阅读说明：本技术 用于电子器件的材料 (Material for electronic devices ) 是由 比特·布克哈特 卡特娅·沙伊布勒 尼尔斯·克嫩 霍尔格·海尔 于 2018-06-18 设计创作，主要内容包括：本申请涉及一种包含至少一种式(I)的结构单元的聚合物。所述聚合物适合用于电子器件中。(The present application relates to a polymer comprising at least one structural unit of formula (I). The polymers are suitable for use in electronic devices.)

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

the variables appearing therein are as follows:

u is identical or different on each occurrence and is C (R)¹)₂、CR¹＝CR¹、Si(R¹)₂O or S, wherein is selected from CR¹＝CR¹The groups O and S are not directly bonded to each other;

z is identical or different on each occurrence and, when no radical is bonded to Z, Z is N or CR²And when a group is bonded to Z, Z is C;

Ar¹、Ar²、Ar³、Ar⁴and Ar⁵Identical or different and are selected from the group consisting of those having 5 to 40 aromatic ring atoms which may be substituted by one or more R³A heteroaromatic ring system substituted by radicals, and having from 6 to 40 aromatic ring atoms which may be substituted by one or more R³A group-substituted aromatic ring system;

R¹in each case identical or different and are selected from H, D, F, C (═ O) R⁴，CN，Si(R⁴)₃，N(R⁴)₂，P(＝O)(R⁴)₂，OR⁴，S(＝O)R⁴，S(＝O)₂R⁴A linear alkyl or alkoxy radical having from 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy radical having from 3 to 20 carbon atoms, having from 2 to 20 carbon atomsAlkenyl or alkynyl groups of atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁴Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁴C＝CR⁴-、-C≡C-、Si(R⁴)₂、C＝O、C＝NR⁴、-C(＝O)O-、-C(＝O)NR⁴-、NR⁴、P(＝O)(R⁴) -O-, -S-, SO or SO₂Replacement;

R²、R³in each case identical or different and are selected from H, D, F, C (═ O) R⁴，CN，Si(R⁴)₃，N(R⁴)₂，P(＝O)(R⁴)₂，OR⁴，S(＝O)R⁴，S(＝O)₂R⁴A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁴Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁴C＝CR⁴-、-C≡C-、Si(R⁴)₂、C＝O、C＝NR⁴、-C(＝O)O-、-C(＝O)NR⁴-、NR⁴、P(＝O)(R⁴) -O-, -S-, SO or SO₂Replacement;

R⁴in each case identical or different and are selected from H, D, F, C (═ O) R⁵，CN，Si(R⁵)₃，N(R⁵)₂，P(＝O)(R⁵)₂，OR⁵，S(＝O)R⁵，S(＝O)₂R⁵A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R⁴May be connected to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁵Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁵C＝CR⁵-、-C≡C-、Si(R⁵)₂、C＝O、C＝NR⁵、-C(＝O)O-、-C(＝O)NR⁵-、NR⁵、P(＝O)(R⁵) -O-, -S-, SO or SO₂Replacement;

R⁵identical or different on each occurrence and selected from the group consisting of H, D, F, CN, alkyl or alkoxy radicals having from 1 to 20 carbon atoms, alkenyl or alkynyl radicals having from 2 to 20 carbon atoms, aromatic ring systems having from 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having from 5 to 40 aromatic ring atoms; wherein two or more R⁵The groups may be linked to each other and may form a ring; and wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may be substituted by F or CN;

r is 1,2 or 3 when p is 1, and r is 1 when p is 0;

when q is 1, s is 0, 1,2 or 3, and when q is 0, s is 1;

p is 0 or 1; wherein, when p is 0, groups bonded to the unit between the square brackets having the label p are directly bonded to each other;

q is 0 or 1; wherein, when q is 0, groups bonded to the unit between brackets having the label q are directly bonded to each other;

n is 0 or 1; wherein, when n is 0, groups bonded to the unit between the square brackets having the label n are directly bonded to each other;

m is 0 or 1; wherein, when m is 0, groups bonded to the unit between square brackets having the label m are directly bonded to each other;

o is 0 or 1; wherein, when o is 0, groups bonded to the unit between brackets having the label o are directly bonded to each other;

i is identical or different on each occurrence and is 1,2,3,4, 5,6, 7 or 8;

wherein at least one compound containing one or more R is present¹U of the group, said R¹The groups are selected from linear alkyl or alkoxy groups having from 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having from 3 to 20 carbon atoms, alkenyl or alkynyl groups having from 2 to 20 carbon atoms, aromatic ring systems having from 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having from 5 to 40 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁴Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁴C＝CR⁴-、-C≡C-、Si(R⁴)₂、C＝O、C＝NR⁴、-C(＝O)O-、-C(＝O)NR⁴-、NR⁴、P(＝O)(R⁴) -O-, -S-, SO or SO₂And (6) replacing.

2. The polymer of claim 1, wherein Ar is Ar¹、Ar²、Ar³、Ar⁴And Ar⁵In each case identical or different and are selected from the group consisting of benzene, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, indenofluoreneSpirobifluorenes, dibenzofurans, dibenzothiophenes, carbazoles, indenocarbazoles, and indolocarbazoles, each of which may be substituted with one or more R¹And (4) substituting the group.

3. The polymer of claim 1 or 2, wherein R is¹In each case identical or different and are selected from H, D, F, linear alkyl radicals having from 1 to 10 carbon atoms and branched alkyl radicals having from 3 to 10 carbon atoms.

4. Polymer according to one or more of claims 1 to 3, characterized in that those two U groups directly adjacent to the bridgehead carbon atom carry R¹Group R¹The radicals are selected from F, CN, Si (R)⁴)₃，OR⁴Straight-chain alkyl and alkoxy groups having from 1 to 10 carbon atoms, branched-chain alkyl and alkoxy groups having from 3 to 10 carbon atoms, and aromatic ring systems having from 6 to 20 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; and wherein the alkyl and alkoxy groups mentioned and the aromatic ring systems mentioned may each be substituted by one or more R⁴And (4) substituting the group.

5. The polymer according to one or more of claims 1 to 4, characterized in that the units in the structural unit of formula (I)

A unit selected from formula (E-1):

wherein a free bond is a bond to the remainder of the structural unit of formula (I) and wherein the variables present are the same as defined in one or more of claims 1 to 4.

6. The polymer according to one or more of claims 1 to 5, characterized in that the units in the structural unit of formula (I)

Selected from the following units:

wherein the dotted line represents a bond to the remainder of the structural unit of formula (I), and wherein a semicircular bond means that the two R's involved¹The radicals are linked to one another and form a ring, and the variables present therein are the same as defined in one or more of claims 1 to 5.

7. The polymer according to one or more of claims 1 to 6, characterized in that the structural element corresponds to formula (I) of any of the formulae (I-1) to (I-6)

Wherein the variables present are the same as defined in one or more of claims 1 to 6.

8. The polymer according to one or more of claims 1 to 7, characterized in that the proportion of structural units of the formula (I) in the polymer is in the range from 30 to 70 mol%, based on 100 mol% of all copolymerizable monomers present as structural units in the polymer.

9. The polymer according to one or more of claims 1 to 8, characterized in that the polymer comprises at least one structural unit comprising a crosslinkable Q group.

10. The polymer according to claim 9, characterized in that the crosslinkable Q groups are selected from the following formulae:

wherein R is¹¹、R¹²、R¹³And R¹⁴In each case identical or different and selected from H and straight-chain or branched alkyl radicals having from 1 to 6 carbon atoms, s ═ 0 to 8, t ═ 1 to 8, and Ar¹⁰Selected from those having 6 to 40 aromatic ring atoms and which may be substituted by one or more R¹¹Radical-substituted aromatic ring systems and aromatic ring systems having from 5 to 40 aromatic ring atoms which may be substituted by one or more R¹¹A group-substituted heteroaromatic ring system, and wherein the dashed bonds indicate bonds to the remainder of said formula.

