KR20250004913A - Polymers containing specially substituted triarylamine units and electroluminescent devices containing said polymers - Google Patents

Abstract

The present invention relates to polymers containing particularly substituted triarylamine repeating units, to a process for their preparation, and to their use in electronic devices, in particular in organic electroluminescent devices, so-called OLEDs (OLED = organic light emitting diodes). The present invention also relates to organic electroluminescent devices containing said polymer.

Description

Polymers containing specially substituted triarylamine units and electroluminescent devices containing said polymers

The present invention relates to polymers containing particularly substituted repeating triarylamine units, to processes for their preparation, and to their use in electronic or optoelectronic devices, in particular in organic electroluminescent devices so called OLEDs (OLED = organic light emitting diodes). Furthermore, the present invention further relates to organic electroluminescent devices comprising these polymers.

In electronic or optoelectronic devices, especially in organic electroluminescent devices (OLEDs), components of different functionality are required. In OLEDs, the different functionality is usually present in different layers. In this case, reference is made to multilayer OLED systems. The layers in these multilayer OLED systems comprise charge injection layers, for example electron and hole injection layers, charge transport layers, for example electron and hole conducting layers, and layers containing light-emitting components. These multilayer OLED systems are generally manufactured by successive layer-by-layer application.

If more than one layer is applied from the solution, it must be ensured that any layer already applied is not destroyed, after drying, by the subsequent application of the solution for the production of the next layer. This can be achieved, for example, by rendering the layer insoluble, by crosslinking. Methods of this kind are disclosed, for example, in EP 0 637 899 and WO 96/20253.

Furthermore, it is also necessary to match the functionality of the individual layers to each other from a material perspective so that very good results are achieved, for example in terms of lifetime, efficiency, etc. For example, the layer directly adjacent to the emitting layer, in particular the hole-transport layer (HTL = hole transport layer), has a significant influence on the properties of the adjacent emitting layer.

Accordingly, one of the problems addressed by the present invention was to provide compounds which, firstly, when processed from solution, and secondly, when used in electronic or optoelectronic devices, preferably OLEDs, and here in particular in the hole transport layer thereof, lead to improvements in the properties of the devices, i.e. in particular OLEDs.

Surprisingly, it was found that polymers having repeating triarylamine groups substituted with at least one, preferably both, aryl group in the backbone have an increased energy gap compared to a comparable conjugated polymer and a decreased energy gap compared to a comparable polymer in which conjugation has been interrupted, due to twisting caused by the substituents, especially when used in the hole-transport layer of an OLED. Furthermore, the polymers of the present invention have an improved efficiency compared to a comparable conjugated polymer and an improved lifetime compared to a comparable polymer in which conjugation has been interrupted, when used in an OLED.

Accordingly, the present invention provides a polymer having at least one structural unit of the following formula (I):

During the meal

Ar ¹ to Ar ³ are in each case the same or different and are a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, and Ar ³ may be substituted with one or more R radicals;

R is in each case the same or different and is H, D, F, Cl, Br, I, N(R ³ ) ₂ , CN, NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , C(=O)R ³ , P(=O)(R ³ ) ₂ , S(=O)R ³ , S(=O) ₂ R ³ , OSO ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups are R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , P(=O)(R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN), or a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may be substituted by one or more R ³ radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R ³ radicals, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R ³ radicals, or a diarylamino group, a diheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more R ³ radicals or an arylheteroarylamino group; or a bridging group Q, wherein two or more R radicals may also be taken together to form a monocyclic or polycyclic, aliphatic, aromatic and/or benzo fused ring system;

R ³ is in each case the same or different and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, an aromatic and/or heteroaromatic hydrocarbyl radical having 5 to 20 carbon atoms (wherein one or more hydrogen atoms may also be replaced by F); wherein two or more R ³ substituents together may also form a monocyclic or polycyclic, aliphatic or aromatic ring system; and

Dotted lines represent bonds to adjacent structural units in the polymer;

Ar ¹ is substituted by a R ¹ radical and/or Ar ² is substituted by a R ² radical. It is characterized by being substituted, where

R ¹ and R ² are each independently the same or different at each occurrence and are F, Cl, Br, I, N(R ³ ) ₂ , CN, NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , C(=O)R ³ , P(=O)(R ³ ) ₂ , S(=O)R ³ , S(=O) ₂ R ³ , OSO ₂ R ³ , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms which may be substituted by one or more R ³ radicals at each occurrence, wherein one or more non-adjacent CH ₂ groups are R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , P(=O)(R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN.

Preferably, Ar ¹ is substituted by an R ¹ radical and Ar ² is substituted by an R ² radical.

More preferably, Ar ³ is substituted at least in one of the two ortho positions, and preferably in one, by Ar ⁴ , wherein Ar ⁴ is a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R radicals.

Ar ⁴ can be connected to Ar ³ directly, i.e., by a single bond, or else via a linker X.

Therefore, in the first embodiment, the structural unit of formula (I) has the structure of formula (Ia):

During the meal

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and R can assume the definitions given above,

q = 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4,

X = CR ₂ , NR, SiR ₂ , O, S, C=O or P=O, preferably CR ₂ , NR, O or S, and

r = 0 or 1, preferably 0

In the present invention, the term "polymer" is understood to mean polymeric compounds, oligomeric compounds and dendrimers. The polymeric compounds of the present invention preferably have 10 to 10 000, more preferably 10 to 5000 and most preferably 10 to 2000 structural units (i.e. repeating units). The oligomeric compounds of the present invention preferably have 3 to 9 structural units. The branching factor of the polymer is between 0 (linear polymer, no branching sites) and 1 (fully branched dendrimer).

The polymer of the present invention preferably has a molecular weight M _w in the range of 1000 to 2 000 000 g/mol, more preferably a molecular weight M _w in the range of 10 000 to 1 500 000 g/mol and most preferably a molecular weight M _w in the range of 50 000 to 1 000 000 g/mol. The molecular weight M _w is determined by GPC (= gel permeation chromatography) against an internal polystyrene standard.

The polymer of the present invention is a conjugated, semi-conjugated or non-conjugated polymer. Conjugated or semi-conjugated polymers are preferred.

According to the present invention, the structural units of formula (I) and formula (Ia) may be included in the main chain or the side chain of the polymer. However, preferably, the structural units of formula (I) and formula (Ia) are included in the main chain of the polymer. When included in the side chain of the polymer, the structural units of formula (I) and formula (Ia) may be monovalent or divalent, which means that they have one or two bonds to adjacent structural units in the polymer.

In the context of the present application a "conjugated polymer" is a polymer containing predominantly sp ² -hybridized (or, alternatively, optionally sp-hybridized) carbon atoms in the backbone, which may also be replaced by correspondingly hybridized heteroatoms. In the simplest case, this means not only the alternating presence of double bonds and single bonds in the backbone, but also polymers having units such as meta-bonded phenylene, for example, should be considered as conjugated polymers in the context of the present application. What is meant by "predominantly" is that naturally occurring (randomly) occurring effects leading to disruption of conjugation do not invalidate the term "conjugated polymer". A conjugated polymer is likewise considered to be a polymer having a conjugated backbone and non-conjugated side chains. Furthermore, the present invention likewise refers to conjugation (i.e. conjugation via nitrogen, oxygen or sulfur atoms) and/or conjugation (i.e. conjugation via metal atoms) when, for example, arylamine units, arylphosphine units, certain heterocycles are present in the backbone. The same applies to conjugated dendrimers. In contrast, units such as simple alkyl bridges, (thio)ether, ester, amide or imide linkages are clearly defined as non-conjugated segments.

