Ar1.
If the structural unit of the formula (II) or (IIa) or (IIb) contains the crosslinkable group Q, this can be bonded to Ar4, Ar6, Ar7 or Ar8. The crosslinkable group is preferably bonded to one of the monovalent-bonded, mono- or polycyclic, aromatic or heteroaromatic ring systems, i.e. to Ar4 or Ar6 in the case of the formula (IIa) and to Ar6 or Ar7 in the case of the formula (IIb).
The structural unit of the formula (I) particularly preferably contains the crosslinkable group Q, to be precise on the monovalent-bonded, mono- or polycyclic, aromatic or heteroaromatic ring system Ar1.
The crosslinkable group Q can be bonded at any free site, i.e. to any C atom which still has a free valence.
The bonding of the crosslinkable group Q is described in detail below with respect to the bonding to Ar1, the particularly preferred embodiment. However, the same comments also apply to Ar4 and Ar6 in formula (IIa) and to Ar6 and Ar7 in formula (IIb).
The preferred crosslinkable groups Q1 to Q24 here are preferably bonded to the preferred groups E1 to E12 of Ar1. The particularly preferred groups Q1a to Q24a here are preferably bonded to the particularly preferred groups E1a to E12a of Ar1. The very particularly preferred groups Q1b to Q24c here are preferably bonded to the very particularly preferred groups E1b to E12b of Ar1. Each of the said crosslinkable groups Q can be bonded to each of the said groups E.
Preferred crosslinkable, mono- or polycyclic, aromatic or heteroaromatic groups Ar1 in formula (I) are the following:







The radicals R in the formulae VE1 to VE12 can adopt the same meaning as the radicals R in the formulae (I) and (II). X can denote CR2, SiR2, NR, O or S, where here too R can adopt the same meaning as the radicals R in the formulae (I) and (II).
The indices used have the following meaning:

    m=0, 1 or 2;
    n=0, 1, 2 or 3;
    o=0, 1, 2, 3 or 4; and
    p=0, 1, 2, 3, 4 or 5.


Particularly preferred crosslinkable, mono- or polycyclic, aromatic or heteroaromatic groups Ar1 are the following:










The radicals R in the formulae VE1a to VE12a can adopt the same meaning as the radicals R in the formulae (I) and (II). In addition, at least one of the radicals R can also adopt the meaning Q, i.e. can denote a further crosslinkable group Q in the groups Ar1.
The indices used have the following meaning:

    k=0 or 1; and
    n=0, 1, 2 or 3.


Very particularly preferred crosslinkable, mono- or polycyclic, aromatic or heteroaromatic groups Ar1 are the following:













The radicals R3 in the formulae VE1e, VE1f, VE8g, VE8h, VE8i, VE8m, VE9c and VE9d are on each occurrence, identically or differently, H or a straight-chain or branched alkyl group having 1 to 12 C atoms, preferably 1 to 10 C atoms. The radicals R3 are particularly preferably methyl, n-butyl, sec-butyl, tert-butyl, n-hexyl and n-octyl. In addition, at least one of the radicals R3 can also adopt the meaning Q, i.e. can denote a further crosslinkable group Q in the groups Ar1.
The radicals R4 in the formulae VE2d to VE2f, VE3b and VE4b to VE4e are on each occurrence, identically or differently, H or a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radicals R4 are particularly preferably methyl, n-butyl, sec-butyl or tert-butyl. In addition, at least one of the radicals R4 can also adopt the meaning Q, i.e. can denote a further crosslinkable group Q in the groups Ar1.
The radicals R in the formulae VE12b are identical or different on each occurrence and can adopt the same meaning as the radicals R in the formulae (I) and (II).
Preferred crosslinkable structural units of the formula (Iv)




are structural units in which Ar1 is selected from the groups of the formulae VE1 to VE12, Ar2 and Ar3 are selected from the groups of the formulae M1 to M19, where it is particularly preferred for Ar2 and Ar3 to be identical, and Q is selected from the groups Q1 to Q24.

A selection of preferred crosslinkable structural units of the formula (Iv) is shown in the following Table 10.













TABLE 10







Formula (I)
Ar1
Q
Ar2
Ar3









Iv1
VE1
Q1
M1
M1



Iv2
VE1
Q14
M2
M2



Iv3
VE1
Q7
M10
M10



Iv4
VE1
Q2
M12
M12



Iv5
VE1
Q2
M14
M14



Iv6
VE1
Q10
M19
M19



Iv7
VE2
Q13
M1
M1



Iv8
VE2
Q24
M2
M1



Iv9
VE2
Q19
M7
M7



Iv10
VE2
Q2
M12
M12



Iv11
VE2
Q13
M13
M13



Iv12
VE3
Q1
M1
M1



Iv13
VE3
Q14
M13
M13



Iv14
VE4
Q7
M1
M1



Iv15
VE4
Q19
M2
M2



Iv16
VE4
Q24
M14
M14



Iv17
VE5
Q16
M3
M3



Iv18
VE5
Q13
M12
M12



Iv19
VE6
Q9
M6
M6



Iv20
VE6
Q16
M10
M10



Iv21
VE6
Q3
M16
M16



Iv22
VE7
Q9
M2
M2



Iv23
VE7
Q20
M15
M15



Iv24
VE8
Q13
M1
M1



Iv25
VE8
Q19
M2
M2



Iv26
VE8
Q16
M4
M4



Iv27
VE8
Q21
M5
M5



Iv28
VE8
Q2
M10
M10



Iv29
VE8
Q24
M12
M12



Iv30
VE8
Q14
M14
M14



Iv31
VE9
Q4
M1
M1



Iv32
VE9
Q21
M8
M8



Iv33
VE9
Q1
M13
M13



Iv34
VE10
Q9
M10
M10



Iv35
VE11
Q5
M9
M9



Iv36
VE11
Q9
M17
M17



Iv37
VE12
Q1
M7
M7



Iv38
VE12
Q12
M18
M18



Iv39
VE1
Q12
M1
M1










Particularly preferred crosslinkable structural units of the formula (Iv) are structural units in which Ar1 is selected from the groups of the formulae VE1a to VE12a, Ar2 and Ar3 are selected from the groups of the formulae M1a to M17a, where it is particularly preferred for Ar2 and Ar3 to be identical, and Q is selected from the groups Q1a to Q24a.
A selection of particularly preferred crosslinkable structural units of the formula (Iv) is shown in the following Table 11.













TABLE 11







Formula (I)
Ar1
Q
Ar2
Ar3









Iv1a
VE1a
Q1a
M1a
M1a



Iv2a
VE1a
Q14a
M2a
M2a



Iv2b
VE1a
Q14a
M2c
M2c



Iv3a
VE1a
Q7a
M10a
M10a



Iv4a
VE1a
Q2a
M12a
M12a



Iv5a
VE1a
Q2a
M14a
M14a



Iv7a
VE2a
Q13a
M1b
M1b



Iv7b
VE2c
Q13b
M1a
M1a



Iv8a
VE2c
Q24a
M2c
M1a



Iv9a
VE2b
Q19b
M7a
M7a



Iv10a
VE2a
Q2a
M12a
M12a



Iv11a
VE2a
Q13a
M13a
M13a



Iv12a
VE3a
Q1a
M1b
M1b



Iv13a
VE3a
Q14a
M13a
M13a



Iv14a
VE4a
Q7b
M1a
M1a



Iv15a
VE4a
Q19a
M2a
M2a



Iv15b
VE4a
Q19b
M2b
M2b



Iv16a
VE4a
Q24a
M14a
M14a



Iv17a
VE5a
Q16a
M3a
M3a



Iv18a
VE5a
Q13a
M12a
M12a



Iv19a
VE6a
Q9a
M6a
M6a



Iv20a
VE6b
Q16a
M10b
M10b



Iv22a
VE7a
Q9a
M2a
M2a



Iv24a
VE8a
Q13a
M1a
M1a



Iv24b
VE8b
Q13a
M1b
M1b



Iv24c
VE8e
Q13a
M1a
M1a



Iv24d
VE8f
Q13a
M1b
M1b



Iv25a
VE8a
Q19b
M2c
M2c



Iv25b
VE8b
Q19b
M2b
M2b



Iv25c
VE8f
Q19a
M2c
M2c



Iv26a
VE8c
Q16a
M4a
M4a



Iv27a
VE8d
Q21a
M5a
M5a



Iv28a
VE8c
Q2a
M10a
M10a



Iv29a
VE8b
Q24a
M12a
M12a



Iv30a
VE8e
Q14a
M14a
M14a



Iv31a
VE9b
Q4a
M1a
M1a



Iv32a
VE9a
Q21a
M8a
M8a



Iv33a
VE9a
Q1a
M13a
M13a



Iv34a
VE10a
Q9a
M10c
M10c



Iv36a
VE11a
Q9a
M17a
M17a



Iv37a
VE12a
Q1a
M7a
M7a



Iv39a
VE1a
Q12a
M1a
M1a










Very particularly preferred structural units of the formula (Iv) are structural units in which Ar1 is selected from the groups of the formulae VE1b to VE12b, Ar2 and Ar3 are selected from the groups of the formulae M1b to M14c, and Q is selected from the groups Q1b to Q24c.
A selection of very particularly preferred structural units of the formula (Iv) is shown in the following Table 12.