11. A polymer obtainable by a crosslinking reaction of the polymer according to claim 9 or 10.

12. A mixture comprising one or more polymers according to one or more of claims 1 to 11 and one or more further polymeric, oligomeric, dendritic and/or low molecular weight substances.

13. A solution comprising one or more polymers according to one or more of claims 1 to 11 and one or more solvents.

14. Use of a polymer according to one or more of claims 1 to 11 in an electronic device.

15. An electronic device comprising at least one polymer according to one or more of claims 1 to 11.

16. Electronic device according to claim 15, characterized in that the polymer according to one or more of claims 1 to 11 is present in a layer selected from the group consisting of a hole transport layer, a hole injection layer, an electron blocking layer and a light emitting layer.

17. A process for the preparation of a polymer according to one or more of claims 1 to 11, characterized in that a polymerization selected from Suzuki polymerization, Yamamoto polymerization, Stille polymerization, Heck polymerization, Negishi polymerization, Sonogashira polymerization, Hiyama polymerization and Hartwig-Buchwald polymerization is carried out.

18. A monomer of formula (M)

The variables appearing therein are the same as defined in one or more of claims 1 to 6, and wherein X is the same or different in each case and is a leaving group suitable for polymerization.

Technical Field

The present application relates to a polymer comprising at least one structural unit of formula (I) as defined below. The polymers are suitable for use in electronic devices.

Background

Electronic device in the context of the present application refers to a so-called organic electronic device, which contains an organic semiconductor material as functional material. More particularly, these refer to OLEDs. The term OLED refers to an electronic device having one or more layers comprising organic compounds and emitting light upon application of a voltage. The structure and the general principle of action of OLEDs are known to the person skilled in the art.

In electronic devices, in particular OLEDs, there is a great interest in improving the performance data, in particular the lifetime, the efficiency and the operating voltage. In these respects, no fully satisfactory solution has been found.

Therefore, new materials, especially polymers, for OLEDs are constantly being sought.

In the case of OLEDs, two important methods of applying the material in the form of layers are known: from the gas phase by sublimation and from solution. For the latter method, suitable materials include polymers.

For the preparation of such polymers, it is important that the polymers and monomers used have good solubility, since otherwise it is not possible to obtain polymers with high chain length.

When polymers are applied from solution in the manufacture of OLEDs, it is important that they have good solubility in the solvents used. It is also important that they dissolve rapidly in the solvents used. It is also important that they have good film forming properties.

One factor of particular importance in the case of polymers used in OLEDs is that they lead to a long lifetime and high efficiency of the devices. This is especially true when the polymer is used in a hole transport layer of an OLED, especially in combination with a light emitting layer that is also subsequently applied from solution.

It is also important that the polymer has maximum chemical stability and does not decompose.

Disclosure of Invention

It has now been found that at least one, preferably more than one, of the above-mentioned technical problems can be solved by providing novel polymers containing specific structural units as defined below.

Accordingly, the present application provides a polymer comprising at least one structural unit of the formula (I)

The variables appearing therein are as follows:

u is identical or different on each occurrence and is C (R)¹)₂、CR¹＝CR¹、Si(R¹)₂O or S, wherein is selected from CR¹＝CR¹The groups O and S are not directly bonded to each other;

z is identical or different on each occurrence and, when no radical is bonded to Z, Z is N or CR²And when a group is bonded to Z, Z is C;

Ar¹、Ar²、Ar³、Ar⁴and Ar⁵Identical or different and are selected from the group consisting of those having 5 to 40 aromatic ring atoms which may be substituted by one or more R³A heteroaromatic ring system substituted by radicals, and having from 6 to 40 aromatic ring atoms which may be substituted by one or more R³A group-substituted aromatic ring system;

R¹in each case identical or different and are selected from H, D, F, C (═ O) R⁴，CN，Si(R⁴)₃，N(R⁴)₂，P(＝O)(R⁴)₂，OR⁴，S(＝O)R⁴，S(＝O)₂R⁴A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; wherein alkyl, alkoxy, alkenyl and alkynyl radicals are mentioned andand the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more R⁴Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁴C＝CR⁴-、-C≡C-、Si(R⁴)₂、C＝O、C＝NR⁴、-C(＝O)O-、-C(＝O)NR⁴-、NR⁴、P(＝O)(R⁴) -O-, -S-, SO or SO₂Replacement;

R²、R³in each case identical or different and are selected from H, D, F, C (═ O) R⁴，CN，Si(R⁴)₃，N(R⁴)₂，P(＝O)(R⁴)₂，OR⁴，S(＝O)R⁴，S(＝O)₂R⁴A linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁴Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁴C＝CR⁴-、-C≡C-、Si(R⁴)₂、C＝O、C＝NR⁴、-C(＝O)O-、-C(＝O)NR⁴-、NR⁴、P(＝O)(R⁴) -O-, -S-, SO or SO₂Replacement;

R⁴in each case identical or different and are selected from H, D, F, C (═ O) R⁵，CN，Si(R⁵)₃，N(R⁵)₂，P(＝O)(R⁵)₂，OR⁵，S(＝O)R⁵，S(＝O)₂R⁵Straight-chain alkyl or alkoxy having 1 to 20 carbon atomsA group, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R⁴May be connected to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁵Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁵C＝CR⁵-、-C≡C-、Si(R⁵)₂、C＝O、C＝NR⁵、-C(＝O)O-、-C(＝O)NR⁵-、NR⁵、P(＝O)(R⁵) -O-, -S-, SO or SO₂Replacement;

R⁵identical or different on each occurrence and selected from the group consisting of H, D, F, CN, alkyl or alkoxy radicals having from 1 to 20 carbon atoms, alkenyl or alkynyl radicals having from 2 to 20 carbon atoms, aromatic ring systems having from 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having from 5 to 40 aromatic ring atoms; wherein two or more R⁵The groups may be linked to each other and may form a ring; and wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may be substituted by F or CN;

r is 1,2 or 3 when p is 1, and r is 1 when p is 0;

when q is 1, s is 0, 1,2 or 3, and when q is 0, s is 1;

p is 0 or 1; wherein, when p is 0, groups bonded to the unit between the square brackets having the label p are directly bonded to each other;

q is 0 or 1; wherein, when q is 0, groups bonded to the unit between brackets having the label q are directly bonded to each other;

n is 0 or 1; wherein, when n is 0, groups bonded to the unit between the square brackets having the label n are directly bonded to each other;

m is 0 or 1; wherein, when m is 0, groups bonded to the unit between square brackets having the label m are directly bonded to each other;

o is 0 or 1; wherein, when o is 0, groups bonded to the unit between brackets having the label o are directly bonded to each other;

i is identical or different on each occurrence and is 1,2,3,4, 5,6, 7 or 8;

wherein at least one compound containing one or more R is present¹U of the group, said R¹The groups are selected from linear alkyl or alkoxy groups having from 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having from 3 to 20 carbon atoms, alkenyl or alkynyl groups having from 2 to 20 carbon atoms, aromatic ring systems having from 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having from 5 to 40 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁴Substituted by groups; and wherein one or more CH of the alkyl, alkoxy, alkenyl and alkynyl groups mentioned₂The group may be represented by-R⁴C＝CR⁴-、-C≡C-、Si(R⁴)₂、C＝O、C＝NR⁴、-C(＝O)O-、-C(＝O)NR⁴-、NR⁴、P(＝O)(R⁴) -O-, -S-, SO or SO₂And (6) replacing.

In the formula of the structural unit, the dotted line indicates a bond to an adjacent structural unit of the polymer.

In the present application, the term "polymer" encompasses polymeric compounds, oligomeric compounds and dendrimers. The polymers of the present invention preferably have from 10 to 10000, more preferably from 10 to 5000 and most preferably from 10 to 2000 structural units (i.e., repeat 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).

The polymers of the invention preferably haveA molecular weight M in the range from 10000 g/mol to 1000000 g/mol_wMore preferably a molecular weight M in the range of 20000 to 500000 g/mol_wAnd most preferably a molecular weight M in the range from 25000 g/mol to 200000g/mol_w. Molecular weight M_wDetermined by GPC (═ gel permeation chromatography) against internal polystyrene standards.