A semi-conjugated polymer herein is understood to mean a polymer which contains conjugated regions which are separated from each other by non-conjugated sections, deliberate conjugation breakers (e.g. spacer groups) or branches, for example relatively long conjugated sections in the backbone are interrupted by non-conjugated sections, or which contains relatively long conjugated sections in side chains of the polymer which are non-conjugated in the backbone. Conjugated and semi-conjugated polymers may also contain conjugated, semi-conjugated or non-conjugated dendrimers.

The term "dendrimer" herein is to be understood as meaning a highly branched compound formed from a polyfunctional core to which branched monomers are linked in a regular structure such that a tree-like structure is obtained. In this case, both the core and the monomers may assume any desired branched structure consisting of both purely organic units and also organometallic compounds or coordination compounds. "Dendrimers" are generally used herein as defined by, for example, M. Fischer and F. (Angew. Chem., Int. Ed. 1999, 38, 885) should be understood as explained.

The term "structural unit" in this specification is understood to mean a unit which proceeds from a monomer unit having at least two, preferably two, reactive groups by a bond-forming reaction, is incorporated into the polymer base backbone as a part thereof, and thus exists as a repeating unit in the polymer produced.

The term "monocyclic or polycyclic aromatic ring system" is understood herein to mean an aromatic ring system having 6 to 60, preferably 6 to 30 and more preferably 6 to 24 aromatic ring atoms, which does not necessarily contain only aromatic groups, but it is also understood that it is possible for two or more aromatic units to be interrupted by short non-aromatic units (<10 % of atoms other than H, preferably <5 % of atoms other than H), for example ^sp3 -hybridized carbon atoms or oxygen or nitrogen atoms, CO groups etc. For example systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene and 9,9-dialkylfluorene are for example also to be regarded as aromatic ring systems.

Aromatic ring systems can be monocyclic or polycyclic, meaning that they can have one ring (e.g., phenyl), or two or more rings which may be fused (e.g., naphthyl), or two or more rings which may be covalently bonded (e.g., biphenyl), or can contain a combination of fused rings and bonded rings.

Preferred aromatic ring systems are, for example, phenyl, biphenyl, terphenyl, [1,1':3',1"]terphenyl-2'-yl, quaterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene and spirobifluorene.

The term "monocyclic or polycyclic heteroaromatic ring system" herein is understood to mean an aromatic ring system having 5 to 60, preferably 5 to 30, and more preferably 5 to 24 aromatic ring atoms, wherein at least one of these atoms is a heteroatom. The "monocyclic or polycyclic heteroaromatic ring system" does not necessarily contain exclusively aromatic groups, but may also be interrupted by short non-aromatic units (<10% of atoms other than H, preferably <5% of atoms other than H), for example ^sp3 -hybridized carbon atoms or oxygen or nitrogen atoms, CO groups, etc.

Heteroaromatic ring systems can be monocyclic or polycyclic, meaning that they can have one ring, or two or more rings which may be fused or covalently bonded (e.g., pyridylphenyl), or can contain a combination of fused and bonded rings. Fully conjugated heteroaryl groups are preferred.

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 a group having several rings, such as carbazole, indenocarbazole, indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthyimidazole, phenanthridazole, pyrimidazole, pyrazineimidazole, quinoxalineimidazole, 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[2,3-b]thiophene, thieno[3,2-b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene or a combination of these groups.

The monocyclic or polycyclic, aromatic or heteroaromatic ring system may be unsubstituted or substituted. As used herein, "substituted" means that the monocyclic or polycyclic, aromatic or heteroaromatic ring system has one or more R substituents.

R is preferably, in each case, identical or different, and is H, D, F, Cl, Br, I, N(R ³ ) ₂ , CN, NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , C(=O)R ³ , P(=O)(R ³ ) ₂ , S(=O)R ³ , S(=O) ₂ R ³ , OSO ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups are R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , P(=O)(R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ^{3 ,} and one or more hydrogen 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, each of which may be substituted by one or more R ³ radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals, or an aralkyl or heteroaralkyl group having 10 to 40 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals. a diarylamino group, a diheteroarylamino group or an arylheteroarylamino group; or a bridging group Q; and at the same time, two or more R radicals may also together form a monocyclic or polycyclic, aliphatic, aromatic and/or benzo fused ring system;

R is preferably, in each case, identical or different, and is H, D, F, Cl, Br, I, N(R ³ ) ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , C(=O)R ³ , P(=O)(R ³ ) ₂ , a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, each of which may be substituted by one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups are substituted by R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=NR ³ , P(=O)(R ³ ), NR ³ , O or CONR ^{3 .} an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which may be substituted by one or more R ³ radicals, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms which may be substituted by one or more R ³ radicals, or an aralkyl or heteroaralkyl group having 5 to 30 aromatic ring atoms which may be substituted by one or more R ³ radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 20 aromatic ring atoms which may be substituted by one or more R ³ radicals; or a bridging group Q; at the same time two or more R radicals may also together form a monocyclic or polycyclic, aliphatic, aromatic and/or benzofused ring system;

R is preferably, in each case, identical or different, and is H, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or an alkenyl or alkynyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which may be substituted by one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups may be replaced by R ³ C=CR ³ , C≡C, C=O, C=NR ³ , NR ³ , O or CONR ³ , or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which in each case may be substituted by one or more R ³ radicals, or an aryloxy or heteroaryloxy group having 5 to 20 aromatic ring atoms, which may be substituted by one or more R ³ radicals, or a 5 to an aralkyl or heteroaralkyl group having 20 aromatic ring atoms and optionally substituted by one or more R ³ radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 20 aromatic ring atoms and optionally substituted by one or more R ³ radicals; or a bridging group Q; wherein two or more R radicals together may also form a monocyclic or polycyclic, aliphatic, aromatic and/or benzo-fused ring system.

Preferred alkyl groups having 1 to 10 carbon atoms are shown in the table below:

In a second embodiment of the present invention, at least one structural unit of formula (I) in the polymer of the present invention is characterized in that Ar ³ is substituted with Ar ⁴ at one of two ortho positions, and Ar ³ is additionally linked to Ar ⁴ at a meta position adjacent to the substituted ortho position.

Therefore, in the second embodiment, the structural unit of the formula (I) has the structure of the following formula (Ib):

In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and R can assume the definitions given above,

m = 0, 1, 2, 3 or 4,

n = 0, 1, 2 or 3,

X = CR ₂ , NR, SiR ₂ , O, S, C=O or P=O, preferably CR ₂ , NR, O or S, and

s and t are 0 or 1, respectively, where the sum (s + t) = 1 or 2, preferably 1.

In a preferred embodiment, at least one structural unit of formula (I) is selected from structural units of formulae (II), (III) and (IV):

In the formula, Ar ¹ , Ar ² , Ar ⁴ , and R can assume the definitions given above,

m = 0, 1, 2, 3 or 4,

n = 0, 1, 2 or 3, and

X = CR ₂ , NR, SiR ₂ , O, S, C=O or P=O, preferably CR ₂ , NR, O or S.

In a particularly preferred embodiment, at least one structural unit of formula (II) is selected from structural units of formula (V):

In the formula, Ar ¹ , Ar ² , R and m can assume the definitions given above, and

p = 0, 1, 2, 3, 4 or 5.

Examples of preferred structural units of formula (V) are shown in the table below:

In the formula, Ar ¹ , Ar ² , R, m, n and p can assume the definitions given above, and

k = 0, 1 or 2.

