Polymers containing specifically substituted triarylamine units and electroluminescent devices containing same

Abstract

The present invention relates to polymers containing specific substituted triarylamine repeat units, to a method for the production thereof, and to the use thereof in electronic devices, in particular in organic electroluminescent devices, called OLEDs (OLED = Organic Light Emitting Diode). The invention also relates to an organic electroluminescent device containing the polymer.

Description

[0001] The present invention relates to polymers containing specifically substituted repeating triarylamine units, to processes for preparing them, and to their use in electronic or optoelectronic devices, in particular in organic electroluminescent devices known as OLEDs (OLED=organic light emitting diodes). The invention furthermore relates to organic electroluminescent devices comprising these polymers.

[0002] In electronic or optoelectronic devices, in particular in organic electroluminescent devices (OLEDs), components with different functions are required. In OLEDs, the different functions are usually present in different layers. In this case, reference is made to multilayer OLED systems. The layers in these multilayer OLED systems include charge injection layers, such as electron injection layers and hole injection layers, charge transport layers, such as electron conductive layers and hole conductive layers, and layers containing luminescent components. These multilayer OLED systems are usually manufactured by applying layer by layer in sequence.

[0003] If two or more layers are applied from solution, it must be ensured that any layer already applied, once dried, is not destroyed by the solution subsequently applied to make the next layer. This can be achieved, for example, by rendering the layer insoluble, for example by cross-linking. Methods of this type are disclosed, for example, in EP 0637899 and WO 96 / 20253.

[0004] Furthermore, it is necessary to match the functions of the individual layers to one another in terms of materials in order to achieve very good results, for example in terms of lifetime, efficiency, etc. For example, in particular the layers directly adjacent to the emitting layer, in particular the hole-transporting layer (HTL=hole transport layer), have a significant influence on the properties of the adjacent emitting layer.

[0005] One of the problems addressed by the present invention was therefore to provide compounds which, firstly, can be processed from solution and, secondly, when used in electronic or optoelectronic components, preferably in OLEDs, here in particular in their hole-transport layers, lead to an improvement in the properties of the components, i.e. in particular the properties of OLEDs.

[0006] It has surprisingly been found that polymers having repeating triarylamine groups and in which at least one aryl group, preferably two aryl groups, arranged in the main chain are substituted, in particular in the case of use in the hole-transporting layer of an OLED, lead to an increase in the energy gap compared to comparable conjugated polymers due to the distortion caused by the substituents and to a reduction in the energy gap compared to comparable polymers with interrupted conjugation. Furthermore, the polymers according to the invention, when used in OLEDs, lead to an improvement in efficiency compared to comparable conjugated polymers and to an improvement in lifetime compared to comparable polymers with interrupted conjugation.

[0007] Therefore, the present application provides a polymer having at least one structural unit of the following formula (I):

[0008]

[0009] in

[0010] Ar 1 To Ar 3 are in each case identical or different and are monocyclic or polycyclic aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, wherein Ar 3 may be substituted with one or more R groups;

[0011] R is identical or different in each case and is H, D, F, Cl, Br, I, N (R 3 )2,CN,NO2,Si(R 3 )3,B(OR 3 )2,C(=O)R 3 , P(=O)(R 3 )2,S(=O)R 3 , S(=O)2R 3 ,OSO2R 3 , a linear 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 replaced by one or more R 3 group, wherein one or more non-adjacent CH2 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、SO2、NR 3 , O, S or CONR 3 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, or having 5 to 60 aromatic ring atoms and in each case by one or more R 3 A monocyclic or polycyclic aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 3 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and substituted by one or more R 3 an aralkyl or heteroaralkyl group substituted with a group, or having 10 to 40 aromatic ring atoms and which may be replaced by one or more R 3a diarylamino group, a diheteroarylamino group or an arylheteroarylamino group substituted with a radical; or a crosslinkable group Q, wherein two or more R groups together can also form a monocyclic or polycyclic aliphatic, aromatic and / or benzo-fused ring system;

[0012] R 3 are in each case identical or different and are H, D, F, or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, an aromatic and / or heteroaromatic hydrocarbon radical having 5 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; in which two or more R 3 The substituents together may also form a monocyclic or polycyclic aliphatic or aromatic ring system; and

[0013] Dashed lines represent bonds connecting adjacent structural units in the polymer;

[0014] It is characterized in that Ar 1 By R 1 Group substitution and / or Ar 2 By R 2 Group substitution, where

[0015] R 1 and R 2 are independently identical or different at each occurrence and are F, Cl, Br, I, N(R 3 )2,CN,NO2,Si(R 3 )3,B(OR 3 )2,C(=O)R 3 , P(=O)(R 3 )2,S(=O)R 3 , S(=O)2R 3 ,OSO2R 3 , having 1 to 40 carbon atoms and in each case may be replaced by one or more R 3 A straight-chain alkyl, alkoxy or thioalkoxy group substituted with a radical or having 3 to 40 carbon atoms and in each case being substituted with one or more R 3 A branched or cyclic alkyl, alkoxy or thioalkoxy group substituted by a group, wherein one or more non-adjacent CH2 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、SO2、NR 3 , O, S or CONR 3 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN.

[0016] Preferably, Ar 1 By R 1 Group Substitution and Ar 2 By R 2 Group substitution.

[0017] More preferably, Ar 3 At least one of the two ortho positions, preferably one of the two ortho positions, is replaced by Ar 4 Substituted, where Ar 4 R 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 groups.

[0018] Ar 4 X may be directly, ie via a single bond, or alternatively via a linker group to Ar 3 connect.

[0019] Therefore, in a first embodiment, the structural unit of formula (I) has the structure of the following formula (Ia):

[0020]

[0021] in

[0022] Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and R may have the definitions given above,

[0023] q=0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4,

[0024] X═CR2, NR, SiR2, O, S, C═O or P═O, preferably CR2, NR, O or S,

[0025] and

[0026] r=0 or 1, preferably 0.

[0027] In the present application, the term "polymer" is understood to mean polymeric compounds, oligomeric compounds and dendrimers. The polymeric compounds of the invention preferably have 10 to 10000, more preferably 10 to 5000, most preferably 10 to 2000 structural units (i.e. repeating units). The oligomeric compounds of the 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).

[0028] The polymers according to the invention preferably have a molecular weight M in the range from 1000 to 2000000 g / mol. w, more preferably a molecular weight M in the range of 10000 to 1500000 g / mol w , most preferably a molecular weight M in the range of 50,000 to 1,000,000 g / mol w The molecular weight M was determined by means of GPC (=gel permeation chromatography) relative to an internal polystyrene standard. w .

[0029] The polymer of the present invention is a conjugated, semi-conjugated or non-conjugated polymer, preferably a conjugated or semi-conjugated polymer.

[0030] According to the present invention, the structural units of formula (I) and (Ia) can be introduced into the main chain or side chain of the polymer. However, it is preferred that the structural units of formula (I) and (Ia) are introduced into the main chain of the polymer. In the case of introduction into the side chain of the polymer, the structural units of formula (I) and (Ia) may be monovalent or divalent, which means that they have one or two bonds connected to adjacent structural units in the polymer.

[0031] In the context of this application, a "conjugated polymer" is a polymer that contains mainly sp 2 Polymers of hybridized (or optionally additionally sp hybridized) carbon atoms which may also be replaced by correspondingly hybridized heteroatoms. In the simplest case, this means the alternating presence of double bonds and single bonds in the main chain, but in the context of the present application, for example, polymers with units such as meta-bonded phenylene groups are also to be regarded as conjugated polymers. "Predominantly" means that naturally (arbitrarily) occurring effects leading to interruption of conjugation do not invalidate the term "conjugated polymer". Conjugated polymers are likewise regarded as polymers with a conjugated main chain and non-conjugated side chains. In addition, the present application also refers to conjugation when, for example, arylamine units, arylphosphine units, specific heterocycles (i.e., conjugated via nitrogen, oxygen or sulfur atoms) and / or organometallic complexes (i.e., conjugated via metal atoms) are present in the main chain. The same applies to conjugated dendrimers. In contrast, for example, units linked as simple alkyl bridging groups, (thio)ethers, esters, amides or imides are clearly defined as non-conjugated segments.