The polymers of the invention are conjugated, semi-conjugated or non-conjugated polymers. Conjugated or semi-conjugated polymers are preferred.

According to the invention, the structural units of the formula (I) can be incorporated into the main chain or into side chains of the polymer. Preferably, however, the structural unit of formula (I) is incorporated into the backbone of the polymer. In the case of incorporation into the side chains of the polymer, the structural units of formula (I) may be monovalent or divalent, which means that they have one or two bonds to adjacent structural units in the polymer.

"conjugated polymers" in the context of the present application are polymers which contain predominantly sp in the main chain²Polymers of hybridized (or otherwise optionally sp-hybridized) carbon atoms, which may also be replaced by correspondingly hybridized heteroatoms. In the simplest case, this means that double bonds and single bonds are present alternately in the main chain, and polymers having units such as meta-bonded benzylidene groups should also be regarded as conjugated polymers, for example in the context of the present application. By "predominantly" is meant that defects that are naturally (instinctively) present and result in interrupted conjugation do not render the term "conjugated polymer" unsuitable. Conjugated polymers are also considered to be polymers having a conjugated main chain and non-conjugated side chains. In addition, the present application likewise mentions conjugation when, for example, arylamine units, arylphosphine units, in particular heterocycles (i.e. conjugation via a nitrogen, oxygen or sulfur atom) and/or organometallic complexes (i.e. conjugation via a metal atom) are present in the main chain. The same applies to conjugated dendrimers. In contrast, units such as simple alkyl bridging groups, (thio) ether, ester, amide or imide linkages, for example, are explicitly defined as nonconjugated segments.

By a semi-conjugated polymer is meant herein a polymer containing conjugated regions separated from each other by non-conjugated moieties, deliberate conjugate breaking agents (e.g. spacer groups) or branches, for example where the relatively long conjugated moieties in the main chain are interrupted by non-conjugated moieties, or where the relatively long conjugated moieties are contained in side chains of the non-conjugated polymer in the main chain. Conjugated and semi-conjugated polymers may also contain conjugated, semi-conjugated or non-conjugated dendrimers.

The term "dendrimer" refers in the present application to a highly branched compound formed by a multifunctional core bonded to monomers branched in a regular structure, so as to obtain a tree-like structure. In this case, both the core and the monomer may exhibit any desired branched structure consisting of purely organic units and organometallic or coordination compounds. "dendritic" in this context should generally be as for example m.(Angew. chem., int.Ed.1999,38,885).

The term "structural unit" in this application refers to a unit in which the specified structure appears multiple times in the polymer. It may occur more than once in succession in the polymer and/or in isolated form. Preferably, a plurality of structural units having the specified structure are present in the polymer, more preferably from 10 to 1000 times, most preferably from 50 to 500 times.

It is also preferred that the structural units in the context of the present application are derived from monomers used in the polymerization, wherein the reactive groups of the monomers are reacted according to their chemical reactivity and purpose. For example, in the case of a monomer containing two bromine atoms as reactive groups in a Suzuki polymerization reaction, the structural units formed in the polymer are characterized in that they correspond to the monomer structure, except that no bromine atom is present and the bond bonded to the bromine atom now becomes a bond bonded to an adjacent structural unit. In the case of monomers containing a crosslinker group or a precursor group of a crosslinker group, one or more further reactions of the crosslinker group or the corresponding precursor group of the crosslinker group can take place here until the corresponding final structural unit of the polymer is obtained.

In the context of the present invention, an aryl group contains 6 to 40 aromatic ring atoms, none of which is a heteroatom. In the context of the present invention, aryl group means a simple aromatic ring, i.e. benzene, or a fused aromatic polycyclic ring, e.g. naphthalene, phenanthrene or anthracene. In the context of the present application, a fused aromatic polycyclic ring consists of two or more simple aromatic rings fused to one another. Here, fused between rings means that the rings share at least one side with each other.

In the context of the present invention, heteroaryl groups contain 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom of the heteroaryl group is preferably selected from N, O and S. In the context of the present invention, heteroaryl groups refer to simple heteroaromatic rings, such as pyridine, pyrimidine or thiophene, or fused heteroaromatic polycycles, such as quinoline or carbazole. In the context of the present application, a fused heteroaromatic polycyclic consists of two or more simple heteroaromatic rings fused to one another. Here, fused between rings means that the rings share at least one side with each other.

Aryl or heteroaryl groups, each of which may be substituted by the abovementioned groups and may be attached to the aromatic or heteroaromatic system via any desired position, refer in particular to groups derived from: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chicory, perylene, triphenylene, fluoranthene, benzanthracene, triphenylene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, thiophene

Oxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxaloimidazoles,

Azole, benzo

Azoles, naphthoAzoles, anthracenes

Azole, phenanthro

Oxazole, iso

Oxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarbazine, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2,3-

Oxadiazole, 1,2,4-

Oxadiazole, 1,2,5-Oxadiazole, 1,3,4-Oxadiazoles, 1,2, 3-thiadiazoles, 1,2, 4-thiadiazoles, 1,2, 5-thiadiazoles, 1,3, 4-thiadiazoles, 1,3, 5-triazines, 1,2, 4-triazines, 1,2, 3-triazines, tetrazoles, 1,2,4, 5-tetrazines, 1,2,3, 4-tetrazines, 1,2,3, 5-tetrazines, purines, pteridines, indolizines and benzothiadiazoles.

In the context of the present invention, an aromatic ring system contains 6 to 40 carbon atoms in the ring system and does not include any heteroatoms as aromatic ring atoms. Thus, in the context of the present invention, an aromatic ring system does not contain any heteroaryl groups. In the context of the present invention, an aromatic ring system refers to a system which does not necessarily contain only aryl groups, but in which a plurality of aryl groups may also be bonded by single bonds or non-aromatic units, such as one or more optionally substituted C, Si, N, O or S atoms. In this case, the non-aromatic units preferably contain less than 10% of atoms other than H, based on the total number of atoms other than H in the system. For example, systems such as 9,9 '-spirobifluorene, 9' -diarylfluorene, triarylamines, diaryl ethers and stilbene should also be considered as aromatic ring systems in the context of the present invention, and also systems in which two or more aryl groups are linked, for example by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group. Furthermore, systems in which two or more aryl groups are connected to each other by single bonds, for example systems such as biphenyl and terphenyl, should also be considered as aromatic ring systems in the context of the present invention.

Preferably, an aromatic ring system refers to a chemical group in which the aryl groups present are conjugated to each other. This means that the aryl groups present must be bonded to one another by single bonds or by linking units having free pi electron pairs which can participate in conjugation. The linking unit here is preferably selected from the group consisting of a nitrogen atom, a single C ═ C unit, a single C ≡ C unit, a plurality of C ≡ C units conjugated with one another and/or C ≡ C units, -O-and-S-.

In the context of the present invention, heteroaromatic ring systems contain 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and/or S. Heteroaromatic ring systems conform to the definition of aromatic ring systems above, but have at least one heteroatom as one of the aromatic ring atoms. In this way, it differs from an aromatic ring system in the sense defined in the present application, which, according to this definition, cannot contain any heteroatoms as aromatic ring atoms.

An aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms means in particular radicals derived from: the groups mentioned above under aryl and heteroaryl groups, and biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, triindene, isotridecyl, spirotriindene, spiroisotridecyl, indenocarbazole, or combinations of these groups.

In the context of the present invention, wherein the individual hydrogen atoms or CH₂Straight-chain alkyl radicals having from 1 to 20 carbon atoms and branched or cyclic alkyl radicals having from 3 to 20 carbon atoms and alkenyl or alkynyl radicals having from 2 to 40 carbon atoms, which radicals may also be substituted by the radicals mentioned above under the definition of the radicals, preferably mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, heptenyl, cycloheptenyl, cyclooctenyl, ethynyl, propynyl, butynyl, Pentynyl, hexynyl or octynyl groups.