In a further particularly preferred embodiment, at least one structural unit of formula (III) is selected from structural units of formula (VI):

In the formula, Ar ¹ , Ar ² , R, X, m and n can assume the definitions given above.

Examples of preferred structural units of formula (VI) are shown in the table below:

In the formula, Ar ¹ , Ar ² , R, m, n and p can assume the definitions given above.

In a further particularly preferred embodiment, at least one structural unit of formula (IV) is selected from structural units of formula (VII):

In the formula, Ar ¹ , Ar ² , R, X, m and n can assume the definitions given above.

Examples of preferred structural units of formula (VII) are shown in the table below:

In the formula, Ar ¹ , Ar ² , R, m, n and p can assume the definitions given above.

Preferably, Ar ¹ and Ar ² are in each case the same or different and are a monocyclic or polycyclic aromatic or heteroaromatic ring system having 5 to 30, preferably 5 to 24 aromatic ring atoms.

More preferably, Ar ¹ and Ar ² are the same or different at each occurrence and are independently at each occurrence a monocyclic or polycyclic aromatic ring system having 5 to 14 aromatic carbon atoms selected from phenyl, biphenyl, terphenyl, [1,1':3',1'']terphenyl-2'-yl, quaterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzpyrene, fluorene, indene, indenofluorene and spirobifluorene, preferably selected from phenyl and biphenyl, more preferably selected from phenyl.

Furthermore, Ar ¹ and Ar ² are in each case identical or different and are independently substituted in their ortho or meta positions by R ¹ and R ² identically or differently, preferably identically in each case in the ortho or meta position, more preferably identically in the meta position with respect to the bond to the nitrogen atom of the respective chemical formulae.

In a very particularly preferred embodiment, at least one structural unit of formula (V) is selected from structural units of formula (VII):

In the equation, R, R ¹ , R ² , m and p can assume the definitions given above.

Examples of preferred structural units of formula (VIII) are shown in the table below:

In the equation, R, R ¹ , R ² , k, m, n and p can assume the definitions given above.

In a further particularly preferred embodiment, at least one structural unit of formula (VI) is selected from structural units of formula (IX):

In the equation, R, R ¹ , R ² , X, m and n can assume the definitions given above.

Examples of preferred structural units of chemical formula (IX) are shown in the table below:

In the equation, R, R ¹ , R ² , m, n and p can assume the definitions given above, and

v = 1 to 20, preferably 1 to 10.

In a further particularly preferred embodiment, at least one structural unit of formula (VII) is selected from structural units of formula (X):

In the equation, R, R ¹ , R ² , X, m and n can assume the definitions given above.

Examples of preferred structural units of chemical formula (X) are shown in the table below:

In the equation, R, R ¹ , R ² , m and n can assume the definitions given above.

Preferably, R ¹ and R ² are the same or different at each occurrence and are independently at each occurrence a straight-chain alkyl or alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl or alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups may be replaced by RR ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , P(=O)(R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN.

More preferably, R ¹ and R ² are the same or different at each occurrence and are independently at each occurrence a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40, preferably 1 to 20 and more preferably 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40, preferably 3 to 20 and more preferably 3 to 10 carbon atoms.

Examples of preferred structural units -Ar ¹ -N-Ar ² - in chemical formulas (I), (Ia), (Ib) and (II) to (X) are shown in the table below:

When structural units (a) to (c), (e), (i) and (j) are preferred, structural units (a) and (e) are particularly preferred, and structural unit (a) is very particularly preferred.

Examples of particularly preferred structural units of formula (II) are shown in the table below:

When structural units A1 to A11, A14, A15, A18 and A19 are preferred, structural units A1 to A10, A14, A15, A18 and A19 are particularly preferred, and structural units A6, A9 and A18 are very particularly preferred.

In preferred embodiments of formulae (VIII), (IX) and (X), and formulae (VIIIa) to (VIIIh), (IXa) to (IXg) and (Xa) to (Xc), the dashed lines represent bonds to adjacent structural units in the polymer. These can be arranged independently in the ortho, meta or para positions, preferably identically in the ortho, meta or para positions, more preferably in the meta or para positions, and most preferably in the para position.

The proportion of structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer is in the range of 1 to 100 mol%.

In a first preferred embodiment, the polymer of the present invention contains only one structural unit of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X), i.e. its proportion in the polymer is 100 mol%. In this case, the polymer of the present invention is a homopolymer.

In a second preferred embodiment, the proportion of structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer is in the range of 50 to 95 mol%, more preferably in the range of 60 to 95 mol%, based on 100 mol% of all copolymerizable monomers present as structural units in the polymer, i.e. the polymer of the present invention has not only one or more structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X) but also additional structural units other than the structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X).

In a third preferred embodiment, the proportion of structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer is in the range of 5 to 50 mol%, more preferably in the range of 25 to 50 mol%, based on 100 mol% of all copolymerizable monomers present as structural units in the polymer, i.e. the polymer of the present invention has not only one or more structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X), but also additional structural units other than the structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X).

Structural units other than those of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) include those comprehensively disclosed and listed in WO 02/077060 A1 and WO 2005/014689 A2. These are considered to form part of the present invention by reference. Additional structural units may for example come from the following classes:

Group 1: Units affecting the hole injection and/or hole transport properties of the polymer;

Group 2: Units affecting the electron injection and/or electron transport properties of the polymer;

Army 3: Units having a combination of individual units from Army 1 and Army 2;

Group 4: Units that change the emission characteristics in such a way that electrophosphorescence rather than electrofluorescence can be obtained;

Unit 5: Unit improving the transition from singlet to triplet state;

Group 6: Units affecting the emission color of the produced polymer;

Group 7: Units commonly used as polymer backbones;

Group 8: Units affecting the film morphology and/or rheology properties of the produced polymer.

Preferred polymers of the present invention are those in which at least one structural unit has charge transport properties, i.e., those containing units from groups 1 and/or 2.

Structural units from group 1 having hole injection and/or hole transport properties are, for example, triarylamines, benzidines, tetraaryl-para-phenylenediamines, triarylphosphines, phenothiazines, phenoxazines, dihydrophenazines, thianthrenes, dibenzo-para-dioxines, phenoxathiines, carbazoles, azulenes, thiophenes, pyrrole and furan derivatives and further O-, S- or N-containing heterocycles.

Preferred structural units from group 1 are structural units of the following chemical formulas (1a) to (1q):

In the equation, R, k, m and n can assume the definitions given above.

In the chemical formulae (1a) to (1q), the dotted lines represent possible bonds to adjacent structural units in the polymer. If two dotted lines are present in the chemical formula, the structural unit has 1 or 2, preferably 2, bond(s) to the adjacent structural unit. If three dotted lines are present in the chemical formula, the structural unit has 1, 2 or 3, preferably 2, bond(s) to the adjacent structural unit. If four dotted lines are present in the chemical formula, the structural unit has 1, 2, 3 or 4, preferably 2, bond(s) to the adjacent structural unit. These can be arranged independently in the ortho, meta or para positions, identically or differently.

Structural units from group 2 having electron-injecting and/or electron-transporting properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, peryline, benzimidazole, triazine, ketones, phosphine oxide and phenazine derivatives, as well as triarylboranes and further O-, S- or N-containing heterocycles.

The polymer of the present invention may preferably contain units from group 3, wherein the structures that increase hole mobility and increase electron mobility (i.e., units from groups 1 and 2) are directly bonded to each other, or structures that increase both hole mobility and electron mobility are present. Some of these units can act as emitters and shift the emission color to green, yellow or red. Thus, their use is suitable for producing other emission colors from, for example, an originally blue-emitting polymer.