TABLE 12







Formula (I)
Ar1
Q
Ar2
Ar3









Iv1b
VE1b
Q1b
M1c
M1c



Iv1c
VE1e
Q1c
M1c
M1c



Iv1d
VE1c
Q1b
M1c
M1c



Iv2c
VE1c
Q14b
M2d
M2d



Iv2d
VE1e
Q14d
M2f
M2f



Iv2e
VE1f
Q14d
M2f
M2f



Iv3b
VE1d
Q7c
M10d
M10d



Iv4b
VE1f
Q2b
M12b
M12b



Iv5b
VE1c
Q2b
M14b
M14b



Iv5c
VE1d
Q2c
M14b
M14c



Iv7c
VE2d
Q13b
M1d
M1d



Iv7d
VE2f
Q13e
M1c
M1c



Iv8b
VE2f
Q24b
M2f
M1c



Iv9b
VE2e
Q19d
M7b
M7b



Iv10b
VE2e
Q2c
M12b
M12b



Iv11b
VE2d
Q13c
M13b
M13b



Iv12b
VE3b
Q1b
M1d
M1d



Iv13b
VE3b
Q14c
M13b
M13b



Iv14b
VE4c
Q7d
M1c
M1c



Iv14c
VE4d
Q7d
M1c
M1c



Iv15c
VE4b
Q19d
M2e
M2e



Iv15d
VE4e
Q19c
M2d
M2d



Iv16b
VE4b
Q24c
M14c
M14c



Iv18b
VE5b
Q13b
M12b
M12b



Iv24e
VE8g
Q13e
M1c
M1c



Iv24f
VE8j
Q13b
M1c
M1c



Iv24g
VE8k
Q13d
M1d
M1d



Iv24h
VE8l
Q13c
M1d
M1d



Iv25d
VE8g
Q19d
M2f
M2f



Iv25e
VE8h
Q19d
M2e
M2e



Iv25f
VE8k
Q19c
M2f
M2f



Iv28b
VE8i
Q2b
M10d
M10d



Iv29b
VE8m
Q24c
M12b
M12b



Iv30b
VE8j
Q14e
M14b
M14b



Iv31b
VE9d
Q4b
M1c
M1c



Iv33b
VE9c
Q1b
M13b
M13b



Iv37b
VE12b
Q1c
M7b
M7b



Iv39b
VE1b
Q12b
M1c
M1c










Preferred crosslinkable structural units of the formula (IIva)




are structural units in which Ar4 is selected from the groups of the formulae E1 to E12, Ar5, Ar7 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1 to M19, where it is particularly preferred for Ar5 and Ar7 to be identical, Ar8 is selected from the groups VE1 to VE12 and Q is selected from the groups Q1 to Q24.

Preferred crosslinkable structural units of the formula (IIvb)




are structural units in which Ar7 is selected from the groups of the formulae E1 to E12, Ar4, Ar5 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1 to M19, where it is particularly preferred for Ar4 and Ar5 to be identical, Ar6 is selected from the groups of the formulae VE1 to VE12 and Q is selected from the groups Q1 to Q24.

A selection of preferred structural units of the formula (IIva) or (IIvb) is shown in the following Table 13.










TABLE 13









Formula (IIva)















Ar4
Ar6
Q
Ar5
Ar7
Ar8










Formula (IIvb)















Ar7
Ar6
Q
Ar5
Ar4
Ar8



















IIv1
E1
VE1
Q1
M1
M1
M1



IIv2
E1
VE1
Q13
M1
M1
M2



IIv3
E1
VE1
Q19
M1
M1
M10



IIv4
E1
VE1
Q2
M1
M1
M13



IIv5
E1
VE1
Q13
M1
M1
M14



IIv6
E1
VE1
Q24
M14
M14
M12



IIv7
E2
VE2
Q13
M1
M1
M2



IIv8
E2
VE2
Q7
M2
M2
M12



IIv9
E3
VE3
Q4
M7
M7
M1



IIv10
E3
VE3
Q22
M10
M10
M16



IIv11
E4
VE4
Q4
M1
M1
M7



IIv12
E4
VE4
Q1
M1
M1
M12



IIv13
E4
VE4
Q14
M2
M2
M14



IIv14
E4
VE4
Q24
M10
M10
M13



IIv15
E4
VE8
Q19
M1
M1
M7



IIv16
E5
VE5
Q14
M2
M13
M13



IIv17
E6
VE6
Q21
M3
M3
M6



IIv18
E6
VE6
Q16
M17
M17
M10



IIv19
E7
VE7
Q9
M5
M5
M4



IIv20
E8
VE8
Q14
M1
M1
M1



IIv21
E8
VE8
Q19
M1
M1
M2



IIv22
E8
VE8
Q1
M1
M1
M12



IIv23
E8
VE8
Q9
M2
M2
M10



IIv24
E8
VE8
Q21
M6
M6
M8



IIv25
E8
VE8
Q7
M10
M10
M7



IIv26
E8
VE8
Q13
M13
M13
M2



IIv27
E8
VE8
Q7
M14
M14
M12



IIv28
E9
VE9
Q24
M1
M1
M2



IIv29
E9
VE9
Q22
M9
M9
M11



IIv30
E9
VE9
Q12
M19
M19
M18



IIv31
E10
VE10
Q9
M1
M1
M4



IIv32
E11
VE11
Q16
M2
M2
M10



IIv33
E11
VE11
Q8
M13
M13
M15



IIv34
E12
VE12
Q14
M7
M7
M14



IIv35
E1
VE1
Q12
M1
M1
M2



IIv36
E2
VE2
Q1
M1
M1
M14










Particularly preferred structural units of the formula (IIva) are structural units in which Ar4 is selected from the groups of the formulae E1a to E12a, Ar5, Ar7 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1a to M17a, where it is particularly preferred for Ar5 and Ar7 to be identical, Ar6 is selected from the groups of the formulae VE1a to VE12a and Q is selected from the groups Q1a to Q24a.
Particularly preferred structural units of the formula (IIvb) are structural units in which Ar7 is selected from the groups of the formulae E1a to E12a, Ar4, Ar5 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1a to M17a, where it is particularly preferred for Ar4 and Ar5 to be identical, Ar6 is selected from the groups of the formulae VE1a to VE12a and Q is selected from the groups Q1a to Q24a.
A selection of particularly preferred structural units of the formula (IIva) or (llvb) is shown in the following Table 14.










TABLE 14









Formula (IIa)















Ar4
Ar6
Q
Ar5
Ar7
Ar8










Formula (IIb)















Ar7
Ar6
Q
Ar5
Ar4
Ar8



















IIv1a
E1a
VE1a
Q1a
M1a
M1a
M1a



IIv1b
E1a
VE1a
Q1a
M1b
M1b
M1b



IIv2a
E1a
VE1a
Q13a
M1a
M1a
M2a



IIv3a
E1a
VE1a
Q19b
M1a
M1a
M10a



IIv4a
E1a
VE1a
Q2a
M1a
M1a
M13a



IIv4b
E1a
VE1a
Q2a
M1b
M1b
M13a



IIv5a
E1a
VE1a
Q13a
M1a
M1a
M14a



IIv6a
E1a
VE1a
Q24a
M14a
M14a
M12a



IIv7a
E2a
VE2a
Q13a
M1a
M1a
M2a



IIv7b
E2c
VE2c
Q13a
M1a
M1a
M2a



IIv8a
E2b
VE2b
Q7b
M2b
M2b
M12a



IIv9a
E3a
VE3a
Q4a
M7a
M7a
M1b



IIv11a
E4a
VE4a
Q4a
M1b
M1b
M7a



IIv12a
E4a
VE4a
Q1a
M1b
M1b
M12a



IIv13a
E4a
VE4a
Q14a
M2b
M2b
M14a



IIv14a
E4a
VE4a
Q24a
M10a
M10a
M13a



IIv15a
E4a
VE8a
Q19b
M1b
M1b
M7a



IIv16a
E5a
VE5a
Q14a
M2c
M13a
M13a



IIv17a
E6a
VE6a
Q21a
M3a
M3a
M6a



IIv18a
E6b
VE6b
Q16a
M17a
M17a
M10b



IIv19a
E7a
VE7a
Q9a
M5a
M5a
M4a



IIv20a
E8f
VE8f
Q14a
M1a
M1a
M1a



IIv21a
E8b
VE8b
Q19a
M1a
M1a
M2a



IIv21b
E8e
VE8e
Q19b
M1a
M1a
M2a



IIv22a
E8b
VE8b
Q1a
M1b
M1b
M12a



IIv23a
E8d
VE8d
Q9a
M2b
M2b
M10c



IIv24a
E8f
VE8f
Q21a
M6a
M6a
M8a



IIv25a
E8a
VE8a
Q7a
M10a
M10a
M7a



IIv26a
E8c
VE8c
Q13a
M13a
M13a
M2c



IIv27a
E8b
VE8b
Q7a
M14a
M14a
M12a



IIv28a
E9a
VE9a
Q24a
M1a
M1a
M2a



IIv28b
E9b
VE9b
Q24a
M1a
M1a
M2a



IIv31a
E10a
VE10a
Q9a
M1b
M1b
M4a



IIv32a
E11a
VE11a
Q16a
M2c
M2c
M10c



IIv34a
E12a
VE12a
Q14a
M7a
M7a
M14a



IIv35a
E1a
VE1a
Q12a
M1a
M1a
M2a



IIv36a
E2a
VE2a
Q1a
M1a
M1a
M14a










Very particularly preferred structural units of the formula (IIva) are structural units in which Ar4 is selected from the groups of the formulae E1b to E12b, Ar5, Ar7 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1b to M14c, where it is particularly preferred for Ar5 and Ar7 to be identical, Ar6 is selected from the groups of the formulae VE1b to VE12b and Q is selected from the groups Q1b to Q24c.
Very particularly preferred structural units of the formula (IIvb) are structural units in which Ar7 is selected from the groups of the formulae E1b to E12b, Ar4, Ar5 and Ar8, independently of one another, identically or differently, are selected from the groups of the formulae M1b to M14c, where it is particularly preferred for Ar4 and Ar5 to be identical, Ar6 is selected from the groups of the formulae VE1b to VE12b and Q is selected from the groups Q1b to Q24c.
A selection of very particularly preferred structural units of the formula (IIva) or (IIvb) is shown in the following Table 15.