Preferred alkyl groups having 1 to 20 carbon atoms are depicted in the following table:

wherein the individual hydrogen atoms or CH₂Alkoxy or thioalkyl radicals having 1 to 20 carbon atoms which radicals may also be replaced by the radicals mentioned above under the definition of radicals, preferably mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, 2-methylbutyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2, 2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, tert-butylthio, tert-pentylthio, n-pentylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, cyclooct, Trifluoromethylthio, pentafluoroethylthio, 2,2, 2-trifluoroethylthio, ethyleneThio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

In the context of the present application, the expression that two or more groups together may form a ring especially means that the two groups are connected to each other by a chemical bond. However, in addition, the above expression also means that if one of the two groups is hydrogen, the second group is bonded to the position to which the hydrogen atom is bonded, thereby forming a ring.

Preferably, U is identical or different on each occurrence and is selected from C (R)¹)₂O and S; more preferably, U is C (R)¹)₂。

Preferably, Z is CR when no group is bonded to Z²And when a group is bonded to Z, Z is C.

Preferably, Ar¹、Ar²、Ar³、Ar⁴And Ar⁵Are identical or different on each occurrence and are selected from the group consisting of those having from 6 to 25 aromatic ring atoms which may be substituted by one or more R¹An aromatic ring system substituted with a group, and having 5 to 25 aromatic ring atoms and which may be substituted by one or more R²A group-substituted heteroaromatic ring system. More preferably, Ar¹、Ar²、Ar³、Ar⁴And Ar⁵In each case identical or different and selected from the group consisting of benzene, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, indenofluorene, spirobifluorene, dibenzofuran, dibenzothiophene, carbazole, indenocarbazole and indolocarbazole, each of which may be substituted by one or more R¹And (4) substituting the group. Even more preferably, Ar⁴And Ar⁵Is benzene, which may be substituted by one or more R¹And (4) substituting the group. Even more preferably, Ar¹、Ar²And Ar³In each case identical or different and are selected from the group consisting of benzene, biphenyl, fluorene, phenanthrene, indenofluorene and spirobifluorene, which may be substituted by one or more R¹And (4) substituting the group. Most preferably, Ar¹And Ar³Selected from benzene, which may be substituted by one or more R¹And (4) substituting the group.

Preferred Ar is¹To Ar⁵The group is selected from the following groups:

wherein the dotted lines indicate the attachment positions, and

wherein R is³The radical being bonded to the aromatic ring in a non-specific manner means R³The radicals can in each case be bonded to any unoccupied position of the ring in question.

A above¹To A¹⁰Preferred embodiments of the groups are as follows:

wherein the dashed lines indicate the attachment locations.

R¹In each case preferably identical or different and selected from H, D, F, CN, Si (R)⁴)₃，OR⁴Straight-chain alkyl and alkoxy groups having from 1 to 10 carbon atoms, branched or cyclic alkyl and alkoxy groups having from 3 to 10 carbon atoms, and aromatic ring systems having from 6 to 20 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; and wherein the alkyl and alkoxy groups mentioned and the aromatic ring systems mentioned may each be substituted by one or more R⁴And (4) substituting the group. More preferably, R¹In each case identical or different and are selected from H, D, F, linear alkyl radicals having from 1 to 10 carbon atoms and branched or cyclic alkyl radicals having from 3 to 10 carbon atoms. Even more preferably, R¹Selected from the group consisting of straight chain alkyl groups having 1 to 10 carbon atoms and branched chains having 3 to 10 carbon atomsAn alkyl group.

Particularly preferably, those two U groups which are directly adjacent to the bridgehead carbon atom, i.e. in the benzyl position, carry R¹Group R¹The radical not being H or D, preferably R¹The radicals are selected from F, CN, Si (R)⁴)₃，OR⁴Straight-chain alkyl and alkoxy groups having from 1 to 10 carbon atoms, branched or cyclic alkyl and alkoxy groups having from 3 to 10 carbon atoms, and aromatic ring systems having from 6 to 20 aromatic ring atoms; wherein two or more R¹Or R²Or R³The groups may be linked to each other and may form a ring; and wherein the alkyl and alkoxy groups mentioned and the aromatic ring systems mentioned may each be substituted by one or more R⁴And (4) substituting the group.

In a preferred embodiment, the structural unit of the formula (I) comprises at least one structural element having two R¹The U group of the group, the two R¹The groups are linked to each other and form a ring, such that the U group is a spiro atom. Preferably, there are two R's in the U group¹The ring formed by the group is selected from the group consisting of cyclopropane, cyclobutane, cyclopentane, cyclohexane, fluorene, dibenzopyran, dihydroacridine and pyran.

Preferred of the structural units of the formula (I)

The units are selected from units of the formula:

wherein the free bond is a bond to the remainder of the structural unit of formula (I).

Furthermore, preferably, the above units are selected from units of the formula:

in which the corresponding freedomEach position can be represented by R²A group and wherein the dotted line is a bond to the remainder of the structural unit of formula (I).

Particularly preferably, the units of the formulae E-a to E-c described above are selected from the following units:

wherein the free bonds are bonds to the remainder of the structural units of formula (I), and wherein the units mentioned are particularly preferred the units E-a-1 and E-b-1, and most preferred the unit E-a-1.

Preferred embodiments of the E-a, E-b and E-c units are the following units:

wherein the dotted line represents a bond to the remainder of the structural unit of formula (I), and wherein the semi-circular bond means that the two R's involved¹The groups are linked to each other and form a ring.

Particularly preferred

The unit is selected from the following formulas:

wherein the dotted line is a bond to the remainder of the structural unit of formula (I). Preferably, in the above formula, the bonds to the remainder of the building blocks are located in the meta and para positions of the two U units, as shown in the E-1 unit.

Among the formulae shown above, the most preferred is formula b.

R²Preferably identical or different on each occurrence and selected from the group consisting of H, D, F, straight-chain alkyl radicals having from 1 to 10 carbon atoms, branched-chain alkyl radicals having from 3 to 10 carbon atoms, aromatic ring systems having from 6 to 20 aromatic ring atoms and heteroaromatic ring systems having from 5 to 20 aromatic ring atoms, where the alkyl radicals, aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R⁴And (4) substituting the group. More preferably, R²In each case identical or different and are selected from H and straight-chain alkyl radicals having from 1 to 10 carbon atoms and branched-chain alkyl radicals having from 3 to 10 carbon atoms.

R³Are preferably identical or different on each occurrence and are selected from the group consisting of H, D, F, linear alkyl radicals having from 1 to 10 carbon atoms, branched alkyl radicals having from 3 to 10 carbon atoms, aromatic ring systems having from 6 to 20 aromatic ring atoms, and heteroaromatic ring systems having from 5 to 20 aromatic ring atoms, where the alkyl radicals, aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R⁴And (4) substituting the group. More preferably, R³In each case identical or different and are selected from H and straight-chain alkyl radicals having from 1 to 10 carbon atoms and branched-chain alkyl radicals having from 3 to 10 carbon atoms.

R⁴In each case preferably identical or different and are selected from H, D, F, CN, Si (R)⁵)₃，OR⁵Having 1 to 10 carbonsLinear alkyl and alkoxy groups of atoms, branched alkyl and alkoxy groups having 3 to 10 carbon atoms, aromatic ring systems having 6 to 20 aromatic ring atoms, and heteroaromatic ring systems having 5 to 20 aromatic ring atoms; wherein two or more R⁴The groups may be linked to each other and may form a ring; and wherein the alkyl and alkoxy radicals mentioned and the aromatic and heteroaromatic ring systems mentioned may each be substituted by one or more R⁵And (4) substituting the group.

The index r is preferably 1 or 2, more preferably 1.

The label s is preferably 1 or 2, more preferably 1.

The label p is preferably 1.

The index q is preferably 1.

The index n is preferably 0.

The index m is preferably 1.

The mark o is preferably 1.

The index i is preferably 1,2 or 3, more preferably 1 or 2, and most preferably 1.

Preferred embodiments of the structural elements of the formula (I) are selected from the structural elements of the formulae (I-1) to (I-6)

Among the above formulae, the formula (I-1) is particularly preferred.