Structural units of group 4 are those which can emit light with high efficiency from the triplet state even at room temperature, i.e. exhibit electrophosphorescence rather than electrofluorescence, which often leads to an increase in energy efficiency. Suitable for this purpose are first of all compounds containing heavy atoms having an atomic number higher than 36. Preferred compounds are those containing d or f transition metals which satisfy the above conditions. Particular preference is given here to corresponding structural units containing elements of groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt). For example, structural units useful in the polymers of the present invention include various complexes as described, for example, in WO 02/068435 A1, WO 02/081488 A1, EP 1239526 A2 and WO 2004/026886 A2. The corresponding monomers are described in WO 02/068435 A1 and WO 2005/042548 A1.

Structural units of group 5 are those which improve the transition from the singlet to the triplet state and, when used in connection with structural elements of group 4, which improve the phosphorescent properties of these structural elements. Useful units for this purpose are in particular carbazole and bridged carbazole dimer units, as described, for example, in WO 2004/070772 A2 and WO 2004/113468 A1. Also useful for this purpose are ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds, as described, for example, in WO 2005/040302 A1.

Structural units of group 6 are those which, in addition to those mentioned above, have at least one additional aromatic structure or other conjugated structure which do not belong to the aforementioned groups, i.e. those which have little influence on the charge carrier mobility, are not organometallic complexes or do not influence the singlet-triplet transition. Structural elements of this kind can influence the emission color of the resulting polymer. Depending on the unit, they can therefore also be used as emitters. Aromatic structures having 6 to 40 carbon atoms or otherwise tolane, stilbene or bisstyrylarylene derivatives are given preference, which may each be substituted by one or more R radicals. Particular preference is given to those comprising 1,4- or 9,10-anthrylene, 1,6-, 2,7- or 4,9-pyrenylene, 3,9- or 3,10-perylenylene, 4,4'-tolanylene, 4,4'-stilbenylene, benzothiadiazole and the corresponding oxygen derivatives, quinoxalines, phenothiazines, phenoxazines, dihydrophenazines, bis(thiophenyl)arylenes, oligo(thiophenylenes), phenazines, rubrenes, pentacenes or perylene derivatives, these being preferably substituted or preferably conjugated push-pull systems (systems substituted by donor and acceptor substituents) or systems such as preferably substituted quinacridones or squarines.

The structural unit of group 7 is a unit containing an aromatic structure having 6 to 40 carbon atoms, and these are commonly used as a polymer backbone. These include, for example, 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9'-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepin derivatives and cis- and trans-indenofluorene derivatives, as well as 1,2-, 1,3- or 1,4-phenylene, 1,2-, 1,3- or 1,4-naphthylene, 2,2'-, 3,3'- or 4,4'-biphenylylene, 2,2"-, 3,3"- or 4,4"-terphenylylene, 2,2'-, 3,3'- or 4,4'-bi-1,1'-naphthylylene or 2,2"'-, 3,3"'- or 4,4"'-quaterphenylylene derivatives.

Preferred structural units from group 7 are structural units of the following chemical formulas (7a) to (7o):

In the equation, R, k, m, n, and p can assume the definitions given above.

In the chemical formulae (7a) to (7o), the dotted lines represent possible bonds to adjacent structural units in the polymer. When two dotted lines are present in the chemical formulae, the structural unit has 1 or 2, preferably 2, bond(s) to the adjacent structural unit. When four or more dotted lines are present in the chemical formulae (chemical formulae (7g), (7h) and (7j)), the structural unit has 1, 2, 3 or 4, preferably 2, bond(s) to the adjacent structural unit. These can be independently arranged in the ortho, meta or para positions, identically or differently.

The structural units of group 8 are those which influence the rheological properties and/or the film morphology of the polymer, for example siloxanes, alkyl chains or fluorinated groups, but are also in particular rigid or flexible units, liquid crystal forming units or crosslinking groups.

At the same time, it is given preference that the polymers of the present invention contain, in addition to structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X), additionally one or more units selected from groups 1 to 8. Likewise, it may be preferred when more than one additional structural unit from one group is present simultaneously.

Here, the polymer of the present invention is given as preferred, which contains not only at least one structural unit of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X), but also a unit from group 7.

Likewise, it is preferred when the polymer of the present invention contains units that improve charge transport or charge injection, i.e., units from Groups 1 and/or 2.

Additionally, it is particularly preferred when the polymer of the present invention contains structural units from group 7 and units from group 1 and/or 2.

The polymer of the present invention is a homopolymer or copolymer of structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X). The polymer of the present invention may be linear or branched, preferably linear. The copolymer of the present invention may contain, in addition to one or more structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X), potentially one or more additional structures from groups 1 to 8 detailed above.

The copolymer of the present invention may have a random, alternating or block structure, or alternatively, may have two or more of these structures alternating. More preferably, the copolymer of the present invention has a random or alternating structure. More preferably, the copolymer is a random or alternating copolymer. The way in which copolymers having a block structure can be obtained and which further structural elements are particularly preferred for this purpose are described in detail, for example, in WO 2005/014688 A2. This is incorporated herein by reference. Likewise, it should be emphasized once again that the polymers in this respect may also have a dendritic structure.

In a further embodiment of the present invention, the polymer of the present invention contains at least one structural unit of the formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X) and optionally further structural units selected from groups 1 to 8 mentioned above, as well as at least one, preferably one, structural unit having a crosslinking group Q.

In the context of the present invention a "crosslinkable Q group" means a functional group which is capable of entering into a reaction to form an insoluble compound. The reaction may be with further identical Q groups, with further different Q groups, or with any other part of the same or another polymer chain. The crosslinkable group is therefore a reactive group. This gives, as a result of the reaction of the crosslinkable group, a correspondingly crosslinked compound. The chemical reaction may also be carried out in layers, thereby generating an insoluble layer. The crosslinking may usually be promoted by UV radiation, microwave radiation, x-radiation or electron beams, optionally in the presence of an initiator, or by heat. "Insoluble" in the context of the present invention preferably means that the polymer of the invention, after the crosslinking reaction, i.e. after the reaction of the crosslinkable group, has a solubility in an organic solvent which is at least a factor of 3, preferably at least a factor of 10, lower at room temperature than the solubility of the corresponding non-crosslinked polymer of the invention in the same organic solvent.

The structural unit having a crosslinkable Q group, in the first embodiment, can be selected from structural units of formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X).

Preferred structural units having a crosslinkable Q group are the following structural units derived from the structural units of formula (Ia) of formulae (XIa1) to (XIa3):

In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R, m, X and r can assume the definitions given above with respect to chemical formula (Ia).

Examples of preferred structural units of formula (XIa) are shown in the table below:

In the equation, R, k, m, n, and p can assume the definitions given above.

In chemical formulas (11a) to (11f), the dotted lines represent possible bonds to adjacent structural units in the polymer. When two dotted lines are present in the chemical formula, the structural unit has one or two, preferably two, bond(s) to the adjacent structural unit.

Additional preferred structural units having a crosslinkable Q group are the following structural units derived from the structural units of formulae (Ib) of formulae (XIb1) to (XI1b4):

In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R n , X, p and q can assume the definitions given above with respect to chemical formula (Ib).

Examples of preferred structural units of chemical formula (XIb) are shown in the table below:

In the equation, R, k, m, n, and p can assume the definitions given above.

In chemical formulae (11g) to (11o), the dotted lines represent possible bonds to adjacent structural units in the polymer. When two dotted lines are present in the chemical formula, the structural unit has one or two, preferably two, bond(s) to the adjacent structural unit.