[0032] Semiconjugated polymers are understood in the present application to mean polymers containing conjugated regions separated from each other by non-conjugated portions, specific conjugation interrupting groups (e.g. spacer groups) or side chains, for example, in which relatively long conjugated portions in the main chain are interrupted by non-conjugated portions, or in which relatively long conjugated portions are contained in the side chains of a polymer that is non-conjugated in the main chain. Conjugated and semiconjugated polymers may also contain conjugated, semiconjugated or non-conjugated dendrimers.

[0033] The term "dendrimer" in the present application is understood to mean a highly branched compound formed from monomers branched in a regular structure to which a polyfunctional core is bonded, so that a tree-like structure is obtained. In this case, both the core and the monomers can have any desired branching structure consisting of purely organic units as well as organometallic compounds or coordination compounds. "Dendrimers" are generally understood here to mean the polyfunctional macromolecules described, for example, by M. Fischer and F. (Angew. Chem., Int. Ed. 1999, 38, 885).

[0034] The term "structural unit" in the present application is understood to mean a unit which, starting from a monomer unit having at least two, preferably two reactive groups, is introduced into the polymer basic skeleton as part thereof by a bonding reaction and is thus bonded as a repeating unit and is present in the prepared polymer.

[0035] The term "monocyclic or polycyclic aromatic ring system" is understood in the present application to mean an aromatic ring system having 6 to 60, preferably 6 to 30, more preferably 6 to 24 aromatic ring atoms and not necessarily containing only aromatic groups, but in which two or more aromatic units may also be replaced by short non-aromatic units (<10% of non-H atoms, preferably <5% of non-H atoms), for example sp 3 Interruptions are by 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 also to be regarded as aromatic ring systems.

[0036] The aromatic ring systems may be monocyclic or polycyclic, which means that they may have one ring (e.g., phenyl), or two or more rings which may be fused (e.g., naphthyl) or covalently bonded (e.g., biphenyl), or contain a combination of fused and bonded rings.

[0037] 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, lettuce, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene and spirobifluorene.

[0038] The term "monocyclic or polycyclic heteroaromatic ring system" is understood in the present application to mean an aromatic ring system having 5 to 60, preferably 5 to 30, more preferably 5 to 24 aromatic ring atoms, wherein one or more of these atoms are heteroatoms. The "monocyclic or polycyclic heteroaromatic ring system" does not necessarily contain only aromatic groups, but can also be short non-aromatic units (<10% of non-H atoms, preferably <5% of non-H atoms), for example sp 3 Hybridized carbon atoms or oxygen or nitrogen atoms, CO groups, etc. are interrupted.

[0039] The heteroaromatic ring systems may be monocyclic or polycyclic, which means that they may have one ring or two or more rings which may also be fused or covalently bonded (e.g. pyridylphenyl), or a combination of fused and bonded rings. Fully conjugated heteroaryl groups are preferred.

[0040] 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-oxadiazole, 2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered ring 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 with several rings such as carbazole, indenocarbazole, indole, Isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazimidazole, quinoxalinoimidazole, benzoxazole, naphthimidazole, anthraxazole, phenanthimidazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline phenanthroline, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazolothiophene, or a combination of these groups.

[0041] The monocyclic or polycyclic aromatic or heteroaromatic ring system may be unsubstituted or substituted. "Substituted" in the present application means that the monocyclic or polycyclic aromatic or heteroaromatic ring system has one or more R substituents.

[0042] R is preferably identical or different in each case and is H, D, F, Cl, Br, I, N (R 3 )2,CN,NO2,Si(R 3 )3,B(OR 3 )2,C(=O)R 3 , P(=O)(R 3 )2,S(=O)R 3 , S(=O)2R 3 ,OSO2R 3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, 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 group, wherein one or more non-adjacent CH2 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、SO2、NR 3 , O, S or CONR 3 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, or having 5 to 60 aromatic ring atoms and in each case by one or more R 3 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and substituted by one or more R 3 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and substituted by one or more R 3 an aralkyl or heteroaralkyl group substituted with a group, or having 10 to 40 aromatic ring atoms and which may be replaced by one or more R 3 or a cross-linkable group Q; at the same time, two or more R groups together can also form a monocyclic or polycyclic aliphatic, aromatic and / or benzo-fused ring system.

[0043] R is more preferably identical or different at each occurrence 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 group, wherein one or more non-adjacent CH2 groups may be replaced 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 CONR3 and wherein one or more hydrogen atoms may be replaced by F, Cl, Br or I, or having 5 to 30 aromatic ring atoms and in each case by one or more R 3 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 30 aromatic ring atoms and substituted by one or more R 3 substituted aryloxy or heteroaryloxy groups, or having 5 to 30 aromatic ring atoms and which may be replaced by one or more R 3 an aralkyl or heteroaralkyl group substituted with a group, or having 10 to 20 aromatic ring atoms and which may be replaced by one or more R 3 At the same time, two or more R groups can also form together a monocyclic or polycyclic aliphatic, aromatic and / or benzo-fused ring system.

[0044] R is most preferably identical or different in each case 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 replaced by one or more R 3 group, wherein one or more non-adjacent CH2 groups may be replaced by R 3 C=CR 3 、C≡C、C=O、C=NR 3 NR 3 , O or CONR 3 or having 5 to 20 aromatic ring atoms and in each case being replaced by one or more R 3 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 20 aromatic ring atoms and substituted by one or more R 3 substituted aryloxy or heteroaryloxy groups, or having 5 to 20 aromatic ring atoms and substituted by one or more R 3 an aralkyl or heteroaralkyl group substituted with a group, or having 10 to 20 aromatic ring atoms and which may be replaced by one or more R 3 At the same time, two or more R groups can also form together a monocyclic or polycyclic aliphatic, aromatic and / or benzo-fused ring system.

[0045] Preferred alkyl groups having 1 to 10 carbon atoms are depicted in the following table:

[0046]

[0047] In a second embodiment of the invention, at least one structural unit of the formula (I) in the polymer according to the invention is characterized in that Ar 3 One of the two adjacent positions is replaced by Ar 4 Replacement, and Ar 3 In the meta position adjacent to the ortho position of the substitution, additionally connected to Ar 4 .

[0048] Therefore, in a second embodiment, the structural unit of formula (I) has the structure of the following formula (Ib):

[0049]

[0050] Among them, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and R may have the definitions given above,

[0051] m = 0, 1, 2, 3 or 4,

[0052] n = 0, 1, 2 or 3,

[0053] X═CR2, NR, SiR2, O, S, C═O or P═O, preferably CR2, NR, O or S,

[0054] and

[0055] s and t are each 0 or 1, wherein the sum of (s+t)=1 or 2, preferably 1.

[0056] In a preferred embodiment, the at least one structural unit of formula (I) is selected from the structural units of the following formulae (II), (III) and (IV):

[0057]

[0058] Among them, Ar 1 ,Ar 2 ,Ar 4 and R may have the definitions given above,

[0059] m = 0, 1, 2, 3 or 4,

[0060] n = 0, 1, 2 or 3, and

[0061] X═CR2, NR, SiR2, O, S, C═O or P═O, preferably CR2, NR, O or S.

[0062] In a particularly preferred embodiment, the at least one structural unit of formula (II) is selected from the structural units of the following formula (V):

[0063]

[0064] Among them, Ar 1 ,Ar 2 , R and m may have the definitions given above, and

[0065] p=0, 1, 2, 3, 4 or 5.

[0066] Examples of preferred structural units of formula (V) are depicted in the table below:

[0067]

[0068] Among them, Ar 1 ,Ar 2 , R, m, n and p may have the definitions given above, and

[0069] k=0, 1 or 2.