TABLE 15









Formula (IIva)















Ar4
Ar6
Q
Ar5
Ar7
Ar8










Formula (IIvb)















Ar7
Ar6
Q
Ar5
Ar4
Ar8



















IIv1c
E1b
VE1b
Q1c
M1c
M1c
M1c



IIv1d
E1e
VE1e
Q1b
M1d
M2d
M1d



IIv2b
E1b
VE1b
Q13b
M1c
M1c
M2d



IIv3b
E1b
VE1b
Q19d
M1c
M1c
M10d



IIv4c
E1b
VE1b
Q2b
M1c
M1c
M13b



IIv4d
E1d
VE1d
Q2c
M1d
M1d
M13b



IIv5b
E1c
VE1c
Q13e
M1c
M1c
M14b



IIv6b
E1f
VE1f
Q24c
M14b
M14b
M12b



IIv7c
E2d
VE2d
Q13d
M1c
M1c
M2d



IIv7d
E2f
VE2f
Q13c
M1c
M1c
M2d



IIv8b
E2e
VE2e
Q7d
M2e
M2e
M12b



IIv9b
E3b
VE3b
Q4b
M7b
M7b
M1d



IIv11b
E4d
VE4d
Q4b
M1d
M1d
M7b



IIv12b
E4c
VE4c
Q1b
M1d
M1d
M12b



IIv13b
E4b
VE4b
Q14d
M2e
M2e
M14c



IIv14b
E4e
VE4e
Q24b
M10d
M10d
M13b



IIv15b
E4d
VE8g
Q19d
M1d
M1d
M7b



IIv16b
E5b
VE5b
Q14e
M2f
M13b
M13b



IIv20b
E8k
VE8k
Q14b
M1c
M1c
M1c



IIv21c
E8h
VE8h
Q19c
M1c
M1c
M2d



IIv21d
E8j
VE8j
Q19d
M1c
M1c
M2d



IIv22b
E8m
VE8m
Q1c
M1d
M1d
M12b



IIv25b
E8g
VE8g
Q7c
M10d
M10d
M7b



IIv26b
E8i
VE8i
Q13e
M13b
M13b
M2f



IIv27b
E8l
VE8l
Q7c
M14c
M14c
M12b



IIv28c
E9c
VE9c
Q24b
M1c
M1c
M2d



IIv28d
E9d
VE9d
Q24c
M1c
M1c
M2d



IIv34b
E12b
VE12b
Q14c
M7b
M7b
M14c



IIv35b
E1b
VE1b
Q12b
M1c
M1c
M2d



IIv36b
E2d
VE2d
Q1b
M1c
M1c
M14b










Preferred polymers according to the invention contain:

    
    
        the preferred structural units (I1) to (I38) of the formula (I);
        the preferred structural units (II1) to (II34) of the formula (II);
        optionally the preferred structural units (III1) to (III19) of the formula (III); and
        the preferred crosslinkable structural units (Iv1) to (Iv39) of the formula (Iv).
    
    


A selection of preferred polymers is shown in the following Table 16.














TABLE 16







Polymer
(I)
(Iv)
(II)
(IIv)
(III)























P1
1
1
1
—
14



P2
—
1
7
—
14



P3
—
1
7
—
12



P4
1
1
4
—
—



P5
1
1
3
—
—



P6
—
1
4
—
14



P7
—
1
3
—
14



P8
—
1
2
—
14



P9
—
1
2
—
7



P10
—
1
2
—
7; 14



P11
1
1
2
—
—



P12
—
1
4; 7
—
—



P13
1
1
4
—
14



P14

1
4; 7

14



P15
1
1
7
—
14



P16
—
1
7
—
17



P17
—
1
21
—
14



P18
1
1
7
—
1



P19
24
2
9; 16
—
—



P20
31
4
26
—
—



P21
37
7
12
—
12



P22
2
8
7
—
—



P23
5
11
21
—
2



P24
12; 14
14
28
—
10



P25
18
16
34
—
13



P26
25
24
21
—
—



P27
29
24
4
—
2



P28
33
39
13
—
—



P29
1
—
8
1
—



P30
15
—
20
2
7



P31
5
—
25
4
—



P32
7
—
28
6
1



P33
31
—
11
7
14



P34
2
—
—
20
10



P35
24
—
—
35
—



P36
—
2
7
—
2; 14



P37
—
5
14
—
7



P38
3
—
—
15
12



P39
9
—
—
28
14



P40
14
1; 2
2
—
—



P41
—
30; 31
22
—
—



P42
—
1
15
13
10



P43
18
25
—
21
2; 12



P44
1
1
35
—
14



P45
1
1
35
—
—



P46
—
39
35
—
14



P47
1
39
21
—
14



P48
—
39
3
—
14



P49
—
1
21
—
—



P50
—
1
7; 35
—
17



P51
—
1
35
—
14



P52
—
39
36
—
14



P53
—
1
28
—
23



P54
—
1
4
—
20



P55
41
39
36
—
14



P56
—
1
38
—
1



P57
—
39
37
—
12










Particularly preferred polymers according to the invention contain:

    
    
        the particularly preferred structural units (I1a) to (I37a) of the formula (I);
        the particularly preferred structural units (II1a) to (II34a) of the formula (II);
        optionally the particularly preferred structural units (III1a) to (III17a) of the formula (III); and
        the particularly preferred crosslinkable structural units (Iv1a) to (Iv39a) of the formula (Iv).
    
    


A selection of particularly preferred polymers is shown in the following Table 17.














TABLE 17







Polymer
(I)
(Iv)
(II)
(IIv)
(III)









P1a
1a
1a
1a
—
14a



P2a
—
1a
7a
—
14a



P2b
—
1a
7b
—
14a



P3a
—
1a
7a
—
12a



P4a
1a
1a
4a
—
—



P5a
1a
1a
3a
—
—



P6a
—
1a
4a
—
14a



P7a
—
1a
3a
—
14a



P8a
—
1a
2a
—
14a



P9a
—
1a
2a
—
7a



P10a
—
1a
2a
—
7a; 14a



P11a
1a
1a
2a
—
—



P12a
—
1a
4a; 7a
—
—



P13a
1a
1a
4a
—
14a



P14a
—
1a
4a; 7a
—
14a



P15a
1a
1a
7a
—
14a



P16a
—
1a
7a
—
17a



P17a
—
1a
21a
—
14a



P18a
1a
1a
7a
—
1a



P19a
24c
2a
9a; 16a
—
—



P20a
31a
4a
26a
—
—



P21a
37a
7a
12a
—
12a



P22a
2a
8a
7b
—
—



P23a
5a
11a
21b
—
2b



P24a
12a;
14a
28b
—
10a



P25a
18a
16a
34a
—
13a



P26a
25a
24a
21a
—
—



P27a
29a
24b
4b
—
2c



P28a
33a
39a
13a
—
—



P29a
1a
—
8a
1b
—



P30a
15a
—
20a
2a
7a



P31a
5a
—
25a
4b
—



P32a
7a
—
28a
6a
1b



P33a
31a
—
11a
7b
14a



P34a
2b
—
—
20a
10a



P35a
24d
—
—
35a
—



P36a
—
2b
7a
—
2a; 14a



P37a
—
5a
14a
—
7a



P38a
3a
—
—
15a
12a



P39a
9a
—
—
28b
14a



P40a
14a
1a; 2a
2a
—
—



P41a
—
30a;
22a
—
—



P42a
—
1a
15a
13a
10a



P43a
18a
25c
—
21a
2c; 12a



P44a
1a
1a
35a
—
14a



P45a
1a
1a
35a
—
—



P46a
—
39a
35a
—
14a



P47a
1a
39a
21a
—
14a



P48a
—
39a
3a
—
14a



P49a
—
1a
21a
—
—



P50a
—
1a
7a; 35a
—
17a



P51a
—
1a
35b
—
14a



P52a
—
39a
36a
—
14a



P53a
—
1a
28b

23a



P54a
—
1a
4a
—
20a



P55a
41a
39a
36a
—
14a



P56a
—
1a
38a
—
1b



P57a
—
39a
37b
—
12a










Very particularly preferred polymers according to the invention contain:

    
    
        the very particularly preferred structural units (I1b) to (I37b) of the formula (I);
        the very particularly preferred structural units (II1c) to (II34b) of the formula (II);
        optionally the very particularly preferred structural units (III1c) to (III14c) of the formula (III); and
        the very particularly preferred crosslinkable structural units (Iv1b) to (Iv39b) of the formula (Iv).
    