Additionally, in the second embodiment, the structural unit having a crosslinkable Q group can be selected from the structural units disclosed in Groups 1 to 8.

A preferred structural unit having a crosslinkable Q group is the following structural unit derived from a triarylamine unit of group 1 of formula (XII):

In the formula, Ar ¹ , Ar ² , and Ar ³ may assume the definitions given above with respect to chemical formula (I).

Examples of preferred structural units of formula (XII) are shown in the table below:

Additional preferred structural units having a crosslinkable Q group are the following structural units derived from group 7 of formula (XIII):

In the formula, Ar ¹ can assume the definition given with respect to the structural unit of chemical formula (I).

Examples of preferred structural units of formula (XIII) are shown in the table below:

As explained above, a crosslinking Q group means a functional group which is capable of entering into a chemical reaction to form an insoluble polymeric compound. It is generally possible to use any Q group known to the skilled person for the purpose. The specific function of this group is to link the polymeric compound of the invention, optionally with a further reactive polymeric compound, to one another by a crosslinking reaction. This leads to a crosslinked compound, or, when the reaction is carried out in a layer, to a crosslinked layer. A crosslinked layer in the context of the present invention is understood to mean a layer obtainable by carrying out a crosslinking reaction from a layer of a crosslinkable polymeric compound of the invention. The crosslinking reaction can generally be initiated by heat and/or by UV radiation, microwave radiation, x-radiation or electron beams and/or by the use of free radical formers, anions, cations, acids and/or photoacids. The presence of a catalyst may likewise be advisable or necessary. Preferably, the crosslinking reaction is a reaction which does not require the addition of an initiator and a catalyst.

According to the present invention, preferred crosslinking Q groups are the following groups:

a) Terminal or cyclic alkenyl or terminal dienyl and alkynyl groups:

Suitable units are units containing a terminal or cyclic double bond, a terminal dienyl group or a terminal triple bond, in particular a terminal or cyclic alkenyl, terminal dienyl or terminal alkynyl group having 2 to 40 carbon atoms, preferably 2 to 10 carbon atoms, wherein individual CH ₂ groups and/or individual hydrogen atoms may also be replaced by the R groups mentioned above. Groups which are to be regarded as precursors and which are capable of in situ formation of double or triple bonds are additionally suitable.

b) Alkenyloxy, dienyloxy or alkynyloxy group:

Additionally, an alkenyloxy, dienyloxy or alkynyloxy group, preferably an alkenyloxy group, is suitable.

c) Acrylic acid group:

Additionally, acrylic acid units in the broadest sense are suitable, preferably acrylic esters, acrylamides, methacrylic esters and methacrylamides. C _1-10 -alkyl acrylates and C _1-10 -alkyl methacrylates are particularly preferred.

The crosslinking reactions of the groups mentioned above under a) to c) can be carried out via free radical, cationic or anionic mechanisms or else via cycloaddition.

It may be advisable to add a suitable initiator to 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, AlCl ₃ , BF ₃ , triphenylmethyl perchlorate or tropylium hexachloroantimonate. Suitable initiators for anionic crosslinking are bases, in particular butyllithium.

However, in a preferred embodiment of the present invention, crosslinking is performed without the addition of an initiator and is initiated solely by thermal means. This is preferred because the absence of an initiator prevents contamination of the layer, which could deteriorate device properties.

d) Oxetane and oxirane:

An additional suitable class of crosslinking groups Q is that of oxetanes and oxiranes that crosslink cationically via ring opening.

It may be advisable to add a suitable initiator to the crosslinking reaction. Suitable initiators are, for example, AlCl ₃ , BF ₃ , triphenylmethyl perchlorate or tropylium hexachloroantimonate. Likewise, it is possible to add a mineral acid as an initiator.

e) Silane:

Additionally suitable as a class of crosslinking groups are silane groups SiR ₃ , wherein at least two R groups, and preferably all three R groups, are Cl or alkoxy groups having 1 to 20 carbon atoms. These groups react in the presence of water to give oligo- or polysiloxanes.

f) Cyclobutane group

The crosslinking Q groups mentioned above are generally known to those skilled in the art, as are suitable reaction conditions used for the reaction of these groups.

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

In the chemical formulae Q1 to Q8 and Q11, the R ¹¹ , R ¹² and R ¹³ radicals are in each case the same or different and are H or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, the R ¹¹ , R ¹² and R ¹³ radicals are H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and most preferably H or methyl. The indices used have the following definitions: s = 0 to 8; and t = 1 to 8.

The dotted bonds in chemical formulas Q1 to Q11 and the dotted bonds in chemical formula Q12 represent the connections of crosslinking groups to structural units.

The crosslinking groups of the chemical formulae Q1 to Q12 may be linked directly, or otherwise indirectly, to the structural unit via an additional monocyclic or polycyclic aromatic or heteroaromatic ring system Ar ¹⁰ as shown in the chemical formulae Q13 to Q24 below:

Here, Ar ¹⁰ in chemical formulas Q13 to Q24 can be assumed to have the same definition as Ar ¹ .

Particularly desirable crosslinking groups Q are:

The R ¹¹ and R ¹² radicals in the formulae Q7a and Q13a to Q19a are, in each case, the same or different, and are H or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, the R ¹¹ and R ¹² radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and most preferably methyl.

The R ¹³ radical in the formulae Q7b and Q19b is in each case a straight-chain or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, the R ¹³ radical is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and most preferably methyl.

The indices used have the following definitions: s = 0 to 8; and t = 1 to 8.

Very particularly desirable crosslinking groups Q are:

In the preferred groups Q1 to Q24, particularly preferred groups Q1a to Q24a and very particularly preferred groups Q1b to Q24c, the dotted lines represent bonds to the structural unit. In this regard, it should be noted that the groups Q12, Q12a, Q12b and Q24 each have two bonds to two adjacent ring carbon atoms in the structural unit. All other crosslinking groups have only one bond to the structural unit.

The proportion of the crosslinkable structural unit in the polymer is in the range of 0.01 to 50 mol%, preferably in the range of 0.1 to 30 mol%, more preferably in the range of 0.5 to 25 mol%, and most preferably in the range of 1 to 20 mol%, based on 100 mol% of all copolymerizable monomers present as structural units in the polymer.

The polymers of the invention containing structural units of the formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and/or (XI) are generally prepared by polymerization of one or more monomer types, wherein at least one monomer leads to the structural units of the formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and/or (XI) in the polymer. Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions leading to C-C and C-N couplings are:

(A) SUZUKI polymerization;

(B) YAMAMOTO polymerization;

(C) STILLE polymerization;

(D) HECK polymerization;

(E) NEGISHI polymerization;

(F) SONOGASHIRA polymerization;

(G) HIYAMA polymerization; and

(H) HARTWIG-BUCHWALD polymerization.

The ways in which polymerization can be carried out by these methods and in which the polymer can subsequently be separated and purified from the reaction medium are known to the person skilled in the art and are 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 coupling is preferably selected from the group of Suzuki coupling, Yamamoto coupling and Stille coupling; the C-N coupling is preferably a coupling according to Hartwig-Buchwald.

Accordingly, the present invention also provides a process for producing the polymer of the present invention, characterized in that the polymer is produced by Suzuki polymerization, Yamamoto polymerization, Stille polymerization or Hartwig-Buchwald polymerization.

The synthesis of the polymer of the present invention requires the corresponding monomer of the chemical formula (MI),

In the formula, Ar ¹ , Ar ² and Ar ³ can assume the definitions given with respect to the structural unit of chemical formula (I).