[0070] In another particularly preferred embodiment, the at least one structural unit of formula (III) is selected from the structural units of the following formula (VI):

[0071]

[0072] Among them, Ar 1 ,Ar 2 , R, X, m and n may have the definitions given above.

[0073] Examples of preferred structural units of formula (VI) are depicted in the table below:

[0074]

[0075] Among them, Ar 1 ,Ar 2 , R, m, n and p may have the definitions given above.

[0076] In a further particularly preferred embodiment, the at least one structural unit of formula (IV) is selected from the structural units of the following formula (VII):

[0077]

[0078] Among them, Ar 1 ,Ar 2 , R, X, m and n may have the definitions given above.

[0079] Examples of preferred structural units of formula (VII) are depicted in the table below:

[0080]

[0081] Among them, Ar1 ,Ar 2 , R, m, n and p may have the definitions given above.

[0082] Preferably, Ar 1 and Ar 2 are identical or different in each case and are mono- or polycyclic, aromatic or heteroaromatic ring systems having 5 to 30, preferably 5 to 24, aromatic ring atoms.

[0083] More preferably, Ar 1 and Ar 2 is, in each case identical or different and independently, 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, lettuce, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene and spirobifluorene, preferably selected from phenyl and biphenyl, more preferably selected from phenyl.

[0084] In addition, Ar 1 and Ar 2 in each case identical or different and independently in its ortho or meta position by R 1 and R 2 Identically or differently substituted, preferably identically substituted in each case in the ortho- or meta-position, more preferably identically substituted in the meta-position of the bond to the nitrogen atom of the corresponding formulae.

[0085] In a very particularly preferred embodiment, the at least one structural unit of the formula (V) is selected from structural units of the following formula (VIII):

[0086]

[0087] Among them, R 1 , R 2 , m and p may have the definitions given above.

[0088] Examples of preferred structural units of formula (VIII) are depicted in the table below:

[0089]

[0090]

[0091] Among them, R 1 , R 2 , k, m, n and p may have the definitions given above.

[0092] In another very particularly preferred embodiment, the at least one structural unit of the formula (VI) is selected from structural units of the following formula (IX):

[0093]

[0094] Among them, R 1 , R 2 , X, m and n may have the definitions given above.

[0095] Examples of preferred structural units of formula (IX) are depicted in the table below:

[0096]

[0097] Among them, R 1 , R 2 , m, n and p may have the definitions given above, and

[0098] v=1-20, preferably 1-10.

[0099] In a further very particularly preferred embodiment, the at least one structural unit of the formula (VII) is selected from structural units of the following formula (X):

[0100]

[0101] Among them, R 1 , R 2 , X, m and n may have the definitions given above.

[0102] Examples of preferred structural units of formula (X) are depicted in the table below:

[0103]

[0104] Among them, R 1 , R 2 , m and n may have the definitions given above.

[0105] Preferably, R 1 and R 2 are identical 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 replaced by one or more R 3 group, wherein one or more non-adjacent CH2 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)(R3 )、SO、SO2、NR 3 , O, S or CONR 3 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN.

[0106] More preferably, R 1 and R 2 are identical or different in each case and independently in each case are straight-chain alkyl, alkoxy or thioalkoxy groups having 1 to 40, preferably 1 to 20, more preferably 1 to 10 carbon atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 40, preferably 3 to 20, more preferably 3 to 10 carbon atoms.

[0107] Preferred structural units in formulae (I), (Ia), (Ib) and (II) to (X) are depicted in the following table: 1 -N-Ar 2 -Example:

[0108]

[0109]

[0110] Among them, the structural units (a) to (c), (e), (i) and (j) are preferred, the structural units (a) and (e) are particularly preferred, and the structural unit (a) is very particularly preferred.

[0111] Examples of very particularly preferred structural units of the formula (II) are depicted in the table below:

[0112]

[0113]

[0114]

[0115] Among them, the structural units A1 to A11, A14, A15, A18 and A19 are preferred, the structural units A1 to A10, A14, A15, A18 and A19 are particularly preferred, and the structural units A6, A9 and A18 are very particularly preferred.

[0116] In the preferred embodiment of formula (VIII), (IX) and (X) and formula (VIIIa) to (VIIIh), (IXa) to (IXg) and (Xa) to (Xc), the dotted line represents the key connected to the adjacent structural unit in the polymer. They can be independently arranged in the ortho position, meta position or para position in the same or different manner, preferably arranged in the ortho position, meta position or para position in the same manner, more preferably arranged in the meta position or para position, most preferably arranged in the para position.

[0117] 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 mol % to 100 mol %.

[0118] In a first preferred embodiment, the polymer according to the invention contains only one structural unit of the 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 according to the invention is a homopolymer.

[0119] In a second preferred embodiment, the proportion of structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer is in the range from 50 to 95 mol %, more preferably in the range from 60 to 95 mol %, based on 100 mol % of all copolymerizable monomers present as structural units in the polymer, i.e. the polymer according to the invention has, in addition to one or more structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), further structural units which are different from the structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X).

[0120] In a third preferred embodiment, the proportion of structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X) in the polymer is in the range of 5 mol % to 50 mol %, more preferably in the range of 25 mol % to 50 mol %, based on 100 mol % of all copolymerizable monomers present as structural units in the polymer, i.e. the polymer according to the invention has, in addition to one or more structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), further structural units which are different from the structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X).

[0121] These structural units which are different from the structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and (X) include those structural units disclosed and comprehensively listed in WO 02 / 077060A1 and WO 2005 / 014689A2. These documents are considered to form a part of the present invention by reference. The other structural units can, for example, come from the following categories:

[0122] Group 1: units that influence the hole injection and / or hole transport properties of the polymer;

[0123] Group 2: units that affect the electron injection and / or electron transport properties of the polymer;

[0124] Group 3: units having a combination of individual units of groups 1 and 2;

[0125] Group 4: units that modify the luminescence properties in such a way that electrophosphorescence rather than electrofluorescence is obtained;

[0126] Group 5: units that improve the transition from the singlet state to the triplet state;

[0127] Group 6: units that affect the emission color of the resulting polymer;

[0128] Group 7: Units commonly used as polymer backbones;

[0129] Group 8: Units which influence the film morphology and / or rheological properties of the resulting polymer.

[0130] Preferred polymers according to the invention are those in which at least one structural unit has charge-transporting properties, ie those polymers which contain units from group 1 and / or group 2.

[0131] The structural units of the first group having hole injection and / or hole transport properties are, for example, triarylamines, benzidines, tetraaryl-p-phenylenediamines, triarylphosphines, phenothiazines, phenoxazines, dihydrophenazines, thianthrenes, dibenzo-p-dioxanes, phenoxathiol, carbazoles, Thiophene, pyrrole and furan derivatives and other O-containing heterocycles, S-containing heterocycles or N-containing heterocycles.

[0132] Preferred structural units from group 1 are the structural units of the following formulae (1a) to (1q):

[0133]

[0134]

[0135] wherein R, k, m and n may have the definitions given above.

[0136] In formulae (1a) to (1q), the dotted lines represent the possible bonds in the polymer that are connected to adjacent structural units. If there are two dotted lines in the formula, the structural unit has one or two, preferably two bonds connected to adjacent structural units. If there are three dotted lines in the formula, the structural unit has one, two or three, preferably two bonds connected to adjacent structural units. If there are four dotted lines in the formula, the structural unit has one, two, three or four, preferably two bonds connected to adjacent structural units. They can be independently arranged in the same or different positions in the ortho, meta or para positions.

[0137] Structural units from group 2 having electron injection and / or electron transport properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide and phenazine derivatives, as well as triarylboranes and other O-containing, S-containing or N-containing heterocycles.