    


A selection of very particularly preferred polymers is shown in the following Table 18.














TABLE 18







Polymer
(I)
(Iv)
(II)
(IIv)
(III)









P1b
1b
1b
1c
—
14b



P2c
—
1b
7c
—
14b



P2d
—
1b
7c
—
14c



P2e
—
1d
7c
—
14b



P2f
—
1b
7c
—
14b; 14c



P2g
—
1b
7d
—
14b



P3b
—
1b
7c
—
12b



P4b
1b
1b
4c
—
—



P5b
1b
1b
3b
—
—



P6b
—
1b
4c
—
14b



P7b
—
1b
3b
—
14b



P8b
—
1b
2b
—
14c



P8c
—
1b
2b
—
14b



P9b
—
1b
2b
—
7b



P10b
—
1b
2b
—
7b; 14b



P11b
1b
1b
2b
—
—



P12b
—
1b
4c; 7c
—
—



P13b
1b
1b
4c
—
14b



P14b
—
1b
4c; 7c
—
14b



P15b
1b
1b
7c
—
14b



P16b
—
1b
7c
—
17b



P17b
—
1b
21c
—
14b



P18b
1c
1c
7c
—
1c



P19b
24f
2c
9b; 16b
—
—



P20b
31b
4b
26b
—
—



P21b
37b
7c
12b
—
12b



P22b
31b
4b
26b
—
—



P23b
37b
7c
12b
—
12b



P24b
2c
8b
7d
—
—



P25b
5b
11b
21d
—
2e



P26b
25d
24e
21c
—
—



P27b
29b
24h
4d
—
2f



P28b
33b
39b
13b
—
—



P29b
1b
—
8b
1d
—



P30b
15d
—
20b
2b
7b



P31b
5c
—
25b
4d
—



P32b
7c
—
28c
6b
1d



P33b
31b
—
11b
7d
14b



P34b
2d
—
—
20b
10d



P35b
24g
—
—
35b
—



P36b
—
2d
7c
—
2d; 14c



P37b
—
5b
14b
—
7b



P38b
3b
—
—
15b
12b



P39b
9b
—
—
28d
14b



P40b
14c
1c; 2c
2b
—
—



P41b
—
30b; 31b
22b
—
—



P42b
—
1b
15b
13b
10d



P43b
18b
25f
—
21c
2f; 12b



P44b
1b
1b
35c
—
14b



P45b
1b
1b
35c
—
—



P46b
—
39b
35c
—
14c



P47b
1b
39b
21c
—
14c



P48b
—
39b
3b
—
14b



P49b
—
1b
21b
—
—



P50b
—
1b
7c; 35c
—
17b



P51b
—
1b
35d
—
14b



P52b
—
39b
36b
—
14b



P53b
—
1b
28d
—
23c



P54b
—
1b
4c
—
20i



P55b
41d
39b
36b
—
14b



P56b
—
1b
38c
—
1d



P57b
—
39c
37d
—
12b










The proportion of structural units of the formula (I) in the polymer is preferably in the range from 1 to 99 mol %, particularly preferably in the range from 3 to 97 mol %, and very particularly preferably in the range from 5 to 95 mol %, based on 100 mol % of all copolymerised monomers present as structural units in the polymer.
The proportion of structural units of the formula (II) in the polymer is preferably in the range from 1 to 99 mol %, particularly preferably in the range from 3 to 97 mol %, and very particularly preferably in the range from 5 to 95 mol %, based on 100 mol % of all copolymerised monomers present as structural units in the polymer.
The proportion of structural units of the formula (Iv) and/or (IIv), preferably of structural units of the formula (Iv), which contain a crosslinkable group Q in the polymer is preferably in the range from 0.1 to 50 mol %, particularly preferably in the range from 0.5 to 40 mol %, and very particularly preferably in the range from 1 to 30 mol %, based on 100 mol % of all copolymerised monomers present as structural units in the polymer.
In a first preferred embodiment, the proportion of structural units of the formulae (I) and (II) in the polymer is 100 mol %, i.e. the polymer consists exclusively of structural units of the formulae (I) and (II). The proportion of structural units of the formula (I) and/or (II), preferably of structural units of the formula (I), which contain a crosslinkable group Q is in the ranges indicated above.
In the first preferred embodiment, the proportion of structural units of the formula (I) is preferably in the range from 30 to 75 mol %, of which 1 to 30 mol % of the structural units of the formula (I) contain crosslinkable groups Q, and the proportion of structural units of the formula (II) is likewise preferably in the range from 25 to 70 mol %. In this embodiment, the proportion of structural units of the formula (I) which contain no crosslinkable group Q is consequently in the range from 0 to 74 mol %.
In a second preferred embodiment, the proportion of structural units of the formulae (I) and (II) in the polymer is in the range from 25 to 75 mol %, i.e. the polymer contains further structural units, either structural units of the formula (III) which are different from structural units (I) and (II) or structural units which are different from the structural units of the formulae (I), (II) and (III). The proportion of these further structural units, preferably of the formula (III), in the polymer is then in the range from 25 to 75 mol %, based on 100 mol % of all copolymerised monomers present as structural units in the polymer.
The polymers according to the invention which contain at least one structural unit of the formula (I), at least one structural unit of the formula (II) and optionally at least one structural unit of the formula (III), where at least one structural unit of the formula (I) and/or (II) contains at least one crosslinkable group Q, are generally prepared by polymerisation of a plurality of different monomers, at least one monomer of which results in structural units of the formula (I) in the polymer, at least one monomer of which results in structural units of the formula (II) in the polymer, and optionally at least one monomer of which results in structural units of the formula (III) in the polymer. Suitable polymerisation reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerisation reactions which result in C—C or C—N links are the following:

    (A) SUZUKI polymerisation;
    (B) YAMAMOTO polymerisation;
    (C) STILLE polymerisation;
    (D) HECK polymerisation;
    (E) NEGISHI polymerisation;
    (F) SONOGASHIRA polymerisation;
    (G) HIYAMA polymerisation; and
    (H) HARTWIG-BUCHWALD polymerisation.


The way in which the polymerisation can be carried out by these methods and the way in which the polymers can then be separated off from the reaction medium and purified is known to the person skilled in the art and is described in detail in the literature, for example in WO 03/048225 A2, WO 2004/037887 A2 and WO 2004/037887 A2.
The C—C linking reactions are preferably selected from the groups of the SUZUKI coupling, the YAMAMOTO coupling and the STILLE coupling. The C—N linking reaction is preferably a HARTWIG-BUCHWALD coupling.
The present invention thus preferably also relates to a process for the preparation of the polymers according to the invention, which is characterised in that they are prepared by SUZUKI polymerisation, YAMAMOTO polymerisation, STILLE polymerisation or HARTWIG-BUCHWALD polymerisation.
Monomers which can be converted into the polymers according to the invention by polymerisation are monomers containing at least two groups, preferably two groups, which are preferably selected, independently of one another, from the group consisting of halogen, preferably Br and I, O-tosylate, O-triflate, O—SO2R2, B(OR2)2 and Sn(R2)3.
R2 is preferably selected on each occurrence, independently of one another, from the group consisting of hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms and a mono- or polycyclic, aromatic ring system having 6 to ring atoms, where two or more radicals R2 may form a ring system with one another. Aliphatic hydrocarbons having 1 to 20 carbon atoms here are linear, branched or cyclic alkyl groups, alkenyl groups, alkynyl groups, in which one or more carbon atoms may be replaced by O, N or S. In addition, one or more hydrogen atoms may be replaced by fluorine. Examples of aliphatic hydrocarbons having 1 to 20 carbon atoms include the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl (1-methylpropyl), tert-butyl, isopentyl, n-pentyl, tert-pentyl (1,1-dimethylpropyl), 1,2-dimethyl propyl, 2,2-dimethylpropyl(neopentyl), 1-ethylpropyl, 2-methylbutyl, n-hexyl, isohexyl, 1,2-dimethylbutyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl.
The term “mono- or polycyclic, aromatic ring system having 6 to 20 ring atoms” with respect to R2 is intended to have the same meaning as defined above in relation to Ar1 to Ar8. Preferred aromatic ring systems are naphthyl and phenyl, where phenyl is particularly preferred.
In the case where two radicals R2 form a ring system, these two linked radicals R2 preferably represent a divalent aliphatic group having 2 to 8 carbon atoms. Examples thereof are compounds of the following formula —CH2(CH2)nCH2—, where n=0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2 or 3.
In the case where more than two radicals R2 form a ring system with one another, these radicals R2 with one another represent a branched tri-, tetra-, penta- or polyvalent aliphatic group having 6 to 20 carbon atoms.
In a particularly preferred embodiment, the reactive groups of the monomers are selected, independently of one another, from Br, I and B(OR2)2.
The dendrimers according to the invention can be prepared by processes known to the person skilled in the art or analogously thereto. Suitable processes are described in the literature, such as, for example, in Frechet, Jean M. J.; Hawker, Craig J., “Hyperbranched polyphenylene and hyperbranched polyesters: new soluble, three-dimensional, reactive polymers”, Reactive & Functional Polymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “The synthesis and characterization of dendritic molecules”, Materials Science and Technology (1999), 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.
The crosslinkable polymers according to the invention which contain at least one structural unit of the formula (I), at least one structural unit of the formula (II) and optionally at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q, can be used as the pure substance, but also as a mixture (blend) together with any desired further polymeric, oligomeric, dendritic or low-molecular-weight substances. Low-molecular-weight substance in the present application is taken to mean compounds having a molecular weight in the range from 100 to 3000 g/mol, preferably 200 to 2000 g/mol. These further substances may, for example, improve the electronic properties or themselves emit. Likewise, a styrene monomer may also be added as low-molecular-weight substance in order to achieve a higher degree of crosslinking. The term mixture above and below denotes a mixture comprising at least one polymeric component. In this way, one or more polymer layers consisting of a mixture (blend) of one or more crosslinkable polymers according to the invention which contain at least one structural unit of the formula (I), at least one structural unit of the formula (II) and optionally at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q, and optionally one or more further polymers can be prepared using one or more low-molecular-weight substances.
The present invention thus furthermore relates to a polymer blend comprising one or more crosslinkable polymers according to the invention which contain at least one structural unit of the formula (I), at least one structural unit of the formula (II) and optionally at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q, and one or more further polymeric, oligomeric, dendritic and/or low-molecular-weight substances.
The present invention furthermore relates to solutions and formulations comprising one or more crosslinkable polymers according to the invention or mixtures in one or more solvents. The way in which such solutions can be prepared is known to the person skilled in the art and is described, for example, in WO 02/072714 A1, WO 03/019694 A2 and the literature cited therein.
Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (−)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphtalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 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 in order to produce thin polymer layers, for example by surface-coating methods (for example spin coating) or by printing processes (for example ink-jet printing).
The crosslinkable polymers according to the invention which contain at least one structural unit of the formula (I), at least one structural unit of the formula (II) and optionally at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q, are particularly suitable for the production of films or coatings, in particular for the production of structured coatings, for example by thermal or light-induced in-situ polymerisation and in-situ crosslinking, such as, for example, in-situ UV photopolymerisation or photopatterning. It is both possible here to use corresponding polymers in pure substance, but also formulations or mixtures of these polymers as described above. These can be used with or without addition of solvents and/or binders. Suitable materials, processes and devices for the methods described above are described, for example, in WO 2005/083812 A2. Possible binders are, for example, polystyrene, polycarbonate, poly(meth)acrylates, polyacrylates, polyvinylbutyral and similar, optoelectronically neutral polymers.
The present invention furthermore relates to the use of a crosslinkable polymer according to the invention which contains at least one structural unit of the formula (I), at least one structural unit of the formula (II) and optionally at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q, for the preparation of a crosslinked polymer.
If the crosslinkable group Q is, for example, a vinyl group or alkenyl group, the crosslinking can take place by free-radical or ionic polymerisation, which can be induced thermally or by radiation. Preference is given to free-radical polymerisation which is induced thermally, preferably at temperatures of less than 250° C., particularly preferably at temperatures of less than 200° C.
The present invention thus also relates to a process for the preparation of a crosslinked polymer which comprises the following steps:

    (a) provision of the crosslinkable polymer according to the invention which contains at least one structural unit of the formula (I), at least one structural unit of the formula (II) and optionally at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q; and
    (b) free-radical or ionic crosslinking, preferably free-radical crosslinking, of the crosslinkable polymer, which can be induced both thermally and also by radiation, preferably thermally.


The crosslinked polymers prepared by the process according to the invention are insoluble in all common solvents. In this way, it is possible to produce defined layer thicknesses which cannot be dissolved or partially dissolved again, even by the application of subsequent layers.
The present invention thus also relates to a crosslinked polymer which is obtainable by the process mentioned above. The crosslinked polymer is, as described above, preferably produced in the form of a crosslinked polymer layer. Owing to the insolubility of the crosslinked polymer in all solvents, a further layer can be applied to the surface of a crosslinked polymer layer of this type.
The crosslinked polymer according to the invention can be used in electronic or opto-electronic devices or for the production thereof.
The present invention thus furthermore relates to the use of the crosslinked polymer according to the invention in electronic or opto-electronic devices, preferably in organic electroluminescent devices (OLED), organic light-emitting electrochemical cells (OLEC), organic field-effect transistors (OFET), organic integrated circuits (O-IC), organic thin-film transistors (TFT), organic solar cells (O-SC), organic laser diodes (O-lasers), organic photovoltaic (OPV) elements or devices or organic photoreceptors (OPC), particularly preferably in organic electroluminescent devices (OLED).
The way in which OLEDs can be produced is known to the person skilled in the art and is described in detail, for example, as a general process in WO 2004/070772 A2, which should be adapted correspondingly for the individual case.
The term OLED here also encompasses a so-called hybrid device, in which one or more polymer layers and one or more layers comprising low-molecular-weight substances may occur. The low-molecular-weight substances here can be processed either by vapour deposition in a high vacuum or from solution.
As described above, the crosslinked polymers according to the invention are very particularly suitable as active materials in OLEDs or displays produced in this way.
Active materials in the sense of the present application are materials which can be used as active layer or in an active layer. Active layer means that the layer is capable of emitting light on application of an electric field (light-emitting layer) and/or that it improves the injection and/or transport of positive and/or negative charges (charge-injection or charge-transport layer) and/or that it blocks the injection and/or transport of positive and/or negative charges (charge-blocking layer).
The present invention therefore preferably also relates to the use of the crosslinked polymer according to the invention in an OLED, as charge-injection or charge-transport material, particularly preferably as hole-injection or hole-transport material.
The present invention furthermore relates to electronic or opto-electronic components, preferably organic electroluminescent devices (OLEDs), organic light-emitting electrochemical cells (OLECs), 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 (OPV) elements or devices and organic photoreceptors (OPCs), particularly preferably organic electroluminescent devices, having one or more active layers, where at least one of these active layers comprises one or more crosslinked polymers according to the invention. The active layer can be, for example, a light-emitting layer, a charge-transport layer and/or a charge-injection layer, or a charge-blocking layer.
The present application text and also the examples below are principally directed to the use of the crosslinked polymers according to the invention in relation to OLEDs and corresponding displays. In spite of this restriction of the description, it is possible for the person skilled in the art, without further inventive step, also to use the crosslinked polymers according to the invention as semiconductors for the further uses described above in other electronic devices.
The following examples are intended to explain the invention in greater detail without restricting it. In particular, the features, properties and advantages described therein of the defined compounds on which the relevant example is based can also be applied to other compounds which are not described in detail, but fall within the scope of protection of the claims, unless stated otherwise elsewhere.


WORKING EXAMPLES
Part A: Synthesis of the Monomers
Biphenyl-2-ylphenylamine can be synthesised in accordance with Organic Letters 2006, 8, 1133. All further starting materials used are commercially available or are prepared in accordance with the literature indicated in Table 19.
Example 1
Preparation of Monomer Mo6
1st Step:




    71.5 g of N4,N4′-bisbiphenyl-4-yl-N4,N4′-diphenylbiphenyl-4,4′-diamine (112 mmol) (CAS: 134008-76-7) are dissolved in 1.5 l of dried tetrahydrofuran (THF) and cooled to 0° C. 40 g of N-bromosuccinimide (224 mmol) are added in portions as a solid, and the solution is stirred at 20° C. for 14 hours.


The solid is filtered and washed with THF. The filtrates are evaporated together, stirred with water, filtered off with suction and dried in a vacuum drying cabinet. The residue is recrystallised twice from dimethylformamide (DMF) (700 ml and 500 ml). The solid is then stirred three times with 700 ml of ethanol and subsequently dried in a drying cabinet, giving 72.7 g (82% of theory) as a pale-coloured solid.
2nd Step:




    58.3 g of N4,N4′-bisbiphenyl-4-yl-N4,N4′-bis-(4-bromophenyl)biphenyl-4,4′-diamine (73 mmol) are dissolved in 1.5 l of dried THF, 44.5 g of bis(pinacolato)diboron (175.2 mmol) and 43 g of potassium acetate (438 mmol) are added successively as solids, and the solution is saturated with argon. 1.2 g of 1,1-bis(diphenylphosphino)ferrocene-Pd(II) dichloride complex is added, and the reaction mixture is stirred under reflux for 22 hours.


The solid is filtered through silica gel and Celite, and the solution is evaporated. 800 ml of dichloromethane are added to the residue. The phases are separated. The organic phase is washed three times with 300 ml of water and dried over Na2SO4, then filtered and evaporated in a rotary evaporator. The product is filtered through silica gel (toluene as eluent). The clean fractions (about 35 g) are recrystallised from a mixture of 50 ml of heptane and 170 ml of toluene. The solid is filtered, washed with heptane and dried, giving 33.5 g (52% of theory) of the product as a colourless powder having a purity of 99.1% according to HPLC.
Examples 2 to 5
Preparation of Monomers Mo16, Mo21, Mo22 and Mo23
1st Step:




    21.7 g of 2,8-dibromo-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2-b]fluorene (25 mmol) are dissolved in 0.2 l of dried toluene, 13.0 g of biphenyl-4-ylphenylamine (52 mmol), 26.3 g of caesium carbonate (80 mmol) and 0.23 g of palladium acetate (1 mmol) are added successively as solids, and the solution is saturated with nitrogen. 2.0 ml of 1 M tri-tert-butylphosphine solution (2 mmol) are added, and the reaction mixture is stirred under reflux for 24 hours.