The monomers of the formula (MI) which lead to the structural unit of the formula (I) in the polymer of the present invention are compounds which have suitable functionality and corresponding substitutions at two positions which allow incorporation of this monomer unit into the polymer. Accordingly, these monomers of the formula (MI) likewise form part of the claimed subject matter of the present invention. The Y groups are identical or different and are leaving groups which are suitable for the polymerization reaction, so that incorporation of the monomer unit into the polymeric compound is possible. Preferably, Y is identical or different and is a chemical functional group selected from the classes of halogen, O-tosylate, O-triflate, O-sulfonate, boric acid ester, partially fluorinated silyl groups, diazonium groups and organotin compounds.

The basic structure of the monomeric compounds can be functionalized by standard methods, for example by Friedel-Crafts alkylation or acylation. Additionally, the basic skeleton can be halogenated by standard methods in organic chemistry. The halogenated compounds can optionally be further converted in additional functionalization steps. For example, the halogenated compounds can be used directly or after conversion into boronic acid derivatives or organotin derivatives as starting materials for conversion into polymers, oligomers or dendrimers.

The above method is merely a selection from reactions known to those skilled in the art who can use them to synthesize the compounds of the present invention, without exercising the techniques of the present invention.

The polymers of the invention can be used as neat substances, or else as mixtures with optionally further polymeric, oligomeric, resinous or low molecular weight substances. Low molecular weight substances are understood in the present invention to mean compounds having a molecular weight in the range from 100 to 3000 g/mol, preferably from 200 to 2000 g/mol. These further substances can, for example, improve the electronic properties or emit them themselves. Mixtures are referred to above and below as mixtures comprising at least one polymeric component. In this way, it is possible to produce at least one polymer layer consisting of a mixture (blend) of at least one polymer of the invention having structural units of the formulae (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and/or (X) and optionally at least one further polymer and at least one low molecular weight substance.

Accordingly, the present invention also provides a polymer blend comprising one or more polymers of the present invention and one or more additional polymeric, oligomeric, resinous and/or low molecular weight materials.

The present invention also provides solutions and formulations comprising one or more polymers or polymer blends of the present invention in one or more solvents. The manner in which such solutions can be prepared is known to those skilled in the art and is described, for example, in WO 02/072714 A1, WO 03/019694 A2 and the references cited therein.

These solutions can be used to produce thin polymer layers, for example, by surface coating methods (e.g., spin coating) or by printing methods (e.g., inkjet printing).

Polymers containing structural units having crosslinkable Q groups are particularly suitable for the production of films or coatings, in particular for the production of structured coatings, for example by thermally or photo-induced in situ polymerization and in situ crosslinking, for example by in situ UV photopolymerization or photopatterning. Here, it is possible to use the corresponding polymers in pure form, or else 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 described processes are described, for example, in WO 2005/083812 A2. Possible binders are, for example, polystyrene, polycarbonate, poly(meth)acrylates, polyacrylates, polyvinyl butyral and similar optoelectronically neutral polymers.

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, (-)-phenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, 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 a mixture of these solvents.

Therefore, the present invention also provides the use of a polymer containing a structural unit having a crosslinkable Q group for the production of a crosslinked polymer. More preferably, the crosslinkable group, which is a vinyl group or an alkenyl group, is incorporated into the polymer by a WITTIG reaction or a WITTIG type reaction. When the crosslinkable group is a vinyl group or an alkenyl group, the crosslinking can take place via a free radical or ionic polymerization which can be induced thermally or radiation-induced. Preferably, a free radical polymerization which is induced thermally at a temperature of less than 250° C., more preferably at a temperature of less than 230° C., is preferred.

Optionally, during the crosslinking process, additional styrene monomer is added to achieve a higher degree of crosslinking. Preferably, the proportion of the added styrene monomer is in the range of 0.01 to 50 mol%, more preferably 0.1 to 30 mol%, based on 100 mol% of all copolymerization monomers present as structural units in the polymer.

Accordingly, the present invention also provides a process for preparing a crosslinked polymer, comprising the following steps:

(a) providing a polymer containing a structural unit having at least one crosslinkable Q group; and

(b) a free radical or ionic crosslinking step, preferably a free radical crosslinking step, which can be induced either thermally or radiation-induced, preferably thermally.

The crosslinked polymers produced by the process of the present invention are insoluble in all standard solvents. In this way, it is possible to produce defined layer thicknesses that are not dissolved or partially dissolved even by the application of subsequent layers.

Therefore, the present invention also relates to a crosslinked polymer obtainable by the above-mentioned process. The crosslinked polymer is preferably prepared in the form of a crosslinked polymer layer - as described above. Due to the insolubility of the crosslinked polymer in all solvents, an additional layer can be applied to the surface of this crosslinked polymer layer from a solvent by the above-mentioned technique.

The present invention also encompasses what are called hybrid devices, which can produce one or more layers processed from solution and one or more layers produced by deposition of low molecular weight materials.

The polymer of the present invention can be used in electronic or optoelectronic devices, or for the manufacture thereof.

Therefore, the present invention also provides the use of the polymer of the present invention in electronic or optoelectronic devices, preferably in organic electroluminescent devices (OLEDs), 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 or organic photoreceptors (OPCs), more preferably in organic electroluminescent devices (OLEDs).

For the above-mentioned hybrid devices, in relation to organic electroluminescent devices, reference is made to a combined PLED/SMOLED (polymeric light-emitting diode/small molecule organic light-emitting diode) system.

The way in which OLEDs can be manufactured is known to the person skilled in the art and is described in detail as a general process in WO 2004/070772 A2, which has to be suitably adapted to the individual case.

As described above, the polymer of the present invention is particularly suitable as an electroluminescent material in OLEDs or displays manufactured in this manner.

In the context of the present invention, an electroluminescent material is considered to mean a material which may find use as an active layer. By "active layer" is meant a layer which is capable of emitting light upon application of an electric field (emissive layer) and/or which improves injection and/or transport of positive and/or negative charges (charge injection or charge transport layer).

Therefore, the present invention also preferably provides the use of the polymer of the present invention in OLEDs, in particular as electroluminescent materials.

The present invention also provides electronic or optoelectronic components, preferably organic electroluminescent devices (OLEDs), 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), more preferably organic electroluminescent devices, which have at least one active layer, at least one of which comprises at least one polymer of the present invention. The active layer can be, for example, an emitting layer, a charge transport layer and/or a charge injection layer.

In the present specification and also in the examples that follow, the primary object is the use of the polymers of the present invention in connection with OLEDs and corresponding displays. Notwithstanding the limitations of this description, it is possible for one skilled in the art to utilize the polymers of the present invention as semiconductors for further described uses in other electronic devices, without further exercising the skills of the invention.

The following examples are intended to illustrate, but not limit, the invention. In particular, the features, properties and advantages described herein with respect to the defined compounds forming the basis of the embodiments are also applicable to other compounds covered by the scope of protection of the claims, although not specifically mentioned, unless the contrary is explicitly stated otherwise.

Examples:

Part A: Synthesis of Monomers

All syntheses are performed in an argon atmosphere and dry solvents unless otherwise stated.