[0138] It may be preferred that the polymer of the present invention contains units from the 3rd group, wherein the structure increasing the hole mobility and the structure increasing the electron mobility (that is, the units from the 1st and 2nd groups) are directly bonded to each other, or there is a structure increasing both the hole mobility and the electron mobility. Some of these units can be used as luminophores and make the luminescent color become green, yellow or red. Its use is therefore applicable to, for example, producing other luminescent colors by the polymer of the initial blue light emission.

[0139] The structural unit of the 4th group is that even at room temperature, it can also emit light efficiently from the triplet state, that is, it shows electrophosphorescence instead of electrofluorescence, thereby generally bringing those structural units that improve energy efficiency. Suitable for this purpose, first of all, it is a compound containing a heavy atom with an atomic number greater than 36. Preferred compounds are those compounds containing d or f transition metals that meet the above conditions. It is particularly preferred here to contain the corresponding structural units of the 8th to 10th family elements (Ru, Os, Rh, Ir, Pd, Pt). Here, the structural unit useful for the polymer of the present invention includes, for example, a variety of complexes, such as described in, for example, WO 02 / 068435A1, WO 02 / 081488A1, EP 1239526A2 and WO 2004 / 026886 A2. The corresponding monomers are described in WO 02 / 068435A1 and in WO 2005 / 042548A1.

[0140] Structural units of group 5 are those which improve the transition from the singlet state to the triplet state and, when used in combination with structural units of group 4, improve the phosphorescent properties of these structural units. Units useful for this purpose are especially 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.

[0141] In addition to those mentioned above, the structural units of the 6th group are those structural units which include at least one other aromatic structure or another conjugated structure, which do not belong to the above groups, i.e. they have only a minimal effect on the charge carrier mobility, are not organometallic complexes or do not affect the singlet-triplet transition. Such structural units can influence the luminescent color of the resulting polymer. Depending on the unit, they can therefore also be used as luminophores. Preferably, there are aromatic structures or other diphenylethylene, diphenylethylene or bisphenylethylene aromatic derivatives having 6 to 40 carbon atoms, each of which can be substituted by one or more R groups. Particular preference is given to introducing 1,4-anthracene or 9,10-anthracene, 1,6-, 2,7- or 4,9-pyrene, 3,9- or 3,10-perylene, 4,4′-tolanethynylene, 4,4′-stilbene, benzothiadiazole and the corresponding oxygen derivatives, quinoxaline, phenothiazine, phenoxazine, dihydrophenazine, bis(thienyl)arylene, oligo(thienyl), phenazine, rubrene, pentacene or perylene derivatives, which are preferably substituted or preferably conjugated push-pull systems (systems substituted by donor and acceptor substituents) or preferably substituted systems such as squarylium or quinacridone.

[0142] The structural units of group 7 are units comprising aromatic structures having 6 to 40 carbon atoms, which are generally used as polymer backbones. These are, 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-dihydrodibenzoxepinane 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-phenylene, 2,7-, 1,3- or 1,4-phenylene, 2,7-, 1,3- or 1,4-phenylene, 2,7-, 1,3- or 1,4-phenylene, 2,7-, 1,3- or 1,4-phenylene, 2,7-, 1,3- or 1,4-phenylene, 2,7-, 1,3- or 1,4-phenylene, 2,7- or 1,3-phenylene, 2,7- or 1,4-phenylene. 2'-biphenylene, 3,3'-biphenylene or 4,4'-biphenylene, 2,2"-terphenylene, 3,3"-terphenylene or 4,4"-terphenylene, 2,2'-bi-1,1'-naphthalene, 3,3'-bi-1,1'-naphthalene or 4,4'-bi-1,1'-naphthalene, or 2,2"'-quaterphenylene, 3,3"'-quaterphenylene or 4,4"'-quaterphenylene derivatives.

[0143] Preferred structural units from group 7 are structural units of the following formulae (7a) to (7o):

[0144]

[0145]

[0146] wherein R, k, m, n and p may have the definitions given above.

[0147] In formulae (7a) to (7o), the dotted lines represent the possible bonds connecting the adjacent structural units in the polymer. If there are two dotted lines in the formula, the structural unit has one or two, preferably two bonds connecting to the adjacent structural units. If there are four or more dotted lines in the formula (formulae (7g), (7h) and (7j)), the structural unit has one, two, three or four, preferably two bonds connecting to the adjacent structural units. They can be independently arranged in the same or different positions in the ortho, meta or para positions.

[0148] Structural units of group 8 are those which influence the film morphology and / or the rheological properties of the polymer, for example siloxanes, alkyl chains or fluorinated groups, and also particularly rigid or flexible units, liquid crystal-forming units or crosslinkable groups.

[0149] In addition to the structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), the polymers according to the invention preferably also contain one or more units selected from groups 1 to 8. It may likewise be preferred that more than one further structural unit from one group is present simultaneously.

[0150] In addition to at least one structural unit of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), it is preferred that the polymers according to the invention also contain units from group 7.

[0151] It is likewise preferred that the polymers according to the invention contain units which improve charge transport or charge injection, ie units from group 1 and / or group 2.

[0152] It is further particularly preferred that the polymers according to the invention contain structural units from group 7 and units from group 1 and / or group 2.

[0153] The polymers of the present invention are homopolymers of structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) or (X), or copolymers. The polymers of the present invention may be linear or branched, preferably linear. In addition to one or more structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X), the copolymers of the present invention may potentially also contain one or more other structures from Groups 1 to 8 described in detail above.

[0154] The copolymers of the present invention may have a random, alternating or block structure, or may have two or more of these structures in alternation. More preferably, the copolymers of the present invention have a random or alternating structure. More preferably, the copolymers are random or alternating copolymers. For example, the manner in which copolymers with block structures can be obtained and which other structural units are particularly preferred for this purpose are described in detail in WO 2005 / 014688 A2. This document is incorporated into the present application by reference. It should also be emphasized again at this point that the polymers may also have a dendritic structure.

[0155] In another embodiment of the present invention, in addition to one or more structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X) and optionally other structural units selected from the above-mentioned groups 1 to 8, the polymer of the present invention also contains at least one, preferably one, structural unit having a crosslinkable Q group.

[0156] In the context of the present invention, "crosslinkable Q group" refers to a functional group that can participate in the reaction and thus form an insoluble compound. The reaction can be carried out with other identical Q groups, other different Q groups or any other part thereof or another polymer chain. Therefore, the crosslinkable group is a reactive group. As a result of the reaction of the crosslinkable group, the corresponding crosslinked compound is thus obtained. The chemical reaction can also be carried out in the layer, thereby forming an insoluble layer. Crosslinking can usually be promoted by heat or by UV radiation, microwave radiation, X-radiation or electron beam in the presence of an initiator. "Insoluble" in the context of the present invention preferably refers to the polymer of the present invention after the crosslinking reaction, that is, after the crosslinkable group reaction, the solubility in an organic solvent at room temperature is lower than the solubility of the corresponding non-crosslinked polymer of the present invention in the same organic solvent, at least 2 / 3 lower than the solubility of the corresponding non-crosslinked polymer, preferably at least 9 / 10 lower.

[0157] In a first embodiment, the structural units carrying crosslinkable Q groups can be selected from structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X).

[0158] Preferred structural units carrying crosslinkable Q groups are structural units of the following formulae (XIa1) to (XIa3) derived from structural units of the formula (Ia):

[0159]

[0160] Among them, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 , R, m, X and r may have the definitions given above for formula (Ia).

[0161] Examples of preferred structural units of formula (XIa) are depicted in the table below:

[0162]

[0163] wherein R, k, m, n and p may have the definitions given above.

[0164] In formulae (11a) to (11f), the dashed lines represent possible bonds to adjacent structural units in the polymer. If two dashed lines are present in the formula, the structural unit has one or two, preferably two, bonds to adjacent structural units.