Preferred structural units of the formula (I) are the structural units shown in the table below, where the variables Ar appearing in the formula (I) are selected as indicated below¹To Ar⁵M, n, o, p, q, r and s, and wherein the structural units

Selected from one of the formulae specified below.

Preferred embodiments of the structural units of the formula (I) are shown in the following table:

the proportion of structural units of the formula (I) in the polymer is in the range from 1 mol% to 100 mol%. In a preferred embodiment, the proportion of structural units of the formula (I) in the polymer is in the range from 30 to 70 mol%, more preferably in the range from 40 to 60 mol%, based on 100 mol% of the total copolymerizable monomers present as structural units in the polymer, which means that the polymer of the invention, in addition to one or more structural units of the formula (I), also has other structural units than structural units of the formula (I).

Such building blocks which differ from building blocks of formula (I) include those disclosed and listed in WO 2002/077060A1, WO 2005/014689A2 and WO 2013/156130. These are incorporated by reference into the disclosure of the present patent application. Other structural units may for example come from the following classes:

class 1: units that affect the hole injection and/or hole transport properties of the polymer;

class 2: units that affect the electron injection and/or electron transport properties of the polymer;

class 3: a unit having a combination of respective units of class 1 and class 2;

class 4: a unit that changes the light emission characteristics in such a manner that electrophosphorescence can be obtained instead of electroluminescence;

class 5: a unit that improves the transition from the singlet state to the triplet state;

class 6: units that affect the emission color of the resulting polymer;

class 7: units commonly used as polymer backbones;

class 8: units that interrupt the delocalization of pi electrons in the polymer and thus shorten the conjugation length in the polymer.

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

Structural units from class 1 having hole-injecting and/or hole-transporting properties are, for example, triarylamines, benzidines, tetraaryl-p-phenylenediamines, triarylphosphines, phenothiazines, thiophenes

Oxazines, dihydrophenazines, thianthrenes, dibenzo-p-dioxanes, thiophenesThiophene, carbazole, azulene, thiophene, pyrrole and furan derivatives and other O, S or N-containing heterocyclic compounds.

Structural units from class 2 having electron-injecting and/or electron-transporting properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine,

Oxadiazoles, quinolines, quinoxalines, anthracenes, benzanthracenes, pyrenes, perylenes, benzimidazoles, triazines, ketones, phosphine oxides, and phenazine derivatives, as well as triarylboranes and other heterocyclic compounds containing O, S or N.

It may be preferred that the polymer of the present invention contains units from class 3, wherein the structures that increase hole mobility and increase electron mobility (i.e., units from classes 1 and 2) are directly bonded to each other, or there are structures that increase both hole mobility and electron mobility. Some of these units can be used as luminaries and shift the emission color to green, yellow or red. Thus, its use is suitable for producing other luminescent colors, for example from polymers which initially emit blue light.

The structural unit of the 4 th class is a structural unit capable of efficiently emitting light from a triplet state even at room temperature, i.e., a structural unit exhibiting electrophosphorescence rather than electrophosphorescence, which often leads to an increase in energy efficiency. Suitable for this purpose are, above all, compounds containing heavy atoms having an atomic number greater than 36. Preferred compounds are those containing d or f transition metals, which satisfy the above conditions. Particularly preferred here are the corresponding structural units containing elements of groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt). Building blocks which can be used here for the polymers according to the invention include, for example, various complexes, as described, for example, in WO 02/068435A 1, WO 02/081488A 1, EP 1239526A 2 and WO 2004/026886A 2. Corresponding monomers are described in WO 02/068435A 1 and WO 2005/042548A 1.

Structural units of class 5 are those which improve the transition from the singlet state to the triplet state and, when used in combination with structural elements of class 4, improve the phosphorescent properties of these structural elements. Units useful for this purpose are in particular carbazole and bridged carbazole dimer units, as described, for example, in WO2004/070772 a2 and WO 2004/113468 a 1. Further useful for this purpose are ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds as described, for example, in WO 2005/040302 a 1.

A building block of class 6 is a building block (together with those mentioned above) that comprises at least one other aromatic structure or another conjugated structure that is not in the above-mentioned class, i.e. has little effect on the charge carrier mobility, is not an organometallic complex or has no effect on the singlet-triplet transition. Such structural elements may influence the luminescent color of the resulting polymer. Depending on the unit, they can therefore be used as luminophores. Preferably having an aromatic structure of 6 to 40 carbon atoms, or are tolane, stilbene or bisstyrylarylene derivatives which may each be substituted by one or more R groups. Is particularly excellentOptionally incorporating 1, 4-or 9, 10-anthracenylene, 1, 6-or 2, 7-or 4, 9-pyrene, 3, 9-or 3, 10-perylene, 4,4 '-tolane, 4,4' -stilbene, benzothiadiazole and the corresponding oxygen derivatives, quinoxaline, phenothiazine, thiophene

Oxazines, dihydrophenazines, bis (thiophenyl) arylenes, oligo (thiophenylidenes), phenazines, rubrenes, pentacene or perylene derivatives, preferably substituted or preferably conjugated push-pull systems (systems substituted with donor and acceptor substituents) or preferably substituted systems such as squaraines or quinacridones.

The structural unit of the 7 th class is a unit including an aromatic structure having 6 to 40 carbon atoms, which is generally used as a polymer backbone. 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-dihydrodibenzoxepin derivatives and cis-indenofluorene and trans-indenofluorene derivatives, and also 1, 2-phenylene, 1, 3-phenylene or 1, 4-phenylene, 1, 2-naphthylene, 1, 3-naphthylene or 1, 4-naphthylene, 2,2' -biphenylene, 3' -biphenylene or 4,4' -biphenylene, 2,2' -bi-1, 1 '-naphthylene, 3' -bi-1, 1 '-naphthylene or 4,4' -bi-1, 1 '-naphthylene or 2,2' -tetracene, 3 '-tetracene or 4,4' -tetracene derivatives.

Structural units of class 8 are those having a conjugated-interrupting property, for example by meta bonding, steric hindrance or the use of saturated carbon or silicon atoms. Such compounds are disclosed, for example, in WO2006/063852, WO 2012/048778 and WO 2013/093490. The conjugate-breaking properties of the building blocks of class 8 are manifested in particular by a blue-shift of the absorption edge of the polymer.

Preference is given to polymers of the invention which comprise both structural units of the formula (I) and additionally one or more units from the classes 1 to 8. Particularly preferred are the structural units of class 1, class 7 and class 8. It may also be preferred that there is more than one further structural element from one of the above categories.

If the polymer of the invention comprises one or more units selected from classes 1 to 8, one or more of these units, preferably from class 1, may have one or more crosslinkable groups, preferably one crosslinkable group.

The polymers of the invention are homopolymers or copolymers composed of structural units of the formula (I). The polymers of the invention may be linear or branched, which is preferably linear. The copolymers of the present invention may have one or more structural units of formula (I) and potentially one or more other structures from classes 1 to 8 detailed above.

The copolymers of the invention may have random, alternating or block structures, or alternatively two or more of these structures. More preferably, the copolymers of the present invention have a random or alternating structure. More preferably, the copolymer is a random or alternating copolymer. The manner in which copolymers having a block structure can be obtained and further structural elements which are particularly preferred for this purpose are described in detail, for example, in WO 2005/014688A 2. This patent is incorporated by reference into the present application. It should again be emphasized here that the polymers can also have a dendritic structure.

In another embodiment of the present invention, the polymer of the present invention comprises at least one, preferably one, structural unit comprising a crosslinkable Q group.