A1 Preparation of precursor of monomer of the present invention

A1.1 Preparation of Precursor Int-1

30 g (0.18 mmol) of [1,1`-Biphenyl]-2-amine, 63.7 g (0.37 mmol) of m -bromotoluene and 51.1 g (0.53 mmol) of sodium tert-butoxide are dissolved in 600 ml of toluene. After addition of 1.99 g (8.9 mmol) of palladium acetate and 17.7 ml (17.7 mmol) of tri-tert-butylphosphine (1 M in toluene), the reaction mixture is refluxed. After 16 h, the reaction mixture is allowed to cool to room temperature and 300 ml of water are added. The phases formed are separated, the aqueous phase is extracted once with toluene (200 ml), the organic phase is washed twice with water, the combined organic phases are washed with water (2 x 250 ml), dried over magnesium sulfate and concentrated on a rotary evaporator. The residue is filtered through silica gel (eluent: heptane) and the product is crystallized from ethanol.

Yield: 31 g (0.09 mmol, 50% of theory)

The following precursors can be prepared similarly to Example A1.1:

A2. Preparation of the monomer of the present invention

A2.1 Preparation of monomer Inv-Mon-Br-1

Int-1 31.0 g (0.09 mmol) is dissolved in 350 ml of THF and cooled to 0°C. N-bromosuccinimide 31.4 g (176 mmol) is added in portions, and the mixture is gradually cooled to room temperature and stirred for 16 hours. The reaction mixture is then concentrated, heptane is added, and extraction stirring is performed while cooling with ice. The resulting solid is suction filtered, and the filtrate is concentrated. Purification is performed by repeated crystallization from ethanol to a purity of >99.5% (GC-MS).

Yield: 26.3 g (0.05 mol, 60%)

The following monomers can be prepared similarly to Inv-Mon-Br-1:

A3 Additional Monomer

Additional monomers for the preparation of the comparative polymers and the polymers of the present invention are already described in the prior art, are commercially available or prepared by literature methods and are summarized in Table 1 below:

Table 1

Part B: Synthesis of Polymers

Preparation of comparative polymers V-HTL1 and V-HTL2 and polymers HTL1, HTL2, HTL3 and HTL4 of the present invention

The comparative polymers V-HTL1 and V-HTL2 and the polymers HTL1, HTL2, HTL3 and HTL4 of the present invention are prepared from the corresponding monomers by Suzuki coupling according to the process described in WO 2003/048225 A2.

For polymerization, the monomers are used in the percentage ratios of mol% as specified in Table 2. The polymers V-HTL1, V-HTL2, HTL1, HTL2, HTL3 and HTL4 prepared in this manner contain, after removal of the leaving group, the structural units in the percentages (percentage = mol%) reported in Table 2.

For monomers having aldehyde groups, these are converted into crosslinkable vinyl groups after polymerization by the WITTIG reaction by the process described in WO 2010/097155 A1. Accordingly, the polymers listed in Table 2 and used in Part C have crosslinkable vinyl groups rather than the originally present aldehyde groups.

The palladium and bromine contents of the polymer were determined by ICP-MS. The determined values are less than 10 ppm.

Molecular weight M _w and polydispersity D determined by gel permeation chromatography (GPC) (Model: Agilent HPLC system series 1100) (column: PL-RapidH from Polymer Laboratories; solvent: THF with 0.12 vol% o-dichlorobenzene; detection: UV and refractive index; temperature: 40°C). Calibration is performed with polystyrene standards.

The composition of the polymer is given in Table 2 below:

Table 2

Part C: Manufacturing OLEDs

There are already many descriptions of the production of solution-based OLEDs in the literature, for example in WO 2004/037887 A2 and WO 2010/097155 A1. The processes match the situations described below (variations in materials, layer thicknesses).

The material combination of the present invention is used in the following layer sequence:

- Substrate,

- ITO (50 nm),

- Hole injection layer (HIL) (25 nm),

- Hole transport layer (HTL) (20 nm),

- Emissive layer (EML) (60 nm),

- Hole blocking layer (HBL) (10 nm)

- Electron transport layer (ETL) (40 nm),

- Electron injection layer (EIL) (1 nm)

- Cathode (Al) (100 nm).

The substrate used is a glass plate coated with a structured ITO (indium tin oxide) having a thickness of 50 nm. The hole injection layer is applied by spin-coating in an inert atmosphere. For this purpose, a hole-transporting crosslinking polymer and a p-doping salt are dissolved in toluene. The corresponding materials are described, inter alia, in WO 2016/107668 A1, WO 2013/081052 A1 and EP 2325190 A1. For the resulting layer thickness of 25 nm, a solids content of 6 mg/ml is used. Subsequently, the layer is baked on a hotplate at 210° C. for 30 minutes in an inert gas atmosphere.

Afterwards, hole transport and emission layers are applied to these coated substrates.

The hole transport layers used are the compounds of the present invention and the comparative compounds, each dissolved in toluene. The solid content of these solutions is 5 mg/ml, since a layer thickness of 20 nm should be achieved by spin-coating. The layers are spun on in an inert gas atmosphere and baked on a hot plate at 220°C for 30 minutes.

The materials used in this case are shown in Table 2 below, and the monomers used therein are shown in Table 1 below.

The emitting layer consists of host material H1, host material H2 and emitting dopant D1. The materials are present in the emitting layer in a weight ratio of 45% H1, 36% H2 and 19% D1. The mixture for the emitting layer is dissolved in toluene. The solids content of this solution is 19 mg/ml, since a layer thickness of 60 nm has to be achieved by spin-coating. The layers are spun on in an inert gas atmosphere and baked at 150°C for 10 minutes.

Table 3: Structural formulas of materials used in EML

Materials for the hole blocking, electron transport and electron injection layers are applied by thermal vapor deposition in a vacuum chamber and are shown in Table 4. The hole blocking layer is made of ETM1. The electron transport layer is made of two materials, ETM1 and ETM2, which are blended by co-evaporation at a volume ratio of 50% each. The hole injection layer is made of ETM2.

Table 4: HBL and ETL used

The cathode is formed by thermal evaporation of a 100 nm thick aluminum layer.

OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current-voltage-luminance characteristic (IUL characteristic) assuming a Lambertian radiation charateristic and the (operating) lifetime are determined. The IUL characteristic is used to determine parameters, e.g. the external quantum efficiency (in %) at a certain brightness. LD80 @ 1000 cd/m² is the lifetime of an OLED given a starting brightness of 1000 cd/m² until it drops to 80% of the starting intensity, i.e. to 800 cd/m².

The properties of various OLEDs are contrasted in Table 5. Examples V01 and V02 are comparative examples. Example C1 shows the properties of OLEDs having the material combination of the present invention, and the energy gap of individual HTL polymers. Green emitting OLEDs comprising the materials of the present invention as HTLs are fabricated.

The energy gap of individual polymers is determined by the absorption spectrum on their neat films. For this purpose, neat films of the polymers are prepared on quartz glass. For this purpose, the polymers are dissolved in toluene at a concentration of 15 mg/ml and processed into films of 50 nm thickness by spin coating. This is baked at 220°C for 30 minutes under an inert gas atmosphere.

Absorption measurements are performed on a Perkin Elmer Lambda 850 UV-VIS spectrometer. The flanks of the absorption spectrum are used to determine the energy gap (see Figure 1). Likewise, the results are shown in Table 5.

As shown in Table 5, the polymer of the present invention (i.e., HTL1) results in an energy gap between the polymers in which conjugation is interrupted (i.e., V-HTL2) and the conjugated polymer (i.e., V-HTL1). In addition, an improvement in OLED with respect to efficiency for the conjugated polymer and an improvement in lifetime for the polymer in which conjugation is interrupted can be observed.