The solid is filtered off and washed with toluene. The filtrates are evaporated together, stirred with hot ethanol, filtered off with suction and dried in a vacuum drying cabinet, giving 26.8 g (90% of theory) as a yellow solid.
The following intermediates are synthesised analogously:















Dibrominated



Inter-
starting



mediates
material
Amine





Mo16-a










 


Mo21-a










 


Mo22-a










 


Mo23-a













Inter-




mediates
Product
Yield





Mo16-a




90%


 


Mo21-a




68%


 


Mo22-a




74%


 


Mo23-a




81%









2nd Step:





    26.0 g of N,N′-bisbiphenyl-4-yl-6,6,12,12-tetraoctyl-N,N′-diphenyl-6H,12H-indeno[1,2-b]fluorene-2,8-diamine (21 mmol) are dissolved in 0.6 l of dried tetrahydrofuran (THF) and cooled to 0° C. 7.8 g of N-bromosuccinimide (43 mmol) are added in portions as a solid, and the solution is stirred at 20° C. for 14 hours.


The reaction mixture is evaporated. The residue is stirred in hot ethanol. The solid is filtered and recrystallised three times from ethyl acetate (in each case 1 I) and subsequently dried in a drying cabinet, giving 23.0 g (78% of theory) of the product as a yellow powder having a purity of 97.7% according to HPLC.
The following monomers are synthesised analogously:













Monomer
Starting material





Mo16






 


Mo21






 


Mo22






 


Mo23


















Yield




(HPLC


Monomer
Product
purity)





Mo16




78% (97.7%)


 


Mo21




75% (99.3%)


 


Mo22




82% (98.7%)


 


Mo23




71% (99.8%)









Example 6
Preparation of Monomer Mo17
1st Step:




    50.0 g of diphenylamine (295 mmol) are initially introduced in 1000 ml of toluene with 64.5 g of 3-bromobenzonitrile (355 mmol), 20 ml of tri-tert-butylphosphine (1M solution in toluene, 20 mmol), 2.65 g of palladium acetate (11 mmol) and 85.2 g of sodium tert-butoxide (886 mmol) and heated under reflux with stirring for 15 hours. After cooling, the organic phase is washed three times with 1 l of water each time, dried over sodium sulfate and subsequently evaporated to dryness in vacuo. The solid remaining is extracted with about 400 ml of heptane in a continuous hot extractor through a bed of aluminium oxide (basic, activity grade 1). After cooling, the precipitated solid is filtered off, washed twice with about 200 ml of heptane and dried in vacuo, giving 53.0 g (66% of theory) as a pale-coloured solid.

2nd Step;







    53.0 g of 3-diphenylaminobenzonitrile (196 mmol) are dissolved in 500 ml of dry tetrahydrofuran and cooled to 0° C. 69.8 g (392 mmol) of N-bromosuccinimide are added in portions as a solid with ice-cooling and vigorous stirring that the temperature does not exceed 5° C. The cooling is removed, and the mixture is stirred for 12 hours. The solvent is removed in vacuo, and the solid remaining is dissolved in as little ethyl acetate as possible. The solution is washed three times with about 500 ml of aqueous sodium hydroxide solution (5%) and twice with water. The organic phase is evaporated to dryness, giving 70.8 g (84% of theory) as a colourless solid.

3rd Step:







    70.8 g (165 mmol) of 3-[bis-(4-bromophenyl)]benzonitrile are dissolved in 700 ml of dry dichloromethane and cooled to −78° C. 174 ml (174 mmol) of a 1M solution of diisobutylaluminium hydride in toluene are added dropwise at such a rate that the temperature does not exceed −50° C. The cooling is removed, the mixture is allowed to warm to 10° C. and re-cooled to −10° C. After addition of 175 ml of tetrahydrofuran, a mixture of 43 g of concentrated sulfuric acid and 175 ml of water is rapidly added, and the mixture is stirred without further cooling for 12 hours. The mixture is rendered neutral using aqueous sodium hydroxide solution. The organic phase is separated off, washed twice with about 350 ml of water and once with 350 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solvent is removed in a rotary evaporator, leaving a yellow oil, which crystallises over the course of 24 hours. The solid is extracted with about 300 ml of heptane in a continuous hot extractor through a bed of aluminium oxide (basic, activity grade 1) and filtered off after cooling. It is recrystallised three times from isopropanol. Drying in vacuo gives 13.0 g (18% of theory) as a yellow solid.

4th Step:







    13.0 g (30 mmol) of 3-[bis-(4-bromophenyl)amino]benzaldehyde, 33.7 g (137 mmol) of bis(pinacolato)diborane, 14.8 g (151 mmol) of potassium acetate, 0.27 g (1.2 mmol) of palladium acetate and 0.69 g (1.2 mmol) of bis(diphenylphosphino)ferrocene are heated under reflux in 500 ml of dioxane with vigorous stirring for 14 hours. The solvent is removed in vacuo, the solid remaining is taken up in as little ethyl acetate as possible and filtered through silica gel with a mixture of ethyl acetate and heptane (1:1). The solvent is removed in vacuo, and the oil remaining is stirred with about 100 ml for 2 hours. The resultant solid is filtered off, dried in vacuo and subsequently subjected to fractional sublimation at 200° C. and a pressure of 10−5 mbar, giving 3.5 g (22% of theory) of the product as a colourless powder having a purity of 99.8% according to HPLC.


Table 19 below shows the other monomers which are used for the preparation of the polymers according to the invention and whose preparation has already been described in the prior art.









TABLE 19







Synthesis in 


Monomer
Structure
accordance with







Mo1




WO 2010/097155 A1


 


Mo2




WO 99/048160 A1


 


Mo3




WO 2010/097155 A1


 


Mo4




WO 2005/104263 A1


 


Mo5




WO 02/077060 A1


 


Mo7




WO 03/000773 A1


 


Mo8




WO 2005/104263 A1


 


Mo9




Macromolecules, 2000, 33, 2016


 


Mo10




Macromolecules, 2000, 33, 2016


 


Mo11




WO 02/077060 A1


 


Mo12




WO 2004/041901 A1


 


Mo13




WO 2004/041901 A1


 


Mo14




WO 2005/104264 A1


 


Mo15




WO 02/077060 A1


 


Mo18




Tetrahedron, 2009, 50, 182


 


Mo19




EP 1 491 568 A1


 


Mo20




WO 2009/102027









Part B: Synthesis of the Polymers
Examples 7 to 47
Preparation of comparative polymers V1 and V2 and polymers according to the invention Po1 to Po39.
Comparative polymers V1 and V2 and polymers according to the invention Po1 to Po39 are prepared by SUZUKI coupling by the process described in WO 2010/097155 from the monomers in Examples 1 to 6 and the monomers depicted in Table 19.
Polymers V1 and V2 as well as Po1 to Po39 prepared in this way contain the structural units in the percentage proportions (percent data=mol %) indicated in Table 20 after removal of the leaving groups. In the case of the polymers which contain a crosslinkable vinyl group, this is obtained from the aldehyde group by WITTIG reaction by the process described in WO 2010/097155.
The palladium and bromine contents of the polymers are determined by ICP-MS. The values determined are below 10 ppm.
The molecular weights Mw and the polydispersities D are determined by means of gel permeation chromatography (GPC) (model: Agilent HPLC system series 1100) (column: PL-RapidH from Polymer Laboratories; solvent; THF comprising 0.12% by vol. of o-dichlorobenzene; detection: UV and refractive index; temperature: 40° C.). The calibration is carried out using polystyrene standards.
The results are summarised in Table 20













TABLE 20







Structural unit
Structural unit
Structural unit




Example
Polymer
of the formula (I)
of the formula (II)
of the formula (III)
Molecular wt. Mw (g/mol)
Polydisp. D






























