MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application relates to a polymer containing at least one structural unit of a formula (I). The polymer is suitable for use in an electronic device.

Claims

1-18. (canceled)

19. A polymer comprising at least one structural unit of formula (I): ##STR00413## wherein U is the same or different in each instance and is C(R.sup.1).sub.2, CR.sup.1CR.sup.1, Si(R.sup.1).sub.2, O, or S, wherein the groups CR.sup.1CR.sup.1, O, and S are not bonded directly to one another; Z is the same or different in each instance and is N or CR.sup.2 when no group is bonded thereto, and is C when a group is bonded thereto; 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, which have 5 to 40 aromatic ring atoms and which are optionally substituted by one or more R.sup.3 radicals, and aromatic ring systems which have 6 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.3 radicals; 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.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, 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 or R.sup.2 or R.sup.3 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.4 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO, or SO.sub.2; R.sup.2 and R.sup.3 are the same or different in each instance and are selected from the group consisting of H, D, F, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, 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 or R.sup.2 or R.sup.3 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.4 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO, or SO.sub.2; R.sup.4 is the same or different in each instance and is selected from the group consisting of H, D, F, C(O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(O)(R.sup.5).sub.2, OR.sup.5, S(O)R.sup.5, S(O).sub.2R.sup.5, 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.4 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.5 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CNR.sup.5, C(O)O, C(O)NR.sup.5, NR.sup.5, P(O)(R.sup.5), O, S, SO, or SO.sub.2; R.sup.5 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; where two or more R.sup.5 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; r is 1, 2, or 3 when p is 1, and is 1 when p is 0; s is 0, 1, 2, or 3 when q is 1, and is 1 when q is 0; p is 0 or 1; wherein, when p is 0, the groups bonded to the unit between square brackets with index p are bonded directly to one another; q is 0 or 1; wherein, when q is 0, the groups bonded to the unit between square brackets with index q are bonded directly to one another; n is 0 or 1, wherein, when n is 0, the groups bonded to the unit between square brackets with index n are bonded directly to one another; m is 0 or 1, wherein, when m is 0, the groups bonded to the unit between square brackets with index m are bonded directly to one another; o is 0 or 1, wherein, when o is 0, the groups bonded to the unit between square brackets with index o are bonded directly to one another; i is the same or different in each instance and is 1, 2, 3, 4, 5, 6, 7, or 8; wherein at least one U group containing one or more R.sup.1 groups selected from the group consisting of 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 is present; wherein two or more R.sup.1 or R.sup.2 or R.sup.3 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.4 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO, or SO.sub.2.

20. The polymer of claim 19, wherein Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, and Ar.sup.5 are the same or different in each instance and are selected from the group consisting of benzene, biphenyl, terphenyl, fluorene, naphthalene, phenanthrene, indenofluorene, spirobifluorene, dibenzofuran, dibenzothiophene, carbazole, indenocarbazole, and indolocarbazole, each of which is optionally substituted by one or more R.sup.1 radicals.

21. The polymer of claim 19, wherein R.sup.1 is the same or different in each instance and is selected from from the group consisting of H, D, F, straight-chain alkyl groups having 1 to 10 carbon atoms, and branched alkyl groups having 3 to 10 carbon atoms.

22. The polymer of claim 19, wherein the two U groups directly adjacent to the bridgehead carbon atom are each substituted with an R.sup.1 radical selected from the group consisting of F, CN, Si(R.sup.4).sub.3, OR.sup.4, straight-chain alkyl and alkoxy groups having 1 to 10 carbon atoms, branched alkyl and alkoxy groups having 3 to 10 carbon atoms, and aromatic ring systems having 6 to 20 aromatic ring atoms, wherein two or more R.sup.1 or R.sup.2 or R.sup.3 radicals are optionally joined to one another and optionally define a ring; and wherein the alkyl and alkoxy groups and the aromatic ring systems are each optionally substituted by one or more R.sup.4 radicals.

23. The polymer of claim 19, wherein the units: ##STR00414## in the structural unit of formula (I) are selected from the group consisting of units of formula (E-1): ##STR00415## wherein the free bond denotes the bond to the rest of the structural unit of formula (I).

24. The polymer of claim 19, wherein the units: ##STR00416## in the structural unit of formula (I) are selected from the group consisting of the following units: ##STR00417## ##STR00418## wherein the dotted line denotes the bond to the rest of the structural unit of formula (I) and wherein the semicircular bond denotes that the two R.sup.1 groups involved are joined to one another and define a ring.

