Materials for electronic devices

Abstract

The present application relates to a polymer containing at least one structural unit of a formula (I) and at least one further structural unit selected from structural units A, B and C. The present application further relates to the use of the polymer in an electronic device and to a process for preparing the polymer. The present application further relates to an electronic device comprising the polymer.

Claims

1. A polymer comprising at least one structural unit of formula (I): ##STR00204## wherein Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, and Ar.sup.5 are the same or different and are selected from the group consisting of heteroaromatic ring systems having 5 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.1 radicals and aromatic ring systems having 6 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.1 radicals, with the proviso that at least one of the two Ar.sup.2 and Ar.sup.4 groups is substituted in each case by an R.sup.4 group in at least one ortho position to the bond to N, wherein the R.sup.4 group optionally defines a ring with the corresponding Ar.sup.2 or Ar.sup.4 group to which it is bonded, and wherein the R.sup.4 group is bonded to the Ar.sup.2 and/or Ar.sup.4 group(s) directly or via a linker group X; R.sup.1 is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 groups are optionally joined to one another so as to define a ring; and wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.2 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2; R.sup.2 is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(═O)(R.sup.3).sub.2, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 and/or R.sup.2 groups are optionally joined to one another so as to define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.3 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO, or SO.sub.2; R.sup.3 is the same or different in each instance and is selected from the group consisting of H, D, F, CN, alkyl, or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.3 groups are optionally joined to one another so as to define a ring; and wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, aromatic ring systems, and heteroaromatic ring systems are optionally substituted by F or CN; R.sup.4 is the same or different in each instance and is selected from the group consisting of heteroaromatic ring systems having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 groups and aromatic ring systems having 6 to 40 aromatic ring atoms and which are optionally substituted by one or more R.sup.2 radicals; X is the same or different in each instance and is selected from the group consisting of C(R.sup.2).sub.2, Si(R.sup.2).sub.2, NR.sup.2, O, S, and C═O; n is 0 or 1; and at least one structural unit selected from the group consisting of structural unit A has a structure of formula (II-A): ##STR00205## wherein there is at least one R.sup.5 group other than H and D; structural units B comprising two groups bonded directly to one another and selected from the group consisting of aryl groups having 6 to 40 aromatic ring atoms and optionally substituted in each case by one or more R.sup.5 groups and heteroaryl groups having 5 to 40 aromatic ring atoms and optionally substituted in each case by one or more R.sup.5 groups, wherein the conjugation plane of the second aryl or heteroaryl group is twisted about the axis of the bond between the two groups with respect to the conjugation plane of the first aryl or heteroaryl group; and structural units C of formula (II-C): wherein ##STR00206## Ar.sup.6 and Ar.sup.7 are the same or different in each instance and are selected from the group consisting of aromatic ring systems having 6 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups; R.sup.5 is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 groups are optionally joined to one another so as to define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.2 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2; k is an integer from 0 to 9, and wherein one or more CH.sub.2 units in the alkylene chain of formula (II-C) are optionally replaced by a divalent unit selected from the group consisting of C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, Si(R.sup.5).sub.2, NR.sup.S, P(═O)(R.sup.5), O, S, SO, and SO.sub.2; and wherein one or more hydrogen atoms in the alkylene chain of formula (II-C) are optionally replaced by an R.sup.5 group.

2. The polymer of claim 1, wherein R.sup.4 is the same or different in each instance and is selected from the group consisting of aromatic ring systems having 6 to 20 aromatic ring atoms and optionally substituted by one or more R.sup.2 groups.

3. The polymer of claim 1, wherein at least one group selected from the group consisting of Ar.sup.2 and Ar.sup.4 groups contains exactly one or exactly two R.sup.4 groups in the ortho position to the nitrogen atom, wherein R.sup.4 is bonded to the Ar.sup.e and/or Ar.sup.4 group(s) directly or via a linker group X.