[0165] Further preferred structural units carrying crosslinkable Q groups are structural units of the following formulae (XIb1) to (XIb4) which are derived from structural units of the formula (Ib):

[0166]

[0167]

[0168] Among them, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 , R, n, X, p and q may have the definitions given above for formula (Ib).

[0169] Examples of preferred structural units of formula (XIb) are depicted in the table below:

[0170]

[0171]

[0172] wherein R, k, m, n and p may have the definitions given above.

[0173] In formulae (11g) to (11o), the dashed lines represent possible bonds to adjacent structural units in the polymer. If two dashed lines are present in the formula, the structural unit has one or two, preferably two, bonds to adjacent structural units.

[0174] Furthermore, the structural unit having a crosslinkable Q group may be selected from the structural units disclosed in Groups 1 to 8 in the second embodiment.

[0175] Preferred structural units carrying crosslinkable Q groups are structural units of the following formula (XII) derived from triarylamine units from group 1:

[0176]

[0177] Among them, Ar 1 ,Ar 2 and Ar 3 may have the definitions given above for formula (I).

[0178] Examples of preferred structural units of formula (XII) are depicted in the table below:

[0179]

[0180] Another preferred structural unit carrying a crosslinkable Q group is a structural unit of the following formula (XIII) derived from Group 7:

[0181]

[0182] Among them, Ar 1 The definitions given for the structural units of formula (I) may apply.

[0183] Examples of preferred structural units of formula (XIII) are depicted in the table below:

[0184]

[0185] As mentioned above, the crosslinkable Q group refers to a functional group that can participate in a chemical reaction and thus form an insoluble polymeric compound. Generally, any Q group known to those of ordinary skill in the art for this purpose can be used. The specific function of this group is to connect the polymeric compounds of the present invention to each other through a crosslinking reaction, optionally connected to other reactive polymeric compounds. Thus a crosslinked compound is obtained, or a crosslinked layer is obtained when reacting in a layer. A crosslinked layer is understood in the context of the present invention to refer to a layer obtainable by a crosslinking reaction from a layer of a crosslinkable polymeric compound of the present invention. The crosslinking reaction can usually be initiated by heat and / or by UV radiation, microwave radiation, X radiation or electron beams and / or by using free radical formers, anions, cations, acids and / or photoacids. The presence of a catalyst can also be helpful or necessary. Preferably, the crosslinking reaction is a reaction without the addition of an initiator and a catalyst.

[0186] Preferred crosslinkable Q groups according to the invention are the following groups:

[0187] a) Terminal or cyclic alkenyl or terminal diene and alkynyl groups:

[0188] Suitable units are those which contain a terminal or cyclic double bond, a terminal diene group or a terminal triple bond, in particular a terminal or cyclic alkenyl, terminal diene or terminal alkynyl group having 2 to 40 carbon atoms, preferably having 2 to 10 carbon atoms, wherein individual CH2 groups and / or individual hydrogen atoms may also be replaced by the abovementioned R groups. Also suitable are groups which are regarded as precursors and are capable of forming double or triple bonds in situ.

[0189] b) Alkenyloxy, dienyloxy or alkynyloxy group:

[0190] Additionally suitable are alkenyloxy, dienoxy or alkynyloxy groups, preferably alkenyloxy groups.

[0191] c) Acrylic Group:

[0192] Also suitable are acrylic acid units in the broadest sense, preferably acrylates, acrylamides, methacrylates and methacrylamides. Particular preference is given to acrylic acid C 1-10 Alkyl esters and methacrylate C 1-10 Alkyl esters.

[0193] The crosslinking reaction of the groups mentioned above under a) to c) can be achieved via free radical, cationic or anionic mechanisms, or via cycloadditions.

[0194] It may be advisable to add a suitable 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 hexachloroantimonate. Suitable initiators for anionic crosslinking are bases, especially butyl lithium.

[0195] However, in a preferred embodiment of the invention, the crosslinking is carried out by thermal initiation only without the addition of an initiator. The reason for this preference is that the absence of an initiator prevents contamination of the layer which could lead to a deterioration in the device performance.

[0196] d) Oxetanes and oxirane:

[0197] Another class of suitable crosslinkable groups Q are oxetanes and oxirane groups which crosslink cationically via ring opening.

[0198] It may be advisable to add a suitable initiator for the crosslinking reaction. Suitable initiators are, for example, AlCl3, BF3, triphenylmethyl perchlorate or hexachloroantimonate. . Photoacids can also be added as initiators.

[0199] e) Silane:

[0200] Also suitable as a type of crosslinkable group are silane groups SiR3, in which at least two R groups, 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 form oligosiloxanes or polysiloxanes.

[0201] f) Cyclobutane group

[0202] The abovementioned crosslinkable Q groups and suitable reaction conditions for the reaction of these groups are generally known to the person skilled in the art.

[0203] Preferred crosslinkable Q groups 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 formula Q5, alkynyloxy groups of the following formula Q6, acrylic groups of the following formulas Q7 and Q8, oxetane groups of the following formulas Q9 and Q10, oxirane groups of the following formula Q11, and cyclobutane groups of the following formula Q12:

[0204]

[0205] R in equations Q1 to Q8 and Q11 11 , R 12and R 13 The radicals are identical or different in each case and are H or a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, R 11 , R 12 and R 13 The radical is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, most preferably H or methyl. The indices used have the following definitions: s=0 to 8; t=1 to 8.

[0206] The dotted bonds in formulae Q1 to Q11 and the dotted bonds in formula Q12 represent the connection of the crosslinkable group to the structural unit.

[0207] The crosslinkable groups of the formulae Q1 to Q12 can be attached directly to the structural unit or via another monocyclic or polycyclic aromatic or heteroaromatic ring system Ar 10 Indirectly connected to the structural unit, as shown in the following formulas Q13 to Q24:

[0208]

[0209] Ar in formulas Q13 to Q24 10 Can have Ar 1 The same definition. Particularly preferred crosslinkable groups Q are as follows:

[0210]

[0211]

[0212] R in Formulas Q7a and Q13a to Q19a 11 and R 12 The radicals are identical or different in each case and are H or a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, R 11 and R 12 The group is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, most preferably methyl.

[0213] R in formulas Q7b and Q19b 13 The radical is in each case a straight-chain or branched alkyl radical having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, R 13 The group is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, most preferably methyl.

[0214] The labels used have the following definitions: s=0-8, t=1-8.

[0215] Very particularly preferred crosslinkable groups Q are as follows:

[0216]

[0217]

[0218] In preferred Q1 to Q24 groups, in particularly preferred Q1a to Q24a groups and in very particularly preferred Q1b to Q24c groups, the dotted line represents the bond to the structural unit. It should be noted in this regard that the Q12, Q12a, Q12b and Q24 groups each have two bonds to two adjacent ring carbon atoms in the structural unit. All other crosslinkable groups have only one bond to the structural unit.

[0219] The proportion of the crosslinkable structural units in the polymer is in the range of 0.01 mol % to 50 mol %, preferably in the range of 0.1 mol % to 30 mol %, more preferably in the range of 0.5 mol % to 25 mol %, most preferably in the range of 1 mol % to 20 mol %, based on 100 mol % of all comonomers present as structural units in the polymer.

[0220] The polymers of the invention containing structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and / or (XI) are generally prepared by polymerizing one or more monomer types, wherein at least one monomer produces structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) and / or (XI) in the polymer. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions leading to CC and CN couplings are as follows:

[0221] (A) SUZUKI polymerization;

[0222] (B) Yamamoto (YAMAMOTO) polymerization;

[0223] (C) STILLE polymerization;

[0224] (D) HECK polymerization;

[0225] (E) NEGISHI polymerization;

[0226] (F) SONOGASHIRA polymerization;

[0227] (G) HIYAMA POLYMERS; and

[0228] (H) Hartwig-Buchwald polymerization.

[0229] How to carry out the polymerization by these processes and how to isolate the polymer from the reaction medium and purify it 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.