"crosslinkable Q group" means in the context of the present invention a functional group which is capable of entering into a reaction and thus forming insoluble compounds. The reaction may be carried out with another identical Q group, another different Q group, or any other portion of the same or another polymer chain. The crosslinkable group is thus a reactive group. As a result of the reaction of the crosslinkable groups, the corresponding crosslinked polymers are provided. Chemical reactions can also be carried out in the layer, resulting in an insoluble layer. Crosslinking can generally be promoted by heating or by UV radiation, microwave radiation, x-radiation or electron beams, and optionally in the presence of initiators. In the context of the present invention, "insoluble" preferably means that the solubility of the polymers of the invention in organic solvents after the crosslinking reaction, i.e. after the reaction of the crosslinkable groups, at room temperature is lower than the solubility of the corresponding uncrosslinked polymers of the invention in the same organic solvents, down to at least 1/3, preferably down to at least 1/10.

The crosslinkable Q group can be incorporated in the polymers of the invention in this way by means of monomers which are correspondingly substituted by crosslinkable groups. Alternatively and also preferably, in particular cases, the crosslinkable Q group may be passed through a precursor Q as part of the monomer^*Groups are introduced into the polymer. In this case, the polymer obtained first carries the precursor Q^*A group. In the reaction on the polymer, Q is subsequently reacted^*The group is converted into the actual crosslinkable Q group. Such a precursor Q^*One example of a group is a terminal aldehyde group, which can be converted to a terminal alkenyl group by, for example, a Wittig reaction. The latter are the actual crosslinkable Q groups.

In a first embodiment, the structural units bearing a crosslinkable Q group may be selected from structural units of formula (I).

Preferred structural units correspond to one of the following formulae (I-Q-1) to (I-Q-6):

wherein Q is a crosslinkable group, and is preferably as defined in the preferred embodiments specified below, and wherein the other variables are as defined above.

Particularly preferred structural units of the formula (I) which comprise a crosslinkable Q group are the following structural units:

wherein Q is a crosslinkable group, and is preferably as defined in the preferred embodiments specified below, and wherein the other variables are as defined above.

In an alternative embodiment, the building block bearing a Q group is selected from the building blocks of classes 1 to 8 described above, preferably from the building blocks of classes 1, 7 and 8 described above, more preferably from the building block of class 1 described above.

Preferred crosslinkable Q groups according to the invention 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, especially a terminal or cyclic alkenyl, terminal dienyl or terminal alkynyl group having 2 to 40 carbon atoms, preferably having 2 to 10 carbon atoms, where the individual CH's are₂The radicals and/or the individual hydrogen atoms may also be replaced by the abovementioned R radicals.

b)Alkenyloxy, dienyloxy or alkynyloxy groups：

Also suitable are alkenyloxy, dienyloxy or alkynyloxy groups, preferably alkenyloxy groups.

c)Acrylic acid group：

Also suitable are acrylic acid units in the broadest sense, preferably acrylates, acrylamides, methacrylates and methacrylamides. Acrylic acid C is particularly preferred_1-10Alkyl esters and methacrylic acid C_1-10-an alkyl ester.

The crosslinking reaction of the groups mentioned under a) to c) above can take place by free-radical, cationic or anionic mechanisms or by cycloaddition.

It may be desirable to add a suitable initiator to the crosslinking reaction. For free-radical crosslinkingSuitable initiators are, for example, dibenzoyl peroxide, AIBN or TEMPO. Suitable initiators for cationic crosslinking are, for example, AlCl₃、BF₃Triphenylmethyl perchlorate or hexachloroantimonic acidSuitable initiators for anionic crosslinking are bases, in particular butyllithium.

However, in a preferred embodiment of the invention, the crosslinking is carried out without addition of an initiator and is initiated exclusively thermally. The reason for this preferred choice is that: the absence of initiator prevents contamination of the layers, which can lead to degradation of device properties.

d)Oxetanes and oxiranes：

Another suitable class of crosslinkable Q groups are oxetanes and oxiranes, which undergo cationic crosslinking by ring opening.

It may be desirable to add a suitable initiator to the crosslinking reaction. Suitable initiators are, for example, AlCl₃、BF₃Triphenylmethyl perchlorate or hexachloroantimonic acid

Photo acids may also be added as initiators.

e)Silane：

Also suitable as a class of crosslinkable groups are silane groups SiR₃Wherein at least two R groups, preferably all three R groups, are Cl or alkoxy groups having 1 to 20 carbon atoms.

The groups are reacted in the presence of water to give oligosiloxanes or polysiloxanes.

f)Cyclobutane radical

The crosslinkable Q groups mentioned above under a) to f) are generally known to the person skilled in the art, as are suitable reaction conditions for the reaction of these groups.

Preferred crosslinkable Q groups include alkenyl groups of formula Q1 below, dienyl groups of formula Q2 below, alkynyl groups of formula Q3 below, alkenyloxy groups of formula Q4 below, dienyloxy groups of formula Q5 below, alkynyloxy groups of formula Q6 below, acrylic groups of formulae Q7 and Q8 below, oxetanyl groups of formulae Q9 and Q10 below, oxirane groups of formula Q11 below, and cyclobutane groups of formulae Q12, Q13 and Q14 below:

r in the above-mentioned Q1 to Q8, Q11, Q13 and Q14¹¹、R¹²、R¹³And R¹⁴The radicals are identical or different on each occurrence and are H or straight-chain or branched alkyl radicals having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. More preferably, R¹¹、R¹²、R¹³And R¹⁴Is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and most preferably is H or methyl. The markers used in formulae Q1 to Q14 are defined as follows: s is 0 to 8; and t is 1 to 8.

Ar in formula Q14¹⁰Selected from those having 6 to 40 aromatic ring atoms and which may be substituted by one or more R¹¹An aromatic ring system substituted with a group, and having 5 to 40 aromatic ring atoms and which may be substituted by one or more R¹¹A group-substituted heteroaromatic ring system.

The dotted bonds in formulae Q1 to Q11 and Q14 and in formulae Q12 and Q13 represent the attachment of the crosslinkable group to the structural unit.

The crosslinkable groups of the formulae Q1 to Q14 may be linked directly to the structural unit or via further mono-or polycyclic aromatic or heteroaromatic ring systems Ar¹⁰Indirectly to a structural unit as shown in formulas Q15 through Q28 below:

wherein Ar is¹⁰Selected from those having 6 to 40 aromatic ring atoms and which may be substituted by one or more R¹¹An aromatic ring system substituted with a group, and having 5 to 40 aromatic ring atoms and which may be substituted by one or more R¹¹A group-substituted heteroaromatic ring system, and wherein:

R¹¹、R¹²、R¹³and R¹⁴The radicals are identical or different on each occurrence and are H or straight-chain or branched alkyl radicals having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. More preferably, R¹¹、R¹²、R¹³And R¹⁴Is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and most preferably is H or methyl. The markers used in formulae Q15 to Q28 are defined as follows: s is 0 to 8; and t is 1 to 8.

Particularly preferred crosslinkable Q groups are the following:

R¹¹、R¹²、R¹³and R¹⁴The radicals are identical or different on each occurrence and are H or straight-chain or branched alkyl radicals having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. More preferably, R¹¹、R¹²、R¹³And R¹⁴The group is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and most preferably methyl.

The markers used in formulae Q1a to Q28a are defined as follows: s is 0 to 8, and t is 1 to 8.

Very particularly preferred crosslinkable Q groups are the following:

the polymers of the invention comprising structural units of formula (I) are generally prepared by polymerization of one or more monomer types, wherein at least one monomer gives rise to a structural unit of formula (I) 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 or C-N coupling are the following:

(A) polymerizing SUZUKI;

(B) YAMAMOTO polymerization;

(C) STILLE polymerization;

(D) HECK polymerization;

(E) polymerizing NEGISHI;

(F) SONOGASHIRA polymerization;

(G) carrying out HIYAMA polymerization; and

(H) HARTWIG-BUCHWALD polymerization.

How the polymerization can be carried out by these methods, and how the polymer can subsequently be isolated and purified from the reaction medium, is known to the person skilled in the art and is described in detail in documents such as WO 03/048225a2, WO 2004/037887a2 and WO 2004/037887a 2.

The C-C coupling is preferably selected from the group consisting of SUZUKI coupling, YAMAMOTO coupling and STILLE coupling; the C-N coupling is preferably a HARTWIG-BUCHWALD coupling.