4. The polymer of claim 1, wherein the structural unit of formula (I) has a structure of one of formulae (I-1-A), (I-2-A-1), (I-2-A-2), or (I-2-A-3): ##STR00207## wherein i is 0 or 1.

5. The polymer of claim 1, wherein the structural unit of formula (I) has a structure of one of formulae (I-1-B), (I-2-B-1), (I-2-B-2), or (I-2-B-3): ##STR00208## wherein i is 0 or 1; and Y in each instance is the same or different and is selected from the group consisting of a single bond, C(R.sup.2).sub.2, Si(R.sup.2).sub.2, NR.sup.2, O, S, and C═O.

6. The polymer of claim 1, wherein the structural unit of formula (I) has a structure of one of formulae (I-1-A-A), (I-1-A-B), or (I-1-B-A): ##STR00209## wherein i is 0 or 1; Y is the same or different in each instance and is selected from the group consisting of a single bond, C(R.sup.2).sub.2, Si(R.sup.2).sub.2, NR.sup.2, O, S, and C═O; and the aromatic six-membered rings are each optionally substituted at the positions shown as unsubstituted by an R.sup.1 or R.sup.2 group.

7. A polymer comprising at least one structural unit of formula (I): ##STR00210## wherein Ar.sup.i, Ar.sup.e, Ar.sup.a, Ar.sup.4, and Ar.sup.5 are the same or different and are selected from the group consisting of heteroaromatic ring systems having 5 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.1 radicals and aromatic ring systems having 6 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.1 radicals, with the proviso that at least one of the two Ar.sup.2 and Ar.sup.4 groups is substituted in each case by an R.sup.4 group in at least one ortho position to the bond to N, wherein the R.sup.4 group optionally defines a ring with the corresponding Ar.sup.2 or Ar.sup.4 group to which it is bonded, and wherein the R.sup.4 group is bonded to the Ar.sup.2 and/or Ar.sup.4 group(s) directly or via a linker group X; R.sup.1 is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 groups are optionally joined to one another so as to define a ring; and wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.2 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2; R.sup.2 is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(═O)(R.sup.3).sub.2, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 and/or R.sup.2 groups are optionally joined to one another so as to define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.3 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO, or SO.sub.2; R.sup.3 is the same or different in each instance and is selected from the group consisting of H, D, F, CN, alkyl, or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.3 groups are optionally joined to one another so as to define a ring; and wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, aromatic ring systems, and heteroaromatic ring systems are optionally substituted by F or CN; R.sup.4 is the same or different in each instance and is selected from the group consisting of heteroaromatic ring systems having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 groups and aromatic ring systems having 6 to 40 aromatic ring atoms and which are optionally substituted by one or more R.sup.2 radicals; X is the same or different in each instance and is selected from the group consisting of C(R.sup.2).sub.2, Si(R.sup.2).sub.2, NR.sup.2, O, S, and C═O; n is 0 or 1; and at least one structural unit selected from the group consisting of structural units A comprising a planar aromatic group selected from the group consisting of aryl groups having 6 to 40 aromatic ring atoms and heteroaryl groups having 6 to 40 aromatic ring atoms, where the planar aromatic group comprises at least one R.sup.5 group which, on account of the space it occupies, brings about twisting of the planar aromatic group with respect to that plane which is formed by the planar aromatic groups of the directly adjacent structural units, and wherein the aryl groups and heteroaryl groups are each optionally substituted by one or more further R.sup.5 groups; structural units B has a structure of formula (II-B): ##STR00211## wherein R.sup.5A is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 groups are optionally joined to one another so as to define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.2 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2; Ar.sup.g and Ar.sup.g are the same or different in each instance and are selected from the group consisting of aromatic ring systems having 6 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups; m and p are the same or different in each instance and are selected from the group consisting of 0 and 1; and the naphthyl groups at the positions shown as unsubstituted are each optionally substituted by an R.sup.5 group; and structural units C of formula (II-C): ##STR00212## wherein Ar.sup.6 and Ar.sup.7 are the same or different in each instance and are selected from the group consisting of aromatic ring systems having 6 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups; R.sup.5 is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 groups are optionally joined to one another so as to define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.2 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2; k is an integer from 0 to 9, and wherein one or more CH.sub.2 units in the alkylene chain of formula (II-C) are optionally replaced by a divalent unit selected from the group consisting of C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, Si(R.sup.5).sub.2, NR.sup.S, P(═O)(R.sup.5), O, S, SO, and SO.sub.2; and wherein one or more hydrogen atoms in the alkylene chain of formula (II-C) are optionally replaced by an R.sup.5 group.