[0230] The CC coupling is preferably selected from the group consisting of the Suzuki coupling, the Yamamoto coupling and the Stiller coupling; the CN coupling is preferably a coupling according to Hartwig-Buchwald.

[0231] The present invention therefore also provides a process for preparing the polymers according to the invention, characterised in that the polymers are prepared by Suzuki polymerisation, Yamamoto polymerisation, Stiller polymerisation or Hartwig-Buchwald polymerisation.

[0232] The synthesis of the polymers of the present invention requires corresponding monomers of formula (MI):

[0233]

[0234] Among them, Ar 1 ,Ar 2 and Ar 3 The definitions given for the structural units of formula (I) may apply.

[0235] The monomers of formula (MI) leading to the structural units of formula (I) in the polymer of the present invention are compounds with corresponding substitutions and with suitable functional groups that allow such monomer units to be incorporated into the polymer at two positions. The monomers of these formulas (MI) thus also form part of the subject matter of the present invention. The Y groups are identical or different and are leaving groups suitable for use in polymerization reactions to enable the monomer units to be incorporated into the polymeric compound. Preferably, Y is identical or different and is selected from the following chemical functional groups: halogen, O-toluenesulfonate, O-trifluoromethanesulfonate, O-sulfonate, borate, partially fluorinated silyl groups, diazo groups and organotin compounds.

[0236] The basic structure of the monomeric compound can be functionalized by standard methods, for example by Friedel-Crafts alkylation or acylation. In addition, the basic skeleton can be halogenated by standard organic chemical methods. The halogenated compound can optionally be further transformed in an additional functionalization step. For example, the halogenated compound can be used directly or after conversion into a boronic acid derivative or an organotin derivative as a starting material for conversion into a polymer, oligomer or dendrimer.

[0237] The methods are selected only from reactions known to the person skilled in the art, who can use them without inventive step to synthesize the compounds of the invention.

[0238] The polymers of the present invention can be used as pure substances or as mixtures with any other polymeric substances, oligomeric substances, dendritic substances or low molecular weight substances. Low molecular weight substances are understood in the present invention to mean compounds with a molecular weight in the range of 100 g / mol to 3000 g / mol, preferably 200 g / mol to 2000 g / mol. These other substances can, for example, improve electronic properties or emit light themselves. In this context, a mixture refers to a mixture comprising at least one polymeric component. In this way, one or more polymer layers can be produced, which are composed of one or more polymers of the present invention having structural units of formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and / or (X) and optionally a mixture (blend) of one or more other polymers and one or more low molecular weight substances.

[0239] The present invention therefore also provides a polymer blend comprising one or more polymers of the present invention and one or more other polymeric, oligomeric, dendritic and / or low molecular weight species.

[0240] The present invention also provides a solution and a formulation consisting of 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 / 072714A1, WO 03 / 019694A2 and the literature cited therein.

[0241] These solutions can be used to produce thin polymer layers, for example by surface coating methods, such as spin coating, or by printing methods, such as inkjet printing.

[0242] Polymers containing structural units with crosslinkable Q groups are particularly suitable for, for example, in-situ polymerization and in-situ crosslinking, for example in-situ UV photopolymerization or photopatterning by heat or light induction to make films or coatings, especially for making structured coatings. The corresponding polymers in pure form, or preparations or mixtures of these polymers as described above, can be used here. These can be used with or without the addition of solvents and / or adhesives. Suitable materials, methods and equipment for the above method are described in, for example, WO 2005 / 083812 A2. Feasible adhesives are, for example, polystyrene, polycarbonate, poly(methyl)acrylate, polyacrylate, polyvinyl butyral and similar photoelectric neutral polymers.

[0243] Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fennel, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, phenethyl Ketone, alpha-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenethyl ether, 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.

[0244] The present invention therefore also provides the use of polymers containing structural units with crosslinkable Q groups for preparing crosslinked polymers. The crosslinkable groups, more preferably vinyl groups or alkenyl groups, are preferably incorporated into the polymer by a Wittig reaction or a Wittig-like reaction. If the crosslinkable groups are vinyl groups or alkenyl groups, the crosslinking can be carried out via free radical or ionic polymerization that can be thermally induced or induced by radiation. Preferably, free radical polymerization is thermally induced at a temperature of less than 250°C, more preferably at a temperature of less than 230°C.

[0245] Optionally, additional styrene monomers are added during the crosslinking process to achieve a higher degree of crosslinking. Preferably, the proportion of styrene monomers added is in the range of 0.01 mol % to 50 mol %, more preferably in the range of 0.1 mol % to 30 mol %, based on 100 mol % of all comonomers present as structural units in the polymer.

[0246] The present invention therefore also provides a method for preparing a cross-linked polymer, the method comprising the following steps:

[0247] (a) providing a polymer comprising structural units having one or more crosslinkable Q groups; and

[0248] (b) Free radical or ionic crosslinking, which may be induced thermally or by radiation, is preferably induced thermally, preferably free radical crosslinking.

[0249] The crosslinked polymers prepared by the process according to the invention are insoluble in all standard solvents. In this way, defined layer thicknesses can be produced without redissolving or only partially dissolving even when subsequent layers are applied.

[0250] The present invention therefore also relates to a crosslinked polymer obtainable by the above method. As mentioned above, the crosslinked polymer is preferably manufactured in the form of a crosslinked polymer layer. Since the crosslinked polymer is insoluble in all solvents, another layer can be applied from a solvent to the surface of such a crosslinked polymer layer by the above techniques.

[0251] The invention also encompasses so-called hybrid devices, in which there may be one or more layers processed from solution and one or more layers produced by vapor deposition of low molecular weight substances.

[0252] The polymers of the invention can be used in or for the manufacture of electronic or optoelectronic devices.

[0253] The present invention therefore also provides the use of the polymers 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).

[0254] In the case of the above hybrid devices, in combination with organic electroluminescent devices, reference is made to a combined PLED / SMOLED (polymer light emitting diode / small molecule organic light emitting diode) system.

[0255] The way in which OLEDs can be produced is known to the person skilled in the art and is described in detail, for example, in WO 2004 / 070772 A2 as a general method which has to be appropriately adapted to the individual case.

[0256] As mentioned above, the polymers according to the invention are very particularly suitable as electroluminescent materials in OLEDs or displays produced in this way.

[0257] Electroluminescent materials are in the context of the present invention taken to mean materials which can be used as active layers. "Active layer" means a layer which is capable of emitting light (luminescent layer) and / or improving the injection and / or transport of positive and / or negative charges (charge injection layer or charge transport layer) when an electric field is applied.

[0258] The present invention therefore preferably also provides for the use of the polymers according to the invention in OLEDs, in particular as electroluminescent material.

[0259] The present invention also provides an electronic or optoelectronic component having one or more active layers, preferably an organic electroluminescent device (OLED), 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 and an organic photoreceptor (OPC), more preferably an organic electroluminescent device, wherein at least one of the active layers comprises one or more polymers of the present invention. The active layer may, for example, be a light-emitting layer, a charge transport layer and / or a charge injection layer.

[0260] In the present application text and in the examples that follow below, the use of the polymers of the invention in OLEDs and corresponding displays is primarily intended. Despite this limitation of the present description, a person skilled in the art will also be able to utilize the polymers of the invention as semiconductors in other electronic devices for the above-mentioned other uses without further creative effort.

[0261] The following examples are intended to illustrate the present invention without limiting it. More particularly, unless otherwise indicated to the contrary, the features, properties and advantages described therein for the defined compounds forming the basis of the discussed examples also apply to other compounds not mentioned in detail but covered by the scope of protection of the claims. Example:

[0262] Part A: Synthesis of Monomers

[0263] Unless otherwise stated, all syntheses were performed under argon atmosphere and in dry solvents.