25. The polymer of claim 19, wherein the structural element corresponds to the formula (I) of any of the formulae (I-1) to (I-6) ##STR00419## ##STR00420##

26. The polymer of claim 19, wherein the proportion of structural units of formula (I) in the polymer is in the range of from 30 to 70 mol %, based on 100 mol % of all copolymerizable monomers present as structural units in the polymer.

27. The polymer of claim 19, wherein the polymer comprises at least one structural unit comprising a crosslinkable Q group.

28. The polymer of claim 27, wherein the crosslinkable Q group is selected from the group consisting of the following formulae: ##STR00421## ##STR00422## wherein R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are the same or different in each instance and are selected from the group consisting of H and straight-chain or branched alkyl groups having 1 to 6 carbon atoms; s is an integer from 0 to 8; t is an integer from 1 to 8; and Ar.sup.10 is selected from the group consisting of aromatic ring systems which have 6 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.11 radicals and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.11 radicals; and wherein the dotted bond denotes the bond to the rest of the formula.

29. A polymer prepared via the crosslinking reaction of a polymer of claim 27.

30. A mixture comprising one or more polymers of claim 19 and one or more further polymeric, oligomeric, dendritic, and/or low molecular weight substances.

31. A solution comprising one or more polymers of claim 19 and one or more solvents.

32. An electronic device comprising at least one polymer of claim 19.

33. The electronic device of claim 32, wherein the at least one polymer is present in a layer selected from the group consisting of hole-transporting layer, hole injection layer, electron blocker layer, and emitting layer.

34. A process for preparing the polymer of claim 19 comprising conducting a polymerization selected from the group consisting of Suzuki polymerization, Yamamoto polymerization, Stille polymerization, Heck polymerization, Negishi polymerization, Sonogashira polymerization, Hiyama polymerization, and Hartwig-Buchwald.

35. A monomer of formula (M): ##STR00423## U is the same or different in each instance and is C(R.sup.1).sub.2, CR.sup.1CR.sup.1, Si(R.sup.1).sub.2, O, or S, wherein groups selected from CR.sup.1CR.sup.1, O, and S are not bonded directly to one another; Z is the same or different in each instance and is N or CR.sup.2 when no group is bonded thereto, and is C when a group is bonded thereto; X is the same or different in each instance and is a leaving group suitable for a polymerization reaction; 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, which have 5 to 40 aromatic ring atoms and which are optionally substituted by one or more R.sup.3 radicals, and aromatic ring systems which have 6 to 40 aromatic ring atoms and are optionally substituted by one or more R.sup.3 radicals; 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.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, 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 or R.sup.2 or R.sup.3 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.4 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO, or SO.sub.2; R.sup.2 and R.sup.3 are the same or different in each instance and are selected from the group consisting of H, D, F, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, 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 or R.sup.2 or R.sup.3 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.4 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO, or SO.sub.2; R.sup.4 is the same or different in each instance and is selected from the group consisting of H, D, F, C(O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(O)(R.sup.5).sub.2, OR.sup.5, S(O)R.sup.5, S(O).sub.2R.sup.5, 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.4 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.5 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CNR.sup.5, C(O)O, C(O)NR.sup.5, NR.sup.5, P(O)(R.sup.5), O, S, SO, or SO.sub.2; R.sup.5 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; where two or more R.sup.5 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; r is 1, 2, or 3 when p is 1, and is 1 when p is 0; s is 0, 1, 2, or 3 when q is 1, and is 1 when q is 0; p is 0 or 1; wherein, when p is 0, the groups bonded to the unit between square brackets with index p are bonded directly to one another; q is 0 or 1; wherein, when q is 0, the groups bonded to the unit between square brackets with index q are bonded directly to one another; n is 0 or 1, wherein, when n is 0, the groups bonded to the unit between square brackets with index n are bonded directly to one another; m is 0 or 1, wherein, when m is 0, the groups bonded to the unit between square brackets with index m are bonded directly to one another; o is 0 or 1, wherein, when o is 0, the groups bonded to the unit between square brackets with index o are bonded directly to one another; i is the same or different in each instance and is 1, 2, 3, 4, 5, 6, 7, or 8; and wherein at least one U group containing one or more R.sup.1 groups selected from the group consisting of 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 is present; wherein two or more R.sup.1 or R.sup.2 or R.sup.3 radicals are optionally joined to one another and optionally define a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups and the aromatic ring systems and heteroaromatic ring systems are each optionally substituted by one or more R.sup.4 radicals; and wherein one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl, and alkynyl groups are optionally replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO, or SO.sub.2.