Table 5: OLED characteristics

Claims (22)

A polymer having at least one structural unit of the following chemical formula (I):

During the meal
Ar ¹ to Ar ³ are in each case the same or different and are a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, and Ar ³ may be substituted with one or more R radicals;
R is in each case the same or different and is H, D, F, Cl, Br, I, N(R ³ ) ₂ , CN, NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , C(=O)R ³ , P(=O)(R ³ ) ₂ , S(=O)R ³ , S(=O) ₂ R ³ , OSO ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups are R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , P(=O)(R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN), or a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may be substituted by one or more R ³ radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R ³ radicals, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R ³ radicals, or a diarylamino group, a diheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more R ³ radicals or an arylheteroarylamino group; or a bridging group Q, wherein two or more R radicals may also be taken together to form a monocyclic or polycyclic, aliphatic, aromatic and/or benzo fused ring system;
R ³ is in each case the same or different and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, an aromatic and/or heteroaromatic hydrocarbyl radical having 5 to 20 carbon atoms, wherein one or more hydrogen atoms may also be replaced by F; wherein two or more R ³ substituents together may also form a monocyclic or polycyclic, aliphatic or aromatic ring system; and
Dotted lines represent bonds to adjacent structural units in the polymer;
Ar ¹ is substituted by a R ¹ radical and/or Ar ² is substituted by a R ² radical. It is characterized by being substituted, where
R ¹ and R ² are each independently the same or different at each occurrence and are F, Cl, Br, I, N(R ³ ) ₂ , CN, NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , C(=O)R ³ , P(=O)(R ³ ) ₂ , S(=O)R ³ , S(=O) ₂ R ³ , OSO ₂ R ³ , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms which may be substituted by one or more R ³ radicals at each occurrence, wherein one or more non-adjacent CH ₂ groups are R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , P(=O)(R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN. In paragraph 1,
Ar ¹ is substituted by the R ¹ radical and Ar ² is substituted by the R ² radical. A polymer characterized by being substituted. In claim 1 or 2,
A polymer characterized in that Ar ³ is substituted by Ar ⁴ at least in one of the two ortho positions, and preferably in one, wherein Ar ⁴ is a monocyclic or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R radicals. In one or more of claims 1 to 3,
At least one structural unit of the above formula (I) is selected from the structural units of the following formula (Ia):

In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and R may assume the definitions given in clauses 1 and 3,
q = 0, 1, 2, 3, 4, 5 or 6,
X = CR ₂ , NR, SiR ₂ , O, S, C=O or P=O, and
A polymer characterized in that r = 0 or 1. In one or more of claims 1 to 4,
A polymer characterized in that Ar ³ is substituted with Ar ⁴ at one of two ortho positions, and Ar ³ is additionally linked to Ar ⁴ at a meta position adjacent to the substituted ortho position. In one or more of claims 1 to 5,
At least one structural unit of the above formula (I) is selected from the structural units of the following formula (Ib):

In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R and X may assume the definitions given in clauses 1, 3 and 4,
m = 0, 1, 2, 3 or 4, and
n = 0, 1, 2 or 3, and
A polymer characterized in that s and t are each 0 or 1, and the sum of (s + t) is 1 or 2. In one or more of claims 1 to 6,
At least one structural unit of the above formula (I) is selected from structural units of the following formulas (II), (III) and (IV):

A polymer characterized in that Ar ¹ , Ar ² , Ar ⁴ , R, m, n and X in the formula can assume the definitions given in clauses 1, 3, 4 and 6. In paragraph 7,
At least one structural unit of the above chemical formula (II) is selected from the structural units of the following chemical formula (V):

In the formula, Ar ¹ , Ar ² , R and m may assume the definitions given in clauses 1 and 6, and
A polymer characterized in that p = 0, 1, 2, 3, 4 or 5. In paragraph 7,
At least one structural unit of the above chemical formula (III) is selected from the structural units of the following chemical formula (VI):

A polymer characterized in that in the formula, Ar ¹ , Ar ² , R, m and n can assume the definitions given in clauses 1 and 6. In paragraph 7,
At least one structural unit of the above chemical formula (IV) is selected from the structural units of the following chemical formula (VII):

A polymer characterized in that Ar ¹ , Ar ² , R, m, n and X in the formula can assume the definitions given in claims 1 and 6. In one or more of claims 1 to 10,
A polymer characterized in that Ar ¹ and Ar ² are in each case the same or different and are a monocyclic or polycyclic aromatic or heteroaromatic ring system having 5 to 30, preferably 5 to 24 aromatic ring atoms. In one or more of claims 1 to 11,
A polymer characterized in that Ar ¹ and Ar ² are the same or different in each case and are each independently selected from phenyl, biphenyl, terphenyl, [1,1':3',1'']terphenyl-2'-yl, quaterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzpyrene, fluorene, indene, indenofluorene and spirobifluorene, preferably selected from phenyl and biphenyl, more preferably selected from phenyl, and are a monocyclic or polycyclic aromatic ring system having 5 to 14 aromatic carbon atoms. In one or more of claims 1 to 12,
A polymer characterized in that Ar ¹ and Ar ² are in each case identical or different and are independently substituted in their ortho or meta positions by R ¹ and R ² identically or differently, preferably identically in each case in the ortho or meta position, more preferably identically in the meta position with respect to the bond to the nitrogen atom of the general formula (I). In one or more of claims 1 to 13,
A polymer characterized in that R ¹ and R ² are the same or different in each case and are independently in each case a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups may be replaced by R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , C=O, C=S, C=NR ³ , P(=O)(R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ , and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN. In one or more of claims 1 to 14,
A polymer characterized in that R ¹ and R ² are in each case the same or different and in each case independently represent a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40, preferably 1 to 20 and more preferably 1 to 10 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40, preferably 3 to 20 and more preferably 3 to 10 carbon atoms. In one or more of claims 1 to 15,
A polymer characterized in that the proportion of the structural unit of chemical formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII) in the polymer is in the range of 50 to 95 mol% based on 100 mol% of all copolymerizable monomers present as structural units in the polymer. In one or more of claims 1 to 16,
A polymer characterized in that the polymer has, in addition to the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII), an additional structural unit other than the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII). A process for producing a polymer as described in one or more of claims 1 to 17,
A process for producing a polymer, characterized in that the polymer is produced by Suzuki polymerization, Yamamoto polymerization, Stille polymerization or Hartwig-Buchwald polymerization. A polymer blend comprising at least one polymer as defined in one or more of claims 1 to 17 containing at least one structural unit of formula (I) and at least one additional polymeric, oligomeric, resinous and/or low molecular weight material. A solution or formulation comprising a polymer blend as described in claim 19 or one or more polymers as described in one or more of claims 1 to 17 in one or more solvents. Use of a polymer as claimed in one or more of claims 1 to 17 in an electronic or optoelectronic device, preferably in an organic electroluminescent device (OLED), an organic light-emitting electrochemical cell (OLEC), an organic field-effect transistor (OFET), an organic integrated circuit (O-IC), an organic thin-film transistor (TFT), an organic solar cell (O-SC), an organic laser diode (O-laser), an organic photovoltaic (OPV) element or device or an organic photoreceptor (OPC), more preferably in an organic electroluminescent device (OLED). An electronic or optoelectronic device, preferably an organic electroluminescent device (OLED), an organic light-emitting electrochemical cell (OLEC), an organic field-effect transistor (OFET), an organic integrated circuit (O-IC), an organic thin-film transistor (TFT), an organic solar cell (O-SC), an organic laser diode (O-laser), an organic photovoltaic (OPV) element or device or an organic photoreceptor (OPC), more preferably an organic electroluminescent device, having one or more active layers, at least one of which comprises one or more polymers as described in one or more of claims 1 to 17.