8. The polymer of claim 1, wherein the structural unit B has a structure of formula (II-B): ##STR00213## wherein R.sup.5A is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 groups are optionally joined to one another so as to define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.2 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2; Ar.sup.g and Ar.sup.g are the same or different in each instance and are selected from the group consisting of aromatic ring systems having 6 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups; m and p are the same or different in each instance and are selected from the group consisting of 0 and 1; and the naphthyl groups at the positions shown as unsubstituted are each optionally substituted by an R.sup.5 group.

9. The polymer of claim 1, wherein the sum total of the proportions of those structural units that correspond to a structural unit A, B or C in the polymer is between 20 and 75 mol %, based on 100 mol % of all copolymerized monomers present as structural units in the polymer.

10. The polymer of claim 1, wherein the sum total of the proportions of those structural units that correspond to a structural unit of the formula (I) in the polymer is between 10 and 60 mol %, based on 100 mol % of all copolymerized monomers present as structural units in the polymer.

11. The polymer of claim 1, wherein the polymer contains at least one structural unit having a crosslinkable group Q.

12. The polymer of claim 11, wherein the at least one structural unit having a crosslinkable group Q is a structural unit of formula (I), a structural unit A, a structural unit B, a structural unit C, or a structural unit selected from the group consisting of triarylamine, fluorene, indenofluorene, and spirobifluorene structural units.

13. The polymer of claim 11, wherein the proportion of structural units having a crosslinkable group Q in the polymer is in the range from 1 to 50 mol %, based on 100 mol % of all copolymerized monomers present as structural units in the polymer.

14. A polymer prepared by crosslinking the polymer of claim 11.

15. A mixture comprising at least one monomer of formula (M-I) and at least one monomer selected from the group consisting of monomers of formulae (M-II-A), (M-II-B), and (M-II-C): ##STR00214## wherein R.sup.5A is the same or different in each instance and is selected from the group consisting of H, D, F, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon 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 R.sup.1 groups are optionally joined to one another so as to define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic and heteroaromatic ring systems are each optionally substituted by one or more R.sup.2 groups; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO, or SO.sub.2; Ar.sup.g and Ar.sup.g are the same or different in each instance and are selected from the group consisting of aromatic ring systems having 6 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups and heteroaromatic ring systems having 5 to 40 aromatic ring atoms and optionally substituted by one or more R.sup.5 groups; m and p are the same or different in each instance and are selected from the group consisting of 0 and 1; and Z is the same or different in each instance and is a leaving group suitable for a polymerization reaction.

16. A mixture comprising at least one polymer of claim 1 and one or more further polymeric, oligomeric, dendritic, and/or low molecular weight substances.

17. A solution comprising one or more polymers of claim 1 and one or more solvents.

18. An electronic device comprising at least one polymer of claim 1.

19. The electronic device of claim 18, wherein the polymer is present in a layer selected from the group consisting of hole-transporting layers, hole injection layers, electron blocker layers, and emitting layers.

20. The electronic device of claim 18, wherein the electronic device comprises a blue-fluorescing emitting layer which has been applied from solution.

21. The polymer of claim 7, wherein the structural unit A has a structure of formula (II-A): ##STR00215## wherein there is at least one R.sup.5 group other than H and D.