Description

EXAMPLES

A) Synthesis Examples

[0212] 1) Synthesis of the Monomers of the Invention

[0213] 1-1) the Following Building Blocks (BB) are Used for the Synthesis of the Monomers for Preparation of the Polymers of the Invention:

[0214] a) Tetralin-Analogous Building Blocks

##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142##

[0215] b) Amine building blocks

##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147##

[0216] 1-2) Suzuki Reaction of the Tetralin-Analogous Building Blocks and the Amine Building Blocks to Give Coupling Products

[0217] Example Reaction

##STR00148##

[0218] Into a 2 litre four-neck flask with precision glass stirrer, heating bath, reflux condenser and argon connection are weighed 57 g (176 mmol) of BB-501, 57.7 g (176 mmol, 1 eq.) of BB-020, 10.16 g (9 mmol, 0.05 eq) of tetrakis(triphenylphosphine)palladium(0) (CAS: 14221-01-3) and 53.46 g (387 mmol, 2.2 eq) potassium carbonate, and the system is inertized with protective gas. 400 ml of toluene, 250 ml of 1,4-dioxane and 115 ml of water are added, and the reaction mixture is heated under reflux for 24 h. After cooling, the mixture is diluted with water, the organic phase is separated off and the solvent is removed under reduced pressure. The residue is repeatedly recrystallized from heptane and then sublimed. 34.8 g (44.42%, 78 mmol) of the colourless solid DB-1031 are obtained.

[0219] The following structures can be obtained by the same method and with similar yields:

##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210##

##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262##

[0220] 1-3) Buchwald Reaction of the Tetralin-Analogous Building Blocks with Amine Building Blocks to Give Coupling Products

##STR00263##

[0221] Into a 2 litre four-neck flask with precision glass stirrer, reflux condenser and argon connection are weighed 81 g (288 mmol) of BB-051, 53.61 g (317 mmol, 1.1 eq) of BB-750, 41.5 g (432 mmol, 1.5 eq) of sodium tert-butoxide, 2.36 g (5.76 mmol, 0.02 eq) of 2-dicyclohexylphosphino-2,6-methoxybiphenyl (SPhos), 647 mg (2.88 mmol, 0.01 eq) of palladium(II) acetate, and 600 ml of toluene, 500 ml of ethanol and 350 ml of water are added. The reaction mixture is boiled under reflux for 48 hours, left to cool, and diluted with 500 ml of water and 500 ml of toluene, and the phases are separated. The organic phase is filtered through neutral alumina and the solvent is removed under reduced pressure. 500 ml of ethanol are added to the residue, which is stirred at 50 C. overnight. The solids are filtered off with suction and dried under reduced pressure. 65.4 g (177 mmol, 61% yield) of a colourless solid BB-2013 are obtained.

[0222] The following structures can be obtained by the same method and with similar yields:

##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276##

[0223] 1-4) Bromination of the Coupling Products to Give the Monomer Compounds

##STR00277##

[0224] In a 4 litre four-neck flask with a reflux condenser, argon connection, precision glass stirrer and heating bath, 130.4 g (292.6 mmol) of BB-1031 are dissolved in 2500 ml of dichloromethane, 0.5 ml of glacial acetic acid is added, and 104.2 g (585.2 mmol, 2 eq) of N-bromosuccinimide (CAS: 128-08-5) are added in portions. The reaction mixture is stirred at room temperature with exclusion of light for 24 h and extracted with water, and the solvent is removed under reduced pressure. The residue is boiled in 1500 ml of ethanol, and the solids are filtered off with suction and recrystallized repeatedly from methyl ethyl ketone and heptane. 115.9 g (192 mmol, 65.6% yield) of the inventive monomer MON-0032 are obtained as a colourless solid.

[0225] The following monomers of the invention can be obtained by the same method and with similar yields:

##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300## ##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346##

##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365## ##STR00366## ##STR00367## ##STR00368## ##STR00369## ##STR00370## ##STR00371## ##STR00372## ##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389##

[0226] 2) Further Monomers Used:

TABLE-US-00004 Synthesis by publication/CAS Monomer Structure number MON-01-Br [00390] WO 2013/156130 MON-01-BE [00391] WO 2013/156130 Mon-02-BE [00392] WO 99/048160 A1 MON-20-BE [00393] CAS 374934-77-7 MON-21-BE [00394] CAS 1257064-91-7 Mon-22-BE [00395] CAS 850264-92-5 MON-30-Br [00396] WO 2010/097155 MON-30-BE [00397] WO 2010/097155 MON-31-Br [00398] WO 2013/156130 MON-31-BE [00399] WO 2013/156130 MON-32-BE [00400] WO 2009/102027 MON-32-Br [00401] CAS 852534-20-4 Mon-40-Br [00402] Macromolecules 2000, 33, 2016-2020 Mon-40-BE [00403] CAS 628303-20-8 Mon-41-BE [00404] WO 2003/020790 Mon-42-BE [00405] WO 2005/104264

[0227] 3) Synthesis of the Polymers

[0228] The comparative polymers V1 and V2 and the inventive polymers Po1 to Po22 are prepared by SUZUKI coupling by the process described in WO 2003/048225 from the monomers disclosed above.