[0264] A1 Preparation of Precursors of Monomers of the Invention

[0265] A1.1 Preparation of Precursor Int-1

[0266]

[0267] 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 adding 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 hours, the reaction mixture is cooled 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 (2×250 ml) and dried over magnesium sulfate and then concentrated on a rotary evaporator. The residue is filtered through silica gel (eluent: heptane) and the product is obtained by crystallization from ethanol.

[0268] Yield: 31 g (0.09 mmol, 50% of theoretical value)

[0269] The following precursors can be prepared analogously to Example A1.1:

[0270]

[0271]

[0272] A2. Preparation of Monomers of the Invention

[0273] A2.1 Preparation of Monomer Inv-Mon-Br-1

[0274]

[0275] 31.0 g (0.09 mmol) of Int-1 was dissolved in 350 ml of THF and cooled to 0°C. 31.4 g (176 mmol) of N-bromosuccinimide was added in portions, the mixture was gradually brought to room temperature and stirred for 16 hours. The reaction mixture was then concentrated, heptane was added, and extraction was stirred while cooling with ice. The resulting solid was filtered off with suction, and the filtrate was concentrated. Purification was performed by repeated crystallization from ethanol until the purity was >99.5% (GC-MS).

[0276] Yield: 26.3 g (0.05 mol, 60%)

[0277] The following monomers can be prepared similarly to Inv-Mon-Br-1:

[0278]

[0279] A3 Other monomers

[0280] Other monomers used to prepare the polymers of the present invention and comparative polymers have been described in the prior art, are commercially available or prepared by literature methods, and are summarized in the following Table 1:

[0281] Table 1

[0282]

[0283] Part B: Synthesis of polymers

[0284] Preparation of comparative polymers V-HTL1 and V-HTL2, and preparation of inventive polymers HTL1, HTL2, HTL3 and HTL4

[0285] The comparative polymers V-HTL1 and V-HTL2 and the inventive polymers HTL1, HTL2, HTL3 and HTL4 were prepared from the corresponding monomers by Suzuki coupling by the method described in WO 2003 / 048225 A2.

[0286] For the polymerization, the monomers were used in the percentages in mol % specified in Table 2. The polymers V-HTL1, V-HTL2, HTL1, HTL2, HTL3 and HTL4 prepared in this way contained, after removal of the leaving group, the percentages of structural units reported in Table 2 (percentage = mol %).

[0287] In the case of monomers with aldehyde groups, these are converted into crosslinkable vinyl groups after polymerization by the Wittig reaction by the method described in WO 2010 / 097155 A1. The polymers listed accordingly in Table 2 and used in Part C therefore have crosslinkable vinyl groups instead of the aldehyde groups originally present.

[0288] The palladium and bromine contents of the polymer were determined by ICP-MS and were less than 10 ppm.

[0289] The molecular weight M was determined by means of gel permeation chromatography (GPC) (model: Agilent HPLC system 1100 series) (column: PL-Rapid H from Polymer Laboratories; solvent: THF with 0.12% by volume of o-dichlorobenzene; detection: UV and refractive index; temperature: 40° C.) w and polydispersity D. Calibration was performed using polystyrene standards.

[0290] The composition of the polymer is given in Table 2 below:

[0291] Table 2

[0292] polymer MON A ％ MON B ％ MON C ％ MON D ％ Mw / D V-HTL1 MON-102-Br 50 MON-1-BE 40 MON-30-BE 10 138K / 2.1 V-HTL2 MON-102-Br 10 MON-1-Br 20 MON-20-BE 50 MON-30-Br 20 88K / 2.5 HTL1 MON-102-BE 40 Inv-MON-Br-1 50 MON-30-BE 10 70K / 2.1 HTL2 MON-102-BE 40 Inv-MON-Br-2 50 MON-30-BE 10 68K / 2.1 HTL3 MON-102-BE 40 Inv-MON-Br-3 50 MON-30-BE 10 57K / 2.3 HTL4 MON-102-BE 40 Inv-MON-Br-4 50 MON-30-BE 10 52K / 2.2

[0293] Part C: OLED Manufacturing

[0294] There are already numerous descriptions of the production of solution-based OLEDs in the literature, for example in WO 2004 / 037887 A2 and WO 2010 / 097155 A1. The methods described are adapted to the conditions described below (layer thicknesses, variation of materials).

[0295] The material combination according to the invention is used in the following layer sequence:

[0296] - substrate,

[0297] -ITO (50nm),

[0298] - Hole injection layer (HIL) (25nm),

[0299] - Hole transport layer (HTL) (20 nm),

[0300] -Emitting layer (EML) (60nm),

[0301] - Hole blocking layer (HBL) (10 nm),

[0302] - Electron Transport Layer (ETL) (40nm),

[0303] - Electron injection layer (EIL) (1 nm),

[0304] - cathode (Al) (100 nm).

[0305] The substrate used is a glass plate coated with structured ITO (indium tin oxide) with a thickness of 50nm. The hole injection layer is applied by spin coating in an inert atmosphere. For this purpose, a hole transport crosslinkable polymer and a p-type doped salt are dissolved in toluene. The corresponding materials are described in particular in WO 2016 / 107668 A1, WO 2013 / 081052 A1 and EP2325190 A1. For the resulting layer thickness of 25nm, a solid content of 6mg / ml is used. The layer is then baked on a hot plate at 210°C for 30 minutes in an inert gas atmosphere.

[0306] Hole transport layers and light-emitting layers are then applied to these coated substrates.

[0307] The hole transport layers used were the compounds according to the invention and the comparative compounds, each dissolved in toluene. Since a layer thickness of 20 nm was to be achieved by spin coating, the solids content of these solutions was 5 mg / ml. The layers were spun in an inert gas atmosphere and baked on a hot plate at 220° C. for 30 minutes.

[0308] The materials used in the present invention are shown in Table 2, and the monomers used are shown in Table 1.

[0309] The luminescent layer is composed of a host material H1, a host material H2 and a luminescent dopant D1. The materials are present in the luminescent layer in a ratio of 45% by weight of H1, 36% by weight of H2 and 19% by weight of D1. The mixture for the luminescent layer is dissolved in toluene. Since a layer thickness of 60 nm is to be achieved by spin coating, the solid content of the solution is 19 mg / ml. The layer is spun in an inert gas atmosphere and baked at 150° C. for 10 minutes.

[0310] Table 3: Structural formulas of materials used in EML

[0311]

[0312] The materials for the hole blocking layer, electron transport layer and electron injection layer were applied by thermal vapor deposition in a vacuum chamber and are shown in Table 4. The hole blocking layer consisted of ETM1. The electron transport layer consisted of two materials, ETM1 and ETM2, which were blended by co-evaporation in a ratio of 50% by volume each. The electron injection layer consisted of ETM2.

[0313] Table 4: HBL materials and ETL materials used

[0314]

[0315] The cathode was formed by thermal evaporation of an aluminum layer with a thickness of 100 nm.

[0316] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current-voltage-luminous density characteristics (IUL characteristics) assuming Lambertian radiation characteristics and the (operating) lifetime were determined. The IUL characteristics are used to determine parameters such as the external quantum efficiency (%) at a specific brightness. At 1000 cd / m 2 The LD80 for OLED is assumed to be 1000cd / m 2 Decreases to 80% of the initial intensity, i.e. to 800 cd / m 2 Life span till now.

[0317] The properties of various OLEDs are summarized in Table 5. Examples V01 and V02 are comparative examples. Example C1 shows the properties of an OLED with the material combination of the invention, and the energy gap of the individual HTL polymers. A green emitting OLED comprising the material of the invention as HTL was produced.

[0318] The energy gap of each polymer was determined by absorption spectroscopy on its pure film. For this purpose, a pure film of the polymer was produced on quartz glass. For this purpose, the polymer was dissolved in toluene at a concentration of 15 mg / ml and processed by spin coating to a 50 nm thick film. It was baked at 220° C. for 30 minutes under an inert gas atmosphere.