Description

EXAMPLES

A) Synthesis Examples

(1) Monomers Used:

(2) TABLE-US-00005 Synthesis by published specification/CAS Monomer Structure number Ortho-substituted amines MON-1-Br WO 2013/156130 MON-1-BE WO 2013/156130 MON-2-Br WO 2013/156130 MON-2-BE Borylation analogously to WO 2013/156130 method MON-3-Br WO 2013/156130 MON-4-Br WO 2013/156130 MON-5-Br WO 2013/156129 MON-6-BE WO 2013/156129 MON-7-Br 0 CAS 2043618-74-0 MON-8-Br Synthesis according to EP17177211.4 MON-8-BE Synthesis according to EP17177211.4 Conjugation interruptors MON-20-Br CAS 117635-21-9 MON-20-BE CAS 374934-77-7 MON-21-Br CAS 255710-07-7 MON-22-BE CAS 897404-05-6 MON-23-Br CAS 49610-35-7 MON-24-BE WO 2006/063852 MON-25-Br 101783-96-4 MON-26-Br 0 CAS 615-59-8 Crosslinkers MON-30-Br WO 2010/097155 MON-30-BE WO 2010/097155 MON-31-Br WO 2013/156130 MON-31-BE WO 2013/156130 MON-32-Br WO 2009/102027 MON-32-BE WO 2009/102027 MON-33-Br For synthesis see below MON-33-BE Borylation analogously to WO 2013/156130 method MON-34-Br For synthesis see below MON-34-BE 0 Borylation analogously to WO 2013/156130 method MON-35-Br For synthesis see below MON-35-BE Borylation analogously to WO 2013/156130 method MON-36-BE For synthesis see below Further monomers, for preparation of the comparative polymers Mon-101-BE WO 99/048160 A1 Mon-102-Br Macromolecules 2000, 33, 2016-2020 Mon-103-Br CAS 16400-51-4
Synthesis of the Monomers
Synthesis MON-33-Br (and Analogously MON-034-Br)

(3) ##STR00197##

(4) 3-Bromobenzaldehyde (75 g, 405 mmol), 4-(diphenylamino)phenylboronic acid (141 g, 486 mmol) and caesium carbonate (291 g, 892 mmol) are initially charged in 540 ml of ethylene glycol dimethyl ether, 430 ml of toluene and 540 ml of water. After degassing for 30 minutes, tetrakis(triphenylphosphine)palladium (11.7 g, 10.1 mmol) is added. The reaction is heated to reflux overnight. After the reaction has ended, the mixture is cooled to room temperature and quenched with N-acetylcysteine solution. This is followed by filtering through silica gel, removal of the organic phase and extraction of the aqueous phase with toluene. The collected organic phases are combined and dried, and the solvent is removed under reduced pressure. The resultant oil is purified by means of zone sublimation. Yield: 57% (80.2 g, 229 mmol).

(5) Int-1 is subsequently dissolved in 1000 ml of THF and cooled to 0° C., and N-bromosuccinimide (81.7 g, 178 mmol) is added in portions. The reaction is then gradually warmed to room temperature. THF is removed under reduced pressure, and the residue is taken up with toluene and washed three times with water. The organic phase is dried and the solvent is again removed under reduced pressure. This is followed by repeated recrystallization from heptane. MON-33-Br is obtained with a yield of 86% (100 g, 200 mmol).

(6) MON-034-Br is prepared analogously by using 3-bromobicyclo[4.2.0]octa-1(6), 2,4-triene rather than 3-bromobenzaldehyde. MON-34-Br is prepared with a yield of 55%.

(7) Synthesis of MON-35-Br

(8) ##STR00198##

(9) The bromo-phenyl derivative (23 g, 100 mmol), 2-chlorophenylboronic acid (16.5 g, 105 mmol) and potassium carbonate (41.6 g, 301 mmol) are initially charged in 140 ml of THF and 50 ml of water. The reaction mixture is degassed and then tetrakis(triphenylphosphine)palladium (1.16 g, 1 mmol) is added. The reaction is stirred at reflux overnight. Thereafter, the mixture is cooled to room temperature, toluene and water are added, the phases are separated and the organic phase is washed with water. After the solvent has been removed under reduced pressure, the solid formed is purified by means of hot extraction (heptane, alumina). Int-2 is obtained with a yield of 80% (20.7 g, 79 mmol).

(10) Int-2 (19.7 g, 76 mmol) and diphenylamine (12.9 g, 76 mmol) are dissolved in 800 ml of toluene, and sodium t-butoxide (10.9 g, 113 mmol) is added. This is followed by degassing with argon for 30 min and addition of tris(dibenzylideneacetone)dipalladium (690 mg, 0.76 mmol). The reaction mixture is heated at reflux overnight, then cooled, and water and toluene are added. The phases are separated, and the organic phase is washed with water and then dried. The solvent is removed under reduced pressure and the resulting crude product is purified using alumina. Int-3 is obtained with a yield of 71% (21.1 g, 53 mmol).

(11) Int-3 (20 g, 50 mmol) is dissolved in 400 ml of acetonitrile, and 75 ml of hydrochloric acid are added. A solid precipitates out, and is filtered off. Int-4: Yield 68% (12.1 g, 35 mmol).

(12) Int-4 (12 g, 35 mmol) is dissolved in 470 ml of THF and cooled to 0° C., and N-bromosuccinimide (12.2 g, 68 mmol) is added in portions. The reaction mixture is warmed to room temperature overnight. The solvent is removed under reduced pressure, taken up again with toluene, and washed with aqueous Na.sub.2SO.sub.3 solution and then with water. The solvent is removed again and the solid residue is repeatedly recrystallized from a toluene/heptane mixture. MON-35-Br is obtained with a yield of 67% (11.7 g, 23 mmol).

(13) Synthesis of MON-36-BE

(14) ##STR00199##

(15) 9,9′-Spirobifluorene-4′-amine (25 g, 75 mmol) and 2-bromo-7-chloro-9,9-dimethylfluorene (48.7 g, 160 mmol) are dissolved in 400 ml of toluene, and then sodium t-butoxide (21.7 g, 226 mmol) is added. The mixture is saturated with protective gas and, after adding [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (1.85 g, 0.2 mmol), heated to reflux. After four hours, the mixture is cooled to room temperature, filtered through Celite and washed through with toluene. The phases are separated, the organic phase is washed with water and dried, and the solvent is removed. For purification, the solids are filtered together with heptane/toluene through silica gel. Int-5 is obtained with a yield of 73% (43 g, 54 mmol).

(16) 41 g of Int-5 (52 mmol) are initially charged together with bis(pinacolato)diborane (30.6 g, 120 mmol) and potassium acetate (25.7 g, 261.8 mmol) in 650 ml of dioxane. The mixture is inertized with argon and then palladium acetate (235 mg, 1.05 mmol) and Sphos (860 mg, 2.09 mmol) are added. The mixture is stirred at reflux overnight. The mixture is cooled to room temperature, filtered through Celite and washed through with toluene. The phases are separated, the organic phase is washed with water and dried, and the solvent is removed. The crude product is subsequently recrystallized (toluene/heptane) and then purified by column chromatography (heptane/EtOAc). MON-36-Br is obtained with a yield of 30% (15 g, 15 mmol).

(17) Synthesis of the Polymers

(18) The comparative polymers V1 and V2 and the inventive polymers Po1 to Po40 are prepared by SUZUKI coupling by the process described in WO 2003/048225 from the monomers disclosed above.

(19) In the preparation of the polymers, the monomers specified below are used in the reaction mixture in the corresponding percentages, as specified below. The polymers V1 and V2 and Po1 to Po40 prepared in this way contain the structural units, after elimination of the leaving groups, in the percentages reported in the table below (percent figures=mol %).

(20) In the case of the polymers which are prepared from monomers having aldehyde groups, the latter are converted to crosslinkable vinyl groups after the polymerization by WITTIG reaction by the process described in WO 2010/097155 (examples with synthesis method on pages 36/37). The polymers listed correspondingly in the table below thus have crosslinkable vinyl groups rather than the aldehyde groups originally present.

(21) The palladium and bromine contents of the polymers are determined by ICP-MS. The values determined are below 10 ppm.

(22) The molecular weights M.sub.w and the polydispersities D are determined by means of gel permeation chromatography (GPC) (model: Agilent HPLC System Series 1100, column: PL-RapidH from Polymer Laboratories; solvent: THF with 0.12% by volume of o-dichlorobenzene; detection: UV and refractive index; temperature: 40° C.). Calibration is effected with polystyrene standards.

(23) TABLE-US-00006 Polymer MON A % MON B % MON C % Mw/D V1 MON-102-Br 50 MON-1-BE 30 MON-30-BE 20 138K/2.1 V2 MON-101-BE 30 MON-20-Br 50 MON-30-BE 20 115K/3.4 Po1 MON-1-Br 30 MON-20-BE 50 MON-30-Br 20 150K/3.9 Po5 MON-2-Br 30 MON-20-BE 50 MON-30-Br 20  65K/2.8 Po18 MON-3-Br 30 MON-20-BE 50 MON-30-Br 20  68K/2.5

(24) In addition, the following polymers of the invention are prepared:

(25) TABLE-US-00007 Polymer MON A % MON B % MON C % MON D % MON E % Mw/D Po2 MON-2-Br 30 MON-20-BE 50 MON-32-Br 20 — — — — 50K/2.3 Po3 MON-5-Br 40 MON-22-BE 50 MON-30-Br 10 — — — — 85K/3.2 Po4 MON-3-Br 30 MON-24-BE 50 MON-31-Br 20 — — — — 43K/3.5 Po6 MON-1-BE 40 MON-23-Br 50 MON-32-BE 10 — — — — 78K/2.3 Po7 — — MON-20-BE 50 MON-4-Br 50 — — — — 53K/3.3 Po8 MON-3-Br 25 MON-24-BE 50 MON-4-Br 25 — — — — 65K/3.7 Po9 MON-1-BE 40 MON-25-Br 50 MON-31-BE 10 — — — — 73K/4.2 Po10 MON-5-Br 30 MON-22-BE 50 MON-30-Br 20 — — — — 105K/2.3  Po11 MON-1-Br 20 MON-20-BE 50 MON-32-Br 10 MON-2-Br 20 — — 95K/2.6 Po12 MON-6-BE 30 MON-25-Br 50 MON-30-BE 10 MON-32-BE 10 — — 67K/3.6 Po13 MON-1-BE 40 MON-21-Br 50 MON-31-BE 10 — — — — 115K/2.1  Po14 MON-1-BE 25 MON-21-Br 50 MON-30-BE 25 — — — — 130K/2.9  Po15 MON-5-Br 40 MON-24-BE 50 MON-4-Br 10 — — — — 75K/3.2 Po16 MON-3-Br 30 MON-20-BE 50 MON-32-Br 20 — — — — 95K/3.4 Po17 MON-1-Br 40 MON-20-BE 50 MON-30-Br 10 — — — — 85K/2.6 Po19 MON-1-BE 30 MON-25-Br 50 MON-31-BE 20 — — — — 66K/2.7 Po20 MON-1-BE 50 MON-20-Br 50 — — — — — — 60K/2.5 Po21 MON-1-BE 50 MON-25-Br 50 — — — — — — 85K/2.8 Po22 MON-1-Br 30 MON-20-BE 50 MON-33-Br 20 — — — — 90K/2.4 Po23 MON-1-Br 30 MON-20-BE 50 MON-34-Br 20 — — — — 75K/3.4 Po24 MON-1-Br 20 MON-102-Br 10 MON-20-BE 50 MON-30-Br 20 — — 88K/2.5 Po25 MON-2-Br 30 MON-20-BE 50 MON-30-Br 10 MON-32-Br 10 — — 70K/2.2 Po26 MON-1-Br 20 MON-102-BE 10 MON-20-Br 10 MON-20-BE 40 MON-30-BE 20 37K/1.9 Po27 MON-2-BE 30 MON-26-Br 50 Mon-30-BE 20 — — — — 65K/2.4 Po28 MON-20-BE 50 MON-35-Br 50 — — — — — — 40K/2.3 Po29 MON-1-Br 30 MON-20-BE 50 MON-35-Br 20 — — — — 25K/2.4 Po30 MON-2-Br 30 MON-20-BE 50 MON-20-Br 10 MON-32-Br 10 — — 70K/2.2 Po31 MON-102-BE 10 MON-1-Br 30 MON-20-BE 40 MON-30-Br 20 — — 70K/2.9 Po32 MON-7-Br 30 MON-20-BE 50 MON-30-Br 20 — — — — 50K/2.1 Po33 MON-35-BE 30 MON-20-Br 50 MON-30-BE 20 — — — — 60K/2.1 Po34 MON-8-BE 40 MON-23-Br 50 MON-32-BE 10 — — — — 78K/2.3 Po35 MON-8-BE 25 MON-21-Br 50 MON-30-BE 25 — — — — 130K/2.9  Po36 MON-8-Br 30 MON-20-BE 50 MON-32-Br 20 — — — — 95K/3.4 Po37 MON-8-Br 40 MON-20-BE 50 MON-30-Br 10 — — — — 85K/2.6 Po38 MON-8-Br 30 MON-20-BE 50 MON-30-Br 20 — — — — 68K/2.5 Po39 MON-2-Br 50 MON-20-BE 50 80K/2.1 Po40 MON-102-Br 10 MON-1-Br 40 MON-20-BE 50 110K/2.2 

B) Device Examples

(26) The general process for producing OLEDs comprising layers that have been applied from solution is described in WO 2004/037887 and WO 2010/097155. This process is matched to the circumstances described hereinafter (variation in layer thickness, materials).

(27) The polymers of the invention are used in OLEDs with the following layer sequence: substrate, ITO (50 nm), hole injection layer (HIL) (20 nm), hole transport layer (HTL) (20 nm), emission layer (EML) (30 nm), hole blocker layer (HBL) (10 nm) electron transport layer (ETL) (40 nm), cathode (Al) (100 nm).

(28) Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. The hole injection layer is applied by means of spin-coating in an inert atmosphere. For this purpose, a hole-transporting crosslinkable polymer and a p-doping salt are dissolved in toluene. Corresponding materials have been described in WO 2016/107668, WO 2013/081052 and EP2325190 inter alia. For a resulting layer thickness of 20 nm, a solids content of 6 mg/ml is used. The layer is subsequently baked on a hotplate at 200° C. in an inert gas atmosphere for 30 minutes.

(29) The hole transport and emission layers are then applied to these coated glass plates.

(30) The hole transport layers used are the compounds of the invention and comparative compounds, each dissolved in toluene. The solids content of these solutions is 5 mg/ml, since layer thicknesses of 20 nm are to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere and baked on a hotplate at 240° C. for 30 minutes.

(31) The emission layer is composed of the host material H1 and the emitting dopant D1. The materials are present in the emission layer in a proportion by weight of 92% H1 and 8% D1. The mixture for the emission layer is dissolved in toluene. The solids content of this solution is 9 mg/ml, since layer thicknesses of 30 nm are to be achieved by means of spin-coating.

(32) The layers are spun on in an inert gas atmosphere and baked at 150° C. for 10 minutes.

(33) The materials used in the present case are shown in the table below.

(34) TABLE-US-00008 Structural formulae of the materials used in the emission layer 00 H1 01 D1

(35) The materials for the hole blocker layer and electron transport layer are applied by thermal vapour deposition in a vacuum chamber and are shown in the table below. The hole blocker layer consists of ETM1. The electron transport layer consists of the two materials ETM1 and ETM2, which are blended by co-evaporation in a proportion by volume of 50% each.

(36) TABLE-US-00009 HBL and ETL materials used 02 ETM1 03 ETM2

(37) The cathode is formed by the thermal evaporation of an aluminium layer of thickness 100 nm.

(38) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics and the (operating) lifetime are determined. The IUL characteristics are used to determine parameters, for example the external quantum efficiency (in %) at a particular brightness. LD80 @ 1000 cd/m.sup.2 is the lifetime until the OLED, given a starting brightness of 1000 cd/m.sup.2, has dropped to 80% of the starting intensity, i.e. to 800 cd/m.sup.2.

(39) The performance data and properties of the OLEDs produced are described hereinafter. The OLEDs produced are blue-emitting OLEDs.

(40) 1) For OLEDs comprising V1, V2, Po1, Po5 and Po18, the following results are obtained for lifetime and efficiency:

(41) TABLE-US-00010 Polymer Efficiency at LD80 at in 1000 cd/m.sup.2 1000 cd/m.sup.2 HTL % EQE [h] V1 4.4 198 V2 7.4 121 Po1 7.6 257 Po5 7.4 279 Po18 7.1 223

(42) As the efficiency data obtained show, the inventive polymer Po1 brings great improvements compared to the comparative polymer V1. The efficiency rises by more than 50% compared to the comparative polymer V1. This shows the effect which is achieved through the use of the conjugation-interrupting substituted phenylene unit derived from the monomer MON-20-BE compared to the use of the indenofluorene unit derived from the monomer MON-102-Br. The indenofluorene unit is not a conjugation-interrupting unit.

(43) Distinct improvements are also apparent with polymers containing other conjugation-interrupting units, for example the MON-21 to MON-26 units shown above, compared to comparative polymers having no conjugation-interrupting unit, for example V1 with the indenofluorene unit MON-102-Br.

(44) As the lifetime data obtained show, the inventive polymers Po1, Po5 and Po18 also bring improvements over the comparative polymer V2. The efficiency remains virtually unchanged. This shows the effect which is achieved through the use of the ortho-substituted triarylamine structural units derived from the monomers MON-1-Br, MON-2-Br and MON-3-Br (in Po1, Po5 and Po18) compared to the use of the para-substituted triarylamine structural unit derived from the monomer MON-101-BE (in V2).

(45) An improved lifetime compared to V2 is also obtained with further polymers of the invention that differ from Po1, Po5 and Po18 in that, rather than the structural units derived from the monomers MON-1-Br, MON-2-Br and MON-3-Br, they contain structural units derived from the monomers MON-4-Br, MON—S—Br, MON-6-BE, MON-7-Br, MON-8-BE and MON-8-Br.

(46) 2) In addition to the examples adduced above, OLEDs comprising the following polymers of the invention are examined:

(47) TABLE-US-00011 Efficiency at LD80 at Polymer 1000 cd/m.sup.2 1000 cd/m.sup.2 in HTL % EQE [h] Po2 7.6 143 Po22 6.8 256 Po23 8.0 129 Po24 7.3 397 Po25 7.5 230 Po26 7.4 192 Po27 6.7 234 Po28 7.0 216 Po37 7.5 216 Po38 7.1 223

(48) It is found here that these likewise have a very good efficiency. The relatively short lifetime in Po2 and Po23 is caused by the monomers MON-32-Br and MON-34-Br present in these polymers.

(49) 3) Finally, OLEDs each comprising one of the abovementioned inventive polymers Po3, Po4, Po6 to Po17, Po19 to Po21, Po29 to Po36, Po39 and Po40 as material for the HTL are produced. This likewise achieves good results for efficiency and lifetime.

(50) In the inventive examples, the polymers of the invention are used in an HTML in combination with an EML which is applied from solution and contains a singlet emitter. This shows the excellent suitability of the polymers in this specific device setup with blue-emitting EML applied from solution.