The present invention therefore also provides a process for preparing the polymers of the invention, which is characterized in that they are prepared by SUZUKI polymerization, YAMAMOTO polymerization or HARTWIG-BUCHWALD polymerization, preferably by SUZUKI polymerization.

The synthesis of the polymers of the invention requires monomeric compounds which introduce the structural units of formula (I) into the polymer.

Accordingly, the present invention also provides monomers of the formula (M)

Wherein the variables present are as defined above, and wherein X is identical or different in each case and is a leaving group suitable for polymerization.

Preferably, X is identical or different on each occurrence and is selected from the group consisting of H, D, halogen, preferably chlorine, bromine or iodine, O-tosylate, O-triflate, O-sulfonate, boronic acid, boronic ester, partially fluorinated silyl group, diazo group and organotin compounds. When m is 1, the X group bonded to the left-hand side is more preferably selected from halogen, preferably chlorine, bromine or iodine, boronic acids and boronic esters. When m is 0, the X group bonded to the left-hand side is more preferably H. When o is 1, the X group bonded to the right hand side is more preferably selected from halogen, preferably chlorine, bromine or iodine, boronic acids and boronic esters. When o is 0, the X group bonded to the right-hand side is more preferably H.

For the other variables present, the preferred embodiments are the same as specified above for the structural unit of formula (I).

Monomers are preferably synthesized using Buchwald coupling, Suzuki coupling and bromination. In a preferred method (scheme 1), an amine bromide is reacted with a boronic acid derivative of the formula

Wherein BS is a boronic acid derivative in a Suzuki coupling reaction. The resulting coupled product is then brominated to give the compound of formula (M) which can be used as a monomer.

Scheme 1

In an alternative preferred process (scheme 2), an amine is reacted with a halogen-substituted derivative of the formula:

in the Buchwald coupling reaction, wherein BS is a boronic acid derivative, and Ar is an aromatic or heteroaromatic ring system, and x is 0 or 1. The resulting coupled product is then brominated to give the compound of formula (M) which can be used as a monomer.

Scheme 2

The monomers of formula (M) are used to prepare the polymers of the invention comprising at least one structural unit of formula (I) as defined above.

The polymers of the invention can be used as pure substances or as mixtures with any other polymeric, oligomeric, dendritic or low molecular weight substance. Low molecular weight substances are understood in the context of the present invention to mean compounds having a molecular weight in the range from 100g/mol to 3000g/mol, preferably from 200g/mol to 2000 g/mol. These other substances may for example improve the electronic properties or emit light themselves. Mixtures are understood in this context to mean mixtures which comprise at least one polymeric component. In this way, one or more polymer layers can be produced which consist of a mixture (blend) of one or more polymers according to the invention having structural units of the formula (I) and optionally one or more further polymers with one or more low molecular weight substances.

Accordingly, the present invention 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.

The invention also provides solutions and formulations consisting of one or more polymers or polymer blends of the invention in one or more solvents. The ways in which such solutions can be prepared are known to the person skilled in the art and are described, for example, in WO 02/072714 a1, WO 03/019694 a2 and the references cited therein.

These solutions can be used for example for the production of thin polymer layers 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 light-induced in-situ polymerization and in-situ crosslinking, for example in-situ UV photopolymerization or photopatterning. The corresponding polymers may be used here in pure form or as preparations or mixtures of these polymers as described above. These may be used with or without the addition of solvents and/or binders. Suitable materials, processes and apparatus for the above process are described, for example, in WO 2005/083812 a 2. Possible binders are, for example, polystyrene, polycarbonate, poly (meth) acrylate, polyacrylate, polyvinyl butyral and similar photoneutral polymers.

Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, bis-xylene

Alkanes, phenoxytoluenes, especially 3-phenoxytoluene, (-) -fenchone, 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, 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, tripropyl dibutyl etherAlcohol 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.

The invention therefore also provides for the use of polymers which contain structural units having crosslinkable Q groups for preparing crosslinked polymers. The crosslinkable group, which is more preferably a vinyl group or an alkenyl group, is preferably incorporated into the polymer by a WITTIG reaction or WITTIG-like reaction. If the crosslinkable group is a vinyl group or an alkenyl group, crosslinking can be carried out by free radical or ionic polymerization, which can be induced by heat or by radiation. Preferred are free radical polymerizations induced under heat, preferably at temperatures below 250 ℃, more preferably below 230 ℃.

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

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

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

(b) free radical or ionic crosslinking, preferably free radical crosslinking, which can be induced thermally or by radiation, preferably thermally.

The crosslinked polymers prepared by the process of the present invention are insoluble in all standard solvents. In this way, a defined layer thickness can be produced which does not dissolve again or partially even by applying subsequent layers.

The invention therefore also relates to a crosslinked polymer obtainable by the above process. As mentioned above, the crosslinked polymer is preferably manufactured in the form of a crosslinked polymer layer. Due to the insolubility of the crosslinked polymer in all solvents, another layer may be applied from the solvent to the surface of such a crosslinked polymer layer by the above-described technique.

The polymers of the invention may be used in electronic or optoelectronic devices or in their manufacture.

The present application therefore also provides for the use of the polymers according to the 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).

The present application also provides a device selected from the above devices comprising at least one polymer of the invention. Preferably, the polymer is present in the hole transport layer.

The organic electroluminescent device may include other layers in addition to the cathode, the anode, the light-emitting layer, and the hole transport layer. These are selected in each case, for example, from one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, electron-blocking layers, exciton-blocking layers, interlayers, Charge-Generation layers (IDMC 2003, Taiwan; Session 21OLED (5), T.Matsumoto, T.Nakada, J.endo, K.Mori, N.Kawamura, A.Yokoi, J.Kido, Multiphoton Organic EL Device Having had Charge Generation Layer) and/or Organic or inorganic p/n junctions.

The layer sequence in the organic electroluminescent device comprising the polymers according to the invention is preferably as follows:

anode-hole injection layer-hole transport layer-optionally further hole transport layer(s) -light-emitting layer-optionally hole blocking layer-electron transport layer-cathode. Additionally, other layers may be present in the OLED.

A preferred embodiment of an OLED comprising the polymers of the invention is a hybrid device in which there are one or more layers processed from solution and one or more layers made by vapor deposition of low molecular weight substances. These are also known as combined PLED/SMOLED (polymer light emitting diode/small molecule organic light emitting diode) systems. Preferably, in the device of the invention, the layers between the anode and the light-emitting layer are applied from solution, and the layers between the light-emitting layer and the cathode are preferably applied by a sublimation method.

The layer from solution is preferably produced by spin coating, or by any printing method, such as screen printing, flexography, nozzle printing or offset printing, more preferably by LITI (photo induced thermal imaging, thermal transfer printing) or inkjet printing.

In the case of the application of layers by sublimation, the material is in a vacuum sublimation system at less than 10^-5Mbar, preferably less than 10^-6An initial pressure of mbar is applied by vapor deposition. However, in this case the initial pressure may also be even lower, e.g. less than 10^-7Millibar.

In an alternative embodiment, the layer or layers are applied by the OVPD (organic vapor deposition) method or by sublimation with the aid of a carrier gas. In this case, the material is at 10^-5Applied at a pressure between mbar and 1 bar. A particular example of such a method is the OVJP (organic vapour jet printing) method, in which the material is applied directly through a nozzle and is thus structured (for example m.s. arnold et al, appl.phys. lett.2008,92,053301).

The ways in which OLEDs can be manufactured are known to the person skilled in the art and are described in detail, for example, as a general method in WO2004/070772 a2, which must be adapted appropriately to the individual case.

The polymers of the invention are particularly suitable for use in hole transport layers of OLEDs. Here, the hole transport layer refers to a layer adjacent to the light-emitting layer on the anode side.