7
V1
Mo2
50%






Mo9
50%


438 000
3.3


8
V2
Mo1
10%
Mo2
40%




Mo9
50%


417 000
3.1


9
Po1
Mo1
10%
Mo2
40%
Mo4
50%






240 000
1.9


10
Po2
Mo1
10%


Mo5
50%


Mo10
40%


174 000
1.9


11
Po3
Mo1
20%


Mo6
30%


Mo9
50%


196 000
2.7


12
Po4
Mo1
10%
Mo2
40%
Mo7
10%


Mo9
40%


375 000
3.1


13
Po5
Mo1
10%


Mo6
40%


Mo9
50%


126 000
2.3


14
Po6
Mo1
10%


Mo6
40%


Mo11
50%


 97 000
2.8


15
Po7
Mo1
10%
Mo2
40%
Mo8
50%






193 000
1.7


16
Po8
Mo1
10%


Mo4
40%


Mo9
50%


196 000
2.6


17
Po9
Mo1
10%


Mo8
40%


Mo9
50%


190 000
2.5


18
Po10
Mo1
10%


Mo6
40%


Mo12
50%


112 000
1.9


19
Po11
Mo3
10%


Mo5
40%


Mo13
50%


126 000
2.1


20
Po12
Mo3
10%


Mo5
40%


Mo14
30%
Mo9
20%
195 000
1.9


21
Po13
Mo1
10%


Mo4
50%
Mo6
40%




 74 000
1.5


22
Po14
Mo1
10%
Mo2
40%
Mo4
30%


Mo9
20%


243 000
2.9


23
Po15
Mo1
10%
Mo2
10%
Mo6
30%


Mo9
50%


161 000
2.5


24
Po16
Mo1
10%
Mo2
20%
Mo4
50%


Mo10
20%


 67 000
2.3


25
Po17
Mo3
10%


Mo15
40%


Mo10
50%


189 000
2.5


26
Po18
Mo1
10%


Mo6
30%


Mo9
50%
M10
10%
125 000
2.1


27
Po19
Mo1
20%
Mo2
30%
Mo4
50%






 89 000
1.6


28
Po20
Mo3
20%


Mo16
30%


Mo10
50%


156 000
2.0


29
Po21
Mo1
20%
Mo2
30%
Mo16
50%






101 000
3.1


30
Po22
Mo1
20%


Mo6
30%
Mo4
20%
Mo9
30%


357 000
4.8


31
Po23
Mo3
20%


Mo4
30%


Mo10
50%


169 000
3.7


32
Po24
Mo1
15%


Mo6
35%


Mo9
50%


190 000
2.6


33
Po25
Mo17
20%


Mo6
30%


Mo9
50%


358 000
3.8


34
Po26
Mo1
20%


Mo6
30%


Mo9
25%
Mo18
25%
220 000
3.1


35
Po27
Mo1
20%


Mo6
30%


Mo19
50%


390 000
5.9


36
Po28
Mo1
14%
Mo3
6%
Mo6
36%


Mo9
44%
Mo12
10%
156 000
3.1


37
Po29
Mo1
20%


Mo6
36%


Mo9
40%
Mo12
20%
150 000
3.8


38
Po30
Mo1
20%


Mo6
36%


Mo9
30%


130 000
4.7


39
Po31
Mo20
10


Mo16
40%


Mo13
50%


210 000
2.9


40
Po32
Mo20
5%
Mo3
5%
Mo15
40%


Mo10
50%


186 000
2.1


41
Po33
Mo20
8%


Mo8
42%


Mo10
50%


175 000
3.2


42
Po34
Mo3
30%


Mo5
20%


Mo13
50%


 58 000
5.8


43
Po35
Mo1
50%


Mo15
50%






 74 000
3.6


44
Po36
Mo1
25%


Mo16
15%
Mo6
25%
Mo19
35%


123 000
2.4


45
Po37
Mo1
10%


Mo21
40%


Mo9
50%


190 000
1.9


46
Po38
Mo20
13%


Mo22
50%


Mo10
37%


133 000
2.7


47
Po39
Mo1
17%


Mo23
33%


Mo9
50%


194 000
2.5









Part C: Checking of the Layer Thicknesses
In the following experiments, it is checked whether the polymers according to the invention produce a completely insoluble layer after crosslinking. Similar experiments are also described in WO 2010/097155.
To this end, the polymers according to the invention are applied to glass supports in a layer thickness of 20 nm by spin coating. For the spin coating, the polymers are dissolved in toluene (concentration: 5 g/l). The layer thickness is measured and checked by scratching the polymer layer with a needle, with the scratch extending as far as the glass substrate. The depth of the scratch and thus the thickness of the polymer layer is subsequently measured twice at each of at least two points with the aid of a profilometer needle (Dektak, Bruker), and the average is formed. If the desired layer thickness has not been reached, the rotational speed of the spin coater is adapted.
For the layer thickness checking experiment, the polymers according to the invention are applied to glass supports which have been coated with 80 nm of PEDOT:PSS (poly(3,4-ethylenedioxy-2,5-thiophene): polystyrene sulfonate), with a layer thickness of 20 nm by spin coating. The PEDOT: PSS, purchased from Heraeus Precious Metals GmbH & Co. KG, Germany, is applied by spin coating from water and dried by heating at 180° C. for 10 minutes.
The polymer film is then crosslinked by heating at 180° C. or at 220° C. for one hour. The glass supports with the crosslinked polymer films are subsequently washed with toluene on the spin coater (rotational speed: 1000 rpm) for one minute. The film is then again dried by heating at 180° C. for 10 minutes in order to remove the solvent. The layer thickness is subsequently measured again as described above in order to check whether the layer thickness has changed.
Table 21 shows the remaining layer thickness of the original 20 nm after the washing process. If the layer thickness has not reduced, the polymer is insoluble and the crosslinking is thus adequate.







TABLE 21







Check of the residual layer thickness from originally


20 nm after washing test











Residual layer thickness




after washing




test [in nm]



Polymer
Crosslinking at 220° C.














V1
3.5



V2
20



Po3
20



Po5
20



Po7
20










As revealed by Table 21, comparative polymer V1, which carries no crosslinking group, undergoes virtually no crosslinking at all at 220° C. Comparative polymer V2 and polymers according to the invention P3, P5 and P7 crosslink completely at 220° C.
Part D: Production of the OLEDs
The polymers according to the invention can be processed from solution and result in OLEDs which can be produced significantly more simply compared with vacuum-processed OLEDs, with nevertheless good properties.
The production of solution-based OLEDs of this type has already been described many times in the literature, for example in WO 2004/037887 and WO 2010/097155. The process is adapted to the circumstances described below (layer-thickness variation, materials).
The polymers according to the invention are used in two different layer sequences:
Structure A is as follows:

    
    
        substrate,
        ITO (50 nm),
        PEDOT (80 nm),
        interlayer (IL) (20 nm),
        emission layer (80 nm),
        electron-injection layer (EIL),
        cathode.
    
    


Structure B is as follows;

    
    
        substrate,
        ITO (50 nm),
        PEDOT (80 nm),
        interlayer (IL) (20 nm),
        emission layer (EML) (60 nm),
        hole-blocking layer (HBL) (10 nm)
        electron-transport layer (ETL) (40 nm),
        cathode.
    
    


The substrate used is glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. For better processing, these are coated with PEDOT:PSS. The spin coating is carried out from water in air. The layer is dried by heating at 180° C. for 10 minutes. PEDOT:PSS is purchased from Heraeus Precious Metals GmbH & Co. KG, Germany. The interlayer and the emission layer are applied to these coated glass plates.
The interlayer used serves for hole injection (HIL). The compounds according to the invention and comparative compounds are used. The interlayer according to the invention is dissolved in toluene. The typical solids content of such solutions is about 5 g/l if, as here, the typical layer thickness of 20 nm for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 180° C. or 220° C. for 60 minutes.
The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Furthermore, mixtures of a plurality of matrix materials and co-dopants may occur. An expression such as TMM-A (92%): dopant (8%) here means that material TMM-A is present in the emission layer in a proportion by weight of 92% and the dopant is present in the emission layer in a proportion by weight of 8%. The mixture for the emission layer is dissolved in toluene. The typical solids content of such solutions is about 18 g/l, if, as here, the typical layer thickness of 60 nm or 80 nm for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 180° C. for 10 minutes. The materials used in the present case are shown in Table 22.







TABLE 22





Structural formulae of the materials used in the emission layer




















TMM-A


 






TMM-B


 






TMM-C


 






TMM-D


 






TEG


 






TER









In structure A, the electron-injection layer and the cathode are formed by a barium layer with a thickness of 3 nm and an aluminium layer with a thickness of 100 nm by thermal evaporation in a vacuum chamber.
The materials for the hole-blocking layer and electron-transport layer in structure B are likewise applied by thermal vapour deposition in a vacuum chamber. The electron-transport layer here can consist, for example, of more than one material which are admixed with one another in a certain proportion by volume by co-evaporation. An expression such as ETM1:ETM2 (50%:50%) here means that materials ETM1 and ETM2 are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in Table 23.







TABLE 23





HBL and ETL materials used




















ETM1


 






ETM2









The cathode is formed by thermal evaporation of an aluminium layer with a thickness of 100 nm.
The precise structure of the OLEDs is shown in Table 24. Column IL shows the polymer used, and the temperature at which the crosslinking is carried out.







TABLE 24







Structure of the OLEDs











IL

EML











Example
Polymer
T [° C.]
Structure
Composition





48
V2
180° C.
A
TMM-A 39%; TMM-B 39%;






TEG 16%; TER 6%


49
Po1
220° C.
A
TMM-A 39%; TMM-B 39%;






TEG 16%; TER 6%


50
Po7
220° C.
A
TMM-A 39%; TMM-B 39%;






TEG 16%; TER 6%


51
Po5
220° C.
A
TMM-A 39%; TMM-B 39%;






TEG 16%; TER 6%


52
Po2
220° C.
A
TMM-A 39%; TMM-B 39%;






TEG 16%; TER 6%


53
Po3
180° C.
A
TMM-A 39%; TMM-B 39%;






TEG 16%; TER 6%


54
V2
180° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%


55
V2
180° C.
B
TMM-C 30%; TMM-D 55%;






TEG 15%


56
Po3
180° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%


57
Po20
180° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%


58
Po21
220° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%


59
Po5
220° C.
B
TMM-C 30%; TMM-D 55%;






TEG 15%


60
Po23
220° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%


61
Po25
180° C.
B
TMM-C 30%; TMM-D 55%;






TEG 15%


62
Po26
220° C.
B
TMM-C 30%; TMM-D 55%;






TEG 15%


63
Po33
220° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%


64
Po22
180° C.
B
TMM-C 30%; TMM-D 55%;






TEG 15%


65
Po24
180° C.
B
TMM-C 30%; TMM-D 55%;






TEG 15%


66
Po37
180° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%


67
Po38
180° C.
B
TMM-C 30%; TMM-D 55%;






TEG 15%


68
Po39
180° C.
B
TMM-C 30%; TMM-D 34%;






TEG 30%; TER 6%









The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics and the (operating) lifetime are determined. From the IUL characteristic lines, characteristic numbers, such as the operating voltage (in V) and the efficiency (in cd/A) or the external quantum efficiency (in %) at a certain luminance, are determined. The electroluminescence spectra are measured at a luminous density of 1000 cd/m2, and the CIE 1931 x and y colour coordinates are calculated therefrom.
LT50 @ 1000 cd/m2 is the lifetime by which the OLED at a starting luminance of 1000 cd/m2 has dropped to 50% of the initial intensity, i.e. to 500 cd/m2. Correspondingly, LT80 @ 8000 cd/m2 is the lifetime by which the OLED at a starting luminance of 8000 cd/m2 has dropped to 80% of the initial intensity, i.e. to 6400 cd/m2, and LT80 @ 10,000 cd/m2 is the lifetime by which the OLED at a starting luminance of 10,000 cd/m2 has dropped to 80% of the initial intensity, i.e. to 8000 cd/m2.
The properties of the various OLEDs are summarised in Tables 25 a, b and c. Examples 48, 54 and 55 are comparative examples, all other examples show properties of OLEDs according to the invention.
Tables 25 a to c: Properties of the OLEDs












