POLYMERS WITH ASYMMETRIC REPEATING UNITS

Abstract

The invention relates to polymers having at least one asymmetrical structural unit of the following formula (I): wherein A, B, Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4, n, m, o and p can have the meaning as defined in claim 1, to methods for the production thereof and to the use thereof in electronic or optoelectronic devices, in particular in organic electroluminescent devices, so-called OLEDs (OLED=Organic Light Emitting Diodes). The present invention also relates to organic electroluminescent devices which contain said polymers.

##STR00001##

Claims

1-18. (canceled)

19. A polymer comprising at least one structural unit of formula (I): ##STR00131## wherein A is a polycyclic aromatic or heteroaromatic ring system having 10 to 60 aromatic or heteroaromatic ring atoms and which is optionally substituted by one or more R radicals; B is a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 10 aromatic or heteroaromatic ring atoms and which is optionally substituted by one or more R radicals; wherein the number of aromatic or heteroaromatic ring atoms in A is greater than the number of aromatic or heteroaromatic ring atoms in B; Ar.sup.1, Ar.sup.2, Ar.sup.3, and Ar.sup.4 are the same or different in each instance and are a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which is optionally substituted by one or more R radicals; n, m, o, and p are the same or different and are each 0 or 1; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, CS, CNR.sup.1, P(O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S, or CONR.sup.1 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which is optionally substituted by one or more R.sup.1 radicals, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms and which is optionally substituted by one or more R.sup.1 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.1 radicals, or a crosslinkable Q group; and wherein two or more R radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, and/or benzofused ring system; R.sup.1 is the same or different in each instance and is H, D, F, or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, an aromatic and/or a heteroaromatic hydrocarbyl radical having 5 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.1 substituents together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; and the dotted lines denote bonds to adjacent structural units in the polymer.

20. The polymer of claim 19, wherein the at least one structural unit of formula (I) is a structural unit of formula (Ia): ##STR00132##

21. The polymer of claim 19, wherein the at least one structural unit of formula (I) is a structural unit of formula (Ib):
------A-B-----(Ib).

22. The polymer of claim 19, wherein the at least one structural unit of formula (I) is a structural unit of formula (Ic): ##STR00133## wherein o is 0 or 1.

23. The polymer of claim 19, wherein the at least one structural unit of formula (I) is a structural unit of formula (Id): ##STR00134## wherein p is 0 or 1.

24. The polymer of claim 19, wherein the polycyclic, aromatic or heteroaromatic ring system A is selected from the group consisting of units A1 through A8: ##STR00135## wherein X is CR.sup.2, NR, SiR.sup.2, O, S, CO, or PO; o is 0, 1, 2, or 3; p is 0, 1, or 2; and q is 0, 1, 2, 3, or 4.

25. The polymer of claim 19, wherein the the mono- or polycyclic, aromatic or heteroaromatic ring system B is selected from the group consisting of units B1 through B4: ##STR00136## wherein X is CR.sup.2, NR, SiR.sup.2, O, S, CO, or PO; o is 0, 1, 2, or 3; p is 0, 1, or 2; and q is 0, 1, 2, 3, or 4.

26. The polymer of claim 19, wherein the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar.sup.2 and Ar.sup.3 are selected from the group consisting of units Ar1 through Ar10: ##STR00137## ##STR00138## wherein X is CR.sup.2, NR, SiR.sup.2, O, S, CO, or PO; o is 0, 1, 2, or 3; r is 0, 1, 2, 3, 4 or 5; and q is 0, 1, 2, 3, or 4.

27. The polymer of claim 19, wherein the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar.sup.1 and Ar.sup.4 are selected from the group consisting of units Ar11 through Ar20: ##STR00139## wherein X is CR.sup.2, NR, SiR.sup.2, O, S, CO, or PO; o is 0, 1, 2, or 3; p is 0, 1, or 2; and q is 0, 1, 2, 3, or 4.

28. The polymer of claim 19, wherein the proportion of structural units of formula (I) in the polymer is in the range of from 50 to 95 mol %, based on 100 mol % of all copolymerizable monomers present as structural units in the polymer.

29. The polymer of claim 19, wherein the polymer, in addition to the the structural units of formula (I), comprises further structural units different than the structural units of the formula (I).

30. The polymer of claim 19, wherein the polymer, in addition to the one or more structural units of the formula (I) and optionally further structural units, further comprises at least one structural unit comprising at least one crosslinkable Q group.