However, the polymers of the invention can also be used in Hole Injection Layers (HIL), Electron Blocking Layers (EBL) and light-emitting layers. When polymers are used in the light-emitting layer, they preferably act as matrix materials and in particular as hole-transporting and/or wide-bandgap matrix materials. The hole injection layer is in particular a layer which directly adjoins the anode and is arranged between the anode and the hole transport layer. The hole blocking layer is in particular a layer which directly adjoins the light-emitting layer on the cathode side and is arranged between the light-emitting layer and the electron transport layer.

Preferred embodiments of different functional materials in electronic devices are listed below.

Preferred fluorescent compounds are selected from the class of arylamines. In the context of the present invention, arylamine or aromatic amine means a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, more preferably a fused ring system having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chicory amines or aromatic chicory diamines. Aromatic anthracenamines are understood to mean compounds in which one diarylamino group is bonded directly to the anthracene group, preferably in the 9 position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 position. Aromatic pyrene amines, pyrene diamines, chicory amines and chicory diamines are defined in a similar manner to this, wherein the diarylamino group is preferably bonded to pyrene in position 1 or in position 1, 6. Other preferred luminescent compounds are indenofluorenylamines or indenofluorenyldiamines, e.g. according to WO2006/108497 or WO 2006/122630; benzindenofluorenamines or benzindenofluorenediamines, for example according to WO 2008/006449; and dibenzoindenofluoreneamines or dibenzoindenofluorenediamines, for example according to WO 2007/140847; and indenofluorene derivatives having a fused aryl group, which are disclosed in WO 2010/012328. Also preferred are pyrene arylamines as disclosed in WO 2012/048780 and WO 2013/185871. Also preferred are the benzaindenofluoreneamines disclosed in WO 2014/037077, the benzafluoreneamines disclosed in WO 2014/106522, the extended benzaindenofluorenes disclosed in WO 2014/111269 and WO 2017/036574, the thiophenes disclosed in WO 2017/028940 and WO 2017/028941

Oxazines, and fluorene derivatives bonded to furan units or thiophene units as disclosed in WO 2016/150544.

The extended benzindenofluorenes disclosed in WO 2014/111269 are particularly preferred for use as fluorescent emitters in the light-emitting layer.

Preferred fluorescent emitters for the light-emitting layer of a device comprising a polymer of the invention are as follows:

useful matrix materials, preferably for fluorescent compounds, include materials from a variety of classes of substances. Preferred matrix materials are selected from the following classes: oligomeric arylenes (e.g. 2,2',7,7' -tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular oligomeric arylenes containing fused aromatic groups, oligomeric arylylidenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypental metal complexes (e.g. according to WO 2004/081017), hole-conducting compounds (e.g. according to WO 2004/058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (e.g. according to WO 2005/084081 and WO 2005/084082), atropisomers (e.g. according to WO 2006/048268), boronic acid derivatives (e.g. according to WO 2006/117052) or benzanthracenes (e.g. according to WO 2008/145239). Particularly preferred matrix materials are selected from the following classes: oligomeric arylenes comprising naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, oligomeric arylenes vinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the group consisting of oligomeric aromatic subunits comprising anthracene, benzanthracene, triphenylene and/or pyrene or atropisomers of these compounds. In the context of the present invention, oligomeric arylidene refers to a compound in which at least three aryl or arylidene groups are bonded to each other. Also preferred are anthracene derivatives as disclosed in WO 2006/097208, WO 2006/131192, WO 2007/065550, WO 2007/110129, WO 2007/065678, WO 2008/145239, WO 2009/100925, WO 2011/054442 and EP 1553154, pyrene compounds as disclosed in EP 1749809, EP 1905754 and US 2012/0187826, benzanthracene compounds as disclosed in WO 2015/158409, indenobenzofurans as disclosed in WO 2017/025165, and phenanthrylanthracenes as disclosed in WO 2017/036573.

Preferred matrix materials for fluorescent emitters for the light-emitting layer of devices comprising the polymers of the invention are as follows:

suitable phosphorescent compounds (═ triplet emitters) are in particular those which emit light under suitable excitation, preferably in the visible region, and which also contain at least one atom having an atomic number of greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular iridium, platinum or copper, are preferably used as phosphorescent compounds. In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered as phosphorescent compounds.

Examples of such luminescent compounds can be found in applications WO 00/70655, WO 01/41512, WO 02/02714, WO02/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US 2005/0258742. In general, all phosphorescent complexes as used for phosphorescent OLEDs according to the prior art and as known to the person skilled in the art of organic electroluminescent devices are suitable.

Preferred matrix materials for phosphorescent compounds are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680; triarylamines, carbazole derivatives, such as CBP (N, N-biscarbazolylbiphenyl) or carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851; indolocarbazole derivatives, for example according to WO 2007/063754 or WO 2008/056746; indenocarbazole derivatives, for example according to WO 2010/136109, WO 2011/000455 or WO 2013/041176; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP1731584, JP 2005/347160; bipolar matrix materials, for example according to WO 2007/137725; silanes, for example according to WO 2005/111172; boron azaheterocyclyls or borates, for example according to WO 2006/117052; triazine derivatives, for example according to WO2010/015306, WO 2007/063754 or WO 2008/056746; zinc complexes, for example according to EP 652273 or WO 2009/062578; silicon-diazacyclo-slow or silicon-tetraazacyclo-slow according to WO 2010/054729; phosphorus diazacyclo-slow derivatives, for example according to WO 2010/054730; bridged carbazole derivatives, for example according to US 2009/0136779, WO2010/050778, WO 2011/042107, WO 2011/088877 or WO 2012/143080; terphenyl fork derivatives, for example according to WO 2012/048781; or lactams, for example according to WO 2011/116865 or WO 2011/137951.

Suitable charge transport materials which can be used in the hole injection or hole transport layer or the electron blocking layer or the electron transport layer of the electronic device according to the invention, in addition to the polymers according to the invention, are also compounds such as are disclosed in Y.Shirota et al, chem.Rev.2007,107(4),953-1010 or other materials such as are used in these layers according to the prior art.

The material for the electron transport layer may be any material used as an electron transport material in the electron transport layer according to the prior art, in addition to the compound of the present invention. Particularly suitable are aluminum complexes, for example Alq₃(ii) a Zirconium complexes, e.g. Zrq₄(ii) a Lithium complexes, such as Liq; a benzimidazole derivative; a triazine derivative; a pyrimidine derivative; a pyridine derivative; pyrazine derivatives; quinoxaline derivatives; a quinoline derivative;

an oxadiazole derivative; an aromatic ketone; a lactam; borane; phosphorus diazacyclo-core derivatives and phosphine oxide derivatives. Other suitable materials are derivatives of the above compounds disclosed in JP 2000/053957, WO 2003/060956, WO2004/028217, WO 2004/080975 and WO 2010/072300.

Preferred cathodes of the electronic devices are metals with a low work function, metal alloys or multilayer structures consisting of various metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, for example alloys composed of magnesium and silver. In the case of a multilayer structure, it is also possible to use other metals having a relatively high work function, such as Ag or Al, in addition to the metals mentioned, in which case, for example, combinations of metals, such as Ca/Ag, Mg/Ag or Ba/Ag, are generally used. It may also be preferred to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali or alkaline earth metal fluorides, and the corresponding oxides or carbonates (e.g. LiF, Li)₂O、BaF₂、MgO、NaF、CsF、Cs₂CO₃Etc.). For this purposeLithium quinolinate (LiQ) may also be used. The layer thickness of the layer is preferably between 0.5nm and 5 nm.

The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5eV relative to vacuum. First, metals with a high redox potential are suitable for this purpose, such as Ag, Pt or Au. Second, metal/metal oxide electrodes (e.g., Al/Ni/NiO)_x、Al/PtO_x) May also be preferred. For some applications, at least one electrode must be transparent or partially transparent in order to be able to irradiate organic materials (organic solar cells) or to emit light (OLED, O-laser). Preferred anode materials herein are conductive mixed metal oxides. Particularly preferred is Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO). Also preferred are conductive doped organic materials, in particular conductive doped polymers. Furthermore, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

According to the present invention, electronic devices comprising one or more polymers of the present invention may be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (e.g., phototherapy).

Detailed Description