[0319] Absorption measurements were performed in a Perkin Elmer Lambda 850 UV-VIS spectrometer. The side of the absorption spectrum was used to determine the energy gap (see Figure 1). The results are also shown in Table 5.

[0320] As shown in Table 5, the polymer of the present invention (i.e., HTL1) creates an energy gap between the polymer with interrupted conjugation (i.e., V-HTL2) and the conjugated polymer (i.e., V-HTL1). In addition, it can be seen that the OLED has an improvement in efficiency relative to the conjugated polymer, and the OLED has an improvement in life relative to the polymer with interrupted conjugation.

[0321] Table 5: Performance of OLED

[0322]

Claims

1. A polymer having at least one structural unit of the following formula (I): in Ar 1 To Ar 3 are in each case identical or different and are monocyclic or polycyclic aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, wherein Ar 3 may be substituted with one or more R groups; R is identical or different in each case and is H, D, F, Cl, Br, I, N (R 3 )2,CN,NO2,Si(R 3 )3,B(OR 3 )2,C(=O)R 3 , P(=O)(R 3 )2,S(=O)R 3 , S(=O)2R 3 ,OSO2R 3 , a linear 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 replaced by one or more R 3 group, wherein one or more non-adjacent CH2 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、SO2、NR 3 , O, S or CONR 3 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, or having 5 to 60 aromatic ring atoms and in each case by one or more R 3 A monocyclic or polycyclic aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 3 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and substituted by one or more R 3 an aralkyl or heteroaralkyl group substituted with a group, or having 10 to 40 aromatic ring atoms and which may be replaced by one or more R 3 a diarylamino group, a diheteroarylamino group or an arylheteroarylamino group substituted with a radical; or a crosslinkable group Q, wherein two or more R groups together can also form a monocyclic or polycyclic aliphatic, aromatic and / or benzo-fused ring system; R 3 are in each case identical or different and are H, D, F, or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, an aromatic and / or heteroaromatic hydrocarbon radical having 5 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; in which two or more R 3 The substituents together may also form a monocyclic or polycyclic aliphatic or aromatic ring system; and Dashed lines represent bonds connecting adjacent structural units in the polymer; It is characterized in that Ar 1 By R 1 Substitution and / or Ar 2 By R 2 Group substitution, where R 1 and R 2 are independently identical or different at each occurrence and are F, Cl, Br, I, N(R 3 )2,CN,NO2,Si(R 3 )3,B(OR 3 )2,C(=O)R 3 , P(=O)(R 3 )2,S(=O)R 3 , S(=O)2R 3 ,OSO2R 3 , having 1 to 40 carbon atoms and in each case may be replaced by one or more R 3 A straight-chain alkyl, alkoxy or thioalkoxy group substituted with a radical or having 3 to 40 carbon atoms and in each case being substituted with one or more R 3 A branched or cyclic alkyl, alkoxy or thioalkoxy group substituted by a group, wherein one or more non-adjacent CH2 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、SO2、NR 3 , O, S or CONR 3 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN.

2. The polymer according to claim 1, characterized in that Ar 1 By R 1 Group Substitution and Ar 2 By R 2 Group substitution.

3. The polymer according to claim 1 or 2, characterized in that Ar 3 At least one of the two ortho positions, preferably one of the two ortho positions, is replaced by Ar 4 Substituted, where Ar 4 R 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 groups.

4. The polymer according to one or more of claims 1 to 3, characterized in that The at least one structural unit of formula (I) is selected from the structural units of the following formula (Ia): Among them, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and R may have the definitions given in claims 1 and 3, q = 0, 1, 2, 3, 4, 5 or 6, X=CR2, NR, SiR2, O, S, C=O or P=O, and r=0 or 1.

5. The polymer according to one or more of claims 1 to 4, characterized in that Ar 3 One of the two adjacent positions is replaced by Ar 4 Replacement, and Ar 3 In the meta position adjacent to the substituted ortho position, additionally connected to Ar 4 .

6. The polymer according to one or more of claims 1 to 5, characterized in that The at least one structural unit of formula (I) is selected from the structural units of the following formula (Ib): Among them, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 , R and X may have the definitions given in claims 1, 3 and 4, m=0, 1, 2, 3 or 4, and n = 0, 1, 2 or 3, and s and t are each 0 or 1, where the sum of (s+t)=1 or 2.

7. The polymer according to one or more of claims 1 to 6, characterized in that The at least one structural unit of formula (I) is selected from the structural units of the following formulae (II), (III) and (IV): Among them, Ar 1 ,Ar 2 ,Ar 4 , R, m, n and X may have the definitions given in claims 1, 3, 4 and 6.

8. The polymer according to claim 7, characterized in that The at least one structural unit of formula (II) is selected from the structural units of the following formula (V): Among them, Ar 1 ,Ar 2 , R and m may have the definitions given in claims 1 and 6, and p=0, 1, 2, 3, 4 or 5.

9. The polymer according to claim 7, characterized in that The at least one structural unit of formula (III) is selected from the structural units of the following formula (VI): Among them, Ar 1 ,Ar 2 , R, m and n may have the definitions given in claims 1 and 6.

10. The polymer according to claim 7, characterized in that The at least one structural unit of formula (IV) is selected from the structural units of the following formula (VII): Among them, Ar 1 ,Ar 2 , R, m, n and X may have the definitions given in claims 1 and 6.

11. The polymer according to one or more of claims 1 to 10, characterized in that Ar 1 and Ar 2 are identical or different in each case and are mono- or polycyclic, aromatic or heteroaromatic ring systems having 5 to 30, preferably 5 to 24, aromatic ring atoms.

12. The polymer according to one or more of claims 1 to 11, characterized in that Ar 1 and Ar 2 is, in each case identical or different and independently, 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, lettuce, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene and spirobifluorene, preferably selected from phenyl and biphenyl, more preferably selected from phenyl.

13. The polymer according to one or more of claims 1 to 12, characterized in that Ar 1 and Ar 2 in each case identical or different and independently in its ortho or meta position by R 1 and R 2 Identically or differently substituted, preferably identically substituted in each case in the ortho- or meta-position, more preferably identically substituted in the meta-position of the bond to the nitrogen atom of formula (I).

14. The polymer according to one or more of claims 1 to 13, characterized in that R 1 and R 2 are identical 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 replaced by one or more R 3 groups, wherein one or more non-adjacent CH2 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、SO2、NR 3 , O, S or CONR 3 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN.

15. The polymer according to one or more of claims 1 to 14, characterized in that R 1 and R 2 are identical or different in each case and independently in each case are straight-chain alkyl, alkoxy or thioalkoxy groups having 1 to 40, preferably 1 to 20, more preferably 1 to 10 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 40, preferably 3 to 20, more preferably 3 to 10 carbon atoms.

16. The polymer according to one or more of claims 1 to 15, characterized in that The proportion of the structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII) in the polymer is in the range of 50 mol % to 95 mol %, based on 100 mol % of all copolymerizable monomers present as structural units in the polymer.

17. The polymer according to one or more of claims 1 to 16, characterized in that In addition to the structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII), the polymer also has other structural units that are different from the structural units of the formula (I), (Ia), (Ib), (II), (III), (IV), (V), (VI) or (VII).

18. A process for preparing a polymer according to one or more of claims 1 to 17, characterized in that The polymers are prepared by Suzuki polymerisation, Yamamoto polymerisation, Stiller polymerisation or Hartwig-Buchwald polymerisation.

19. A polymer blend comprising one or more polymers according to one or more of claims 1 to 17 containing at least one structural unit of the formula (I) and one or more other polymeric, oligomeric, dendritic and / or low molecular weight substances.

20. A solution or formulation consisting of one or more polymers according to one or more of claims 1 to 17 or a polymer blend according to claim 19 in one or more solvents.

21. Use of a polymer according to 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).

22. 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, the electronic or optoelectronic device having one or more active layers, wherein at least one of the active layers comprises one or more polymers according to one or more of claims 1 to 17.

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