[0229] 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 Po22 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 %).

[0230] 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.

[0231] The palladium and bromine contents of the polymers are determined by ICP-MS. The values determined are below 10 ppm.

[0232] 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.

[0233] Direct Comparisons:

TABLE-US-00005 Polymer MON A % MON B % MON C % Mw/D V1 MON-40-Br 50 MON-01-BE 40 MON-30-BE 10 125 K/2.3 V2 MON-01-Br 30 MON-20-BE 50 MON-30-Br 20 65 K/2.7 Po1 MON-40-BE 50 Mon-0032 40 MON-30-Br 10 135 K/2.4 Po2 Mon-0032 30 MON-20-BE 50 MON-30-Br 20 70 K/3.1

[0234] In addition, the following inventive polymers are prepared using the monomer building blocks Mon-0032, Mon-0033, Mon-0036, Mon-0039, Mon-0042, Mon-0043, Mon-0054, Mon-0084, Mon-0164, Mon-0406, Mon-0410, Mon-0429, Mon-1006, Mon-1013, Mon-1031, Mon-1040, Mon-1041 and Mon-1049 (for structures see table above).

TABLE-US-00006 Polymer MON A % MON B % MON C % MON D % Mw/D Po3 MON- 50 Mon- 40 MON- 10 150 K/2.3 40-BE 0042 30-Br Po4 Mon- 30 MON- 50 MON- 20 55 K/3.2 0054 01-BE 32-BE Po5 Mon- 30 MON- 50 MON- 20 80 K/4.1 0032 20-BE 32-Br Po6 MON- 40 Mon- 50 MON- 20 180 K/2.5 041-BE 1031 31-BE Po7 Mon- 20 MON- 50 MON- 20 MON- 10 45 K/3.6 1013 21-BE 01-Br 30-Br Po8 MON- 25 MON- 50 Mon- 25 120 K/4.5 40-Br 22-BE 0406 Po9 MON- 50 Mon- 40 MON- 10 125 K/2.1 40-BE 0429 30-Br Po10 MON- 50 Mon- 40 MON- 10 95 K/2.3 40-BE 0164 30-Br Po11 MON- 50 Mon- 40 MON- 10 90 K/2.6 41-BE 0084 032-Br Po12 MON- 50 Mon- 40 MON- 10 105 K/3.0 40-BE 0036 31-Br Po13 Mon- 50 MON- 50 80 K/2.9 1041 30-BE Po14 Mon- 50 MON- 30 MON- 20 65 K/2.8 1049 01-BE 30-BE Po15 Mon- 50 MON- 30 MON- 20 55 K/4.2 1040 02-BE 32-BE Po16 MON- 50 Mon- 30 MON- 20 85 K/2.5 042-BE 1006 31-Br Po17 Mon- 30 Mon- 20 MON- 30 MON- 20 50 K/3.1 0406 0410 01-BE 30-BE Po18 MON- 50 Mon- 40 MON- 10 105 K/3.0 40-BE 0043 032-Br Po19 MON- 50 Mon- 30 MON- 20 95 K/2.4 42-BE 0033 032-Br Po20 MON- 40 Mon- 50 MON- 10 75 K/2.6 041-BE 0039 30-BE Po21 Mon- 40 MON- 50 MON- 10 85 K/2.6 0032 20-BE 30-Br Po22 Mon- 30 MON- 50 MON- 20 50 K/3.8 0032 01-BE 30-Br

B) Examples of Improved Dissolution Characteristics

[0235] Concentration of the solutions: 7 mg/ml, solvent: 3-phenoxytoluene

TABLE-US-00007 V1 Po1 V2 Po2 Time 47 38 52 42 required for complete dissolution (min) (min) 9 10

[0236] The time before the total amount of polymer has gone into solution is about 20% shorter for the polymers of the invention.

C) Device Examples

[0237] The polymers of the invention can be processed from solution. Solution-processed OLEDs are much more easily producible than vacuum-processed OLEDs and nevertheless have good properties.