31. The polymer of claim 30, wherein the structural unit comprising the at least one crosslinkable group is selected from the group consisting of structural units of formulae (IIa) through (IIf): ##STR00140## wherein Q is a crosslinkable group.

32. A process for preparing the polymer of claim 19, comprising the step of preparing the polymer by SUZUKI polymerization, YAMAMOTO polymerization, STILLE polymerization, or HARTWIG-BUCHWALD polymerization.

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

34. An electronic or optoelectronic device comprising one or more active layers, wherein at least one of the one or more active layers comprises one or more polymers of claim 19.

35. The electronic or optoelectronic device of claim 34, wherein the electronic or optoelectronic device is selected from the group consisting of organic electroluminescent devices, organic light-emitting electrochemical cells, organic field-effect transistors, organic integrated circuits, organic thin-film transistors, organic solar cells, organic laser diodes, organic photovoltaic elements and devices, and organic photoreceptors.

Description

WORKING EXAMPLES

Part A: Synthesis of the Monomers

[0220] All syntheses are conducted in an argon atmosphere and in dry solvents, unless stated otherwise.

Example 1

[0221] Synthesis of Monomer Mon-1

##STR00062##

[0222] To an initial charge of 135 g (293 mmol) of 2-(9,9-dioctyl-9H-fluoren-2-yl)-[1,3,2]dioxaborolane and 87 g (299 mmol, 1.02 eq) of 1-bromo-4-iodobenzene in 2200 ml of ethylene glycol dimethyl ether are added 68 g (655 mmol) of Na.sub.2CO.sub.3 dissolved in 250 ml of H.sub.2O. The mixture is saturated with argon, 10.2 g (8.8 mmol) of tetrakis(triphenylphosphine)palladium(0) are added and the mixture is stirred under reflux for 48 hours. After cooling to room temperature, water and toluene are added to the mixture, and the organic phase is removed. The organic phase is washed three times with 500 ml each time of water, dried over sodium sulfate and freed of the solvent on a rotary evaporator. The crude product is then taken up in heptane and filtered through silica gel. Removing the solvent leaves 130 g (240 mmol, 82% of theory) of a beige solid (1).

[0223] 130 g (240 mmol) of the solid (1) and 42.6 g (240 mmol) of N-bromosuccinimide are dissolved in 3300 ml of DCM, and the mixture is heated to 40 C. Subsequently, 1 ml of 33% HBr solution in acetic acid is added and the mixture is stirred at 40 C. for 12 hours. After cooling to room temperature, the mixture is freed of the solvent on a rotary evaporator, dissolved in hot toluene and filtered. The orange solution is concentrated again on a rotary evaporator and the remaining solids are repeatedly dissolved in hot heptane and precipitated with ethanol. 82 g (130 mmol, 55% of theory) of Mon-1 were obtained.

Examples 2 to 6

[0224] Synthesis of Monomers Mon-2 to Mon-5 and Mon-16

[0225] Analogously to example 1, the reactants shown in table 1 below are used to obtain the monomers Mon-2 to Mon-5 and Mon-16 in the corresponding yields.

TABLE-US-00006 TABLE 1 Product Yield Example name Reactant Product [%] 1 Mon-1 [00063] [00064] 55 2 Mon-2 [00065] [00066] 73 3 Mon-3 [00067] [00068] 48 4 Mon-4 [00069] [00070] 62 5 Mon-5 [00071] [00072] 34 6 Mon-16 [00073] [00074] 52

Example 7

[0226] Synthesis of Monomer Mon-6

##STR00075##

[0227] To an initial charge of 82.4 g (280 mmol) of 2-(9H-fluoren-2-yl)-4,4,5,5-tetramethyl[1,3,2]dioxaborolane and 90.5 g (310 mmol) of 1-bromo-4-iodobenzene in 600 ml of ethylene glycol dimethyl ether are then added 65.7 g (620 mmol) of Na.sub.2CO.sub.3 dissolved in 160 ml of H.sub.2O. The mixture is saturated with argon, 10.2 g (8.8 mmol) of tetrakis(triphenylphosphine)palladium(0) are added and the mixture is stirred under reflux for 48 hours. Subsequently, the mixture is cooled down to room temperature and 500 ml of water and 600 ml of toluene are added. After phase separation, the organic phase is washed three times with 500 ml each time of water, dried over sodium sulfate and freed of the solvent on a rotary evaporator.

[0228] The remaining solids are subjected to extractive stirring in hot heptane and the suspension is filtered with suction. 50.3 g (157 mmol, 56% of theory) of a white solid (2) were obtained.

[0229] 50.3 g (157 mmol) of solid (2) are dissolved