TABLE 25a








Efficiency at
Voltage at
LT50 at




1000 cd/m2
1000 cd/m2
1000 cd/m2



Example
[cd/A]
[V]
[h]





















48
10.82
6.32
13000



49
6.98
5.44
22000



50
8.13
5.44
21000



51
11.09
6.16
25000



52
11.01
6.05
24000



53
10.95
6.09
26000






















TABLE 25b








Efficiency at
Voltage at
LT80 at




1000 cd/m2
1000 cd/m2
8000 cd/m2



Example
% EQE
[V]
[h]









54
11.4
6.0
165



56
12.8
5.6
205



57
12.8
6.1
150



58
13.2
5.7
330



60
12.7
5.7
198



63
11.4
6.3
160



66
12.9
5.5
190



68
12.5
5.8
188






















TABLE 25c








Efficiency at
Voltage at
LT80 at




1000 cd/m2
1000 cd/m2
10 000 cd/m2



Example
% EQE
[V]
[h]









55
17.0
4.2
110



59
18.0
4.4
150



61
17.2
4.2
120



62
17.5
4.5
135



64
16.8
4.3
133



65
17.8
3.9
188



67
18.2
3.9
195










As shown by Tables 25 a to c, the polymers according to the invention give rise to improvements over the prior art, in particular with respect to lifetime and operating voltage, on use as interlayer (IL) in OLEDs. Red- and green-emitting OLEDs are produced with the materials according to the invention.

## Claims

1. A polymer comprising at least one structural unit of the following formula (I):



at least one structural unit of the following formula (II):




and at least one further structural unit of the following formula (III) which is different from structural units (I) and (II):


—Ar9—  (III)


where
Ar1 to Ar8 is on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;
Ar9 in formula (III) is selected from:








where,
X is CR2, SiR2, O or S,
and
the indices used have the following meaning:
k=0 or 1;
m=0, 1 or 2;
n=0, 1, 2 or 3; and
o=0, 1, 2, 3 or 4;

i and j is each 0 or 1, where the sum (i+j) =1;
R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R1)2, CN, NO2, Si(R1)3, B(OR1)2, C(═O)R1, P(═O)(R1)2, S(═O)R1, S(═O)2R1, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by R1C═CR1, C≡C, Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S or CONR1 and where one or more H atoms may be replaced by D, F, Cl , Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may in each be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1; where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another;
R1 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; and
the dashed lines represent bonds to adjacent structural units in the polymer and the dashed lines which are located in brackets represent possible bonds to adjacent structural units in the polymer;
characterised in that at least one of the structural units of the formula (I) and/or (II) contains at least one crosslinkable group Q.

2. The polymer according to claim 1, wherein the structural unit of the formula (II) corresponds either to the structural unit of the following formula (IIa):



or to the structural unit of the following formula (IIb):

3. The polymer according to claim 1, wherein the proportion of structural units of the formulae (I) and (II) in the polymer is 100 mol %.

4. The polymer according to claim 1, wherein the proportion of structural units of the formulae (I) and (II) in the polymer is in the range from 25 to 75 mol %.

5. The polymer according to claim 1, wherein the polymer, besides structural units of the formulae (I), (II) and (III), also contains further structural units which are different from the structural units of the formulae (I), (II) and (III).

6. The polymer according to claim 1, wherein the mono- or polycyclic, aromatic or heteroaromatic groups Ar1 in formula (I), Ar4 and Ar6 in formula (IIa) and Ar6 and Ar7 in formula (IIb) are selected from:






where
X is CR2, SiR2, NR, O or S, and
the indices used have the following meaning:
m=0, 1 or 2;
n=0, 1, 2 or3;
o=0, 1, 2, 3 or 4; and
p=0, 1, 2, 3, 4 or 5.

7. The polymer according to claim 1, wherein the mono- or polycyclic, aromatic or heteroaromatic groups Ar2 and Ar3 in formula (I), Ar5, Ar7 and Ar8 in formula (IIa), Ar4, Ar5 and Ar8 in formula (IIb), are selected from:









where,
X is CR2, SiR2, O or S,
Y is CR2, SiR2, O, S or a straight-chain or branched alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, each of which may be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups, CH groups or C atoms of the alkyl, alkenyl or alkynyl groups may be replaced by Si(R1)2, C═O, C═S, C═NR1, P(═O)(R1), SO, SO2, NR1, O, S, CONR1, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1, where here too the radicals R and R1can adopt the same meanings as the radicals R and R1in the formulae (I) and (II), and the indices used have the following meaning:
k=0 or 1;
m=0, 1 or 2;
n=0, 1, 2 or 3;
o=0, 1, 2, 3 or 4; and
q=0, 1, 2, 3, 4, 5 or 6.

8. The polymer according to claim 1, wherein the crosslinkable group Q is selected from:
terminal or cyclic alkenyl or terminal dienyl and alkynyl groups,
alkenyloxy, dienyloxy or alkynyloxy groups,
acrylic acid groups,
oxetane and oxirane groups,
silane groups, and
cyclobutane groups.

9. The polymer according to claim 8, wherein the crosslinkable group Q is selected from:












where
the radicals R11, R12 and R13 in the formulae Q1 to Q8, Q11, Q13 to Q20 and Q23 are on each occurrence, identically or differently, H, a straight-chain or branched alkyl group having 1 to 6 C atoms;
the indices used have the following meaning:
Ar10is a mono- or polycyclic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;
s=0 to 8;
t=1 to 8; and
the dashed bond in the formulae Q1 to Q11 and Q13 to Q23 and the dashed bonds in the formulae Q12 and Q24 represent the linking of the crosslinkable group to one of the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar1 to Ar8.

10. The polymer according to claim 1, wherein the proportion of structural units of the formula (I) in the polymer is in the range from 1 to 99 mol %, based on 100 mol% of all copolymerised monomers present as structural units in the polymer.

11. The polymer according to claim 1, wherein the proportion of structural units of the formula (II) in the polymer is in the range from 1 to 99 mol %, based on 100 mol % of all copolymerised monomers present as structural units in the polymer.

12. The polymer according to claim 1, wherein the proportion of structural units of the formula (I) and/or (II) which contain a crosslinkable group Q in the polymer is in the range from 0.1 to 50 mol %, based on 100 mol % of all copolymerised monomers present as structural units in the polymer.

13. A process for the preparation of a polymer according to claim 1 comprising preparing the polymer by SUZUKI polymerisation, YAMAMOTO polymerisation, STILLE polymerisation or HARTWIG-BUCHWALD polymerisation.

14. A polymer blend comprising one or more crosslinkable polymers according to claim 1 which comprising at least one structural unit of the formula (I), at least one structural unit of the formula (II) and at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q, and one or more further polymeric, oligomeric, dendritic and/or low-molecular-weight substances.

15. A solutions or formulation comprising one or more crosslinkable poly-mers according to claim 1 in one or more solvents.

16. A solutions or formulation comprising one or more polymer blends according to claim 14 in one or more solvents.

17. A method for the preparation of a crosslinked polymer comprising utilizing a crosslinkable polymer according to claim 1 which comprises at least one structural unit of the formula (I), at least one structural unit of the formula (II) and at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q.

18. A process for the preparation of a crosslinked polymer which comprises the following steps:
(a) providing the crosslinkable polymer according to claim 1 comprising at least one structural unit of the formula (I), at least one structural unit of the formula (II) and at least one structural unit of the formula (III), where at least one structural unit of the formulae (I) and/or (II) contains at least one crosslinkable group Q; and
(b) free-radical or ionic crosslinking of the crosslinkable polymer, which can be induced both thermally and also by radiation.

19. A crosslinked polymer, obtained by the process according to claim 17.

20. A method comprising utilizing the crosslinked polymer according to claim 18 in electronic or opto-electronic devices, preferably in organic electroluminescent devices (OLED), organic light-emitting electrochemical cells (OLEC), organic field-effect transistors (OFET), organic integrated circuits (O-IC), organic thin-film transistors (TFT), organic solar cells (O-SC), organic laser diodes (O-lasers), organic photovoltaic (OPV) elements or devices or organic photoreceptors (OPC), particularly preferably in organic electroluminescent devices (OLED).

21. An electronic or opto-electronic component comprising one or more active layers, wherein at least one of the active layers comprises one or more crosslinked polymers according to claim 18.