[0238] There are already many descriptions of the production of such solution-based OLEDs in the literature, for example in WO 2004/037887 and WO 2010/097155. The process is matched to the circumstances described hereinafter (variation in layer thickness, materials).

[0239] The inventive polymers are used in two different layer sequences:

[0240] Structure A is as follows: [0241] substrate, [0242] ITO (50 nm), [0243] hole injection layer (HIL) (20 nm), [0244] hole transport layer (HTL) (20 nm), [0245] emission layer (EML) (60 nm), [0246] hole blocker layer (HBL) (10 nm) [0247] electron transport layer (ETL) (40 nm), [0248] cathode (Al) (100 nm).

[0249] Structure B is as follows: [0250] substrate, [0251] ITO (50 nm), [0252] hole injection layer (HIL) (20 nm), [0253] hole transport layer (HTL) (20 nm), [0254] emission layer (EML) (30 nm), [0255] hole blocker layer (HBL) (10 nm) [0256] electron transport layer (ETL) (40 nm), [0257] cathode (Al) (100 nm).

[0258] 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. The hole transport and emission layers are then applied to these coated glass plates.

[0259] 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 220 C. for 30 minutes.

[0260] The emission layer for structure A is composed of the host materials H2 and H3 and the emitting dopant D2. All three materials are present in the emission layer in a proportion by weight of 30% H2, 55% H3 and 15% D2. The mixture for the emission layer is dissolved in toluene. The solids content of this solution is 18 mg/ml, since layer thicknesses of 60 nm are to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere and baked at 150 C. for 10 minutes.

[0261] The emission layer for structure B is composed of the host material H1 and the emitting dopant D1. The two 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. The layers are spun on in an inert gas atmosphere and baked at 150 C. for 10 minutes.

[0262] The materials used in the present case are shown in Table C1.

TABLE-US-00008 TABLE C1 Structural formulae of the materials used in the emission layer [00406] H1 [00407] D1 [00408] H2 [00409] H3 [00410] D2

[0263] 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 Table C2. 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.

TABLE-US-00009 TABLE C2 HBL and ETL materials used [00411] ETM1 [00412] ETM2

[0264] The cathode is formed by the thermal evaporation of an aluminium layer of thickness 100 nm.

[0265] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, 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.

[0266] The properties of the different OLEDs are summarized in Tables C3a, C3b and C3c.

[0267] Examples C01 and C02 are comparative examples; all the other examples show properties of OLEDs comprising hole transport polymers of the invention. Blue- and green-emitting OLEDs comprising the materials of the invention as HTL are produced.

TABLE-US-00010 TABLE C3a Properties of the OLEDs Efficiency Voltage at 1000 at 1000 LD80 at HTL Component cd/m.sup.2 cd/m.sup.2 10 000 cd/m.sup.2 Example polymer structure % EQE [V] [h] C01 V1 A 18.2 4.8 552 C03 Po1 A 18.6 4.8 764

TABLE-US-00011 TABLE C3b Properties of the OLEDs Efficiency at LD80 at HTL Component 1000 cd/m.sup.2 1000 cd/m.sup.2 Example polymer structure % EQE [h] C02 V2 B 7.0 204 C04 Po2 B 7.1 223

[0268] As shown by the results in Tables C3a and C3b, the polymers of the invention, when used as hole transport layer in green-phosphorescing and blue-fluorescing OLEDs, result in improvements over the prior art, in particular in relation to lifetime, efficiency and voltage.

TABLE-US-00012 TABLE C3c Properties of the OLEDs Efficiency at Voltage at LD80 at LD80 at HTL Component 1000 cd/m.sup.2 1000 cd/m.sup.2 10 000 cd/m.sup.2 1000 cd/m.sup.2 Example polymer structure % EQE [V] [h] [h] C05 Po21 B 7.5 236 C06 Po5 B 7.6 210 C07 Po22 A 17.7 3.2 537

[0269] Table 3c shows the efficiency and lifetime of OLEDs comprising the inventive polymers Po5, Po21 and Po22. The polymers mentioned achieve good results for these parameters.

[0270] The further polymers Po3, Po4 and Po6-Po20 too can be used in the same way as shown above to produce blue-fluorescing or green-phosphorescing OLEDs. These also have good properties, especially good lifetime and efficiency.

[0271] In addition, it has been found that polymers containing structural units having one or more R.sup.1 groups, especially alkyl groups, as substituents on the ring system consisting of the U groups achieve better properties of the OLEDs than polymers containing structural units unsubstituted on the ring system consisting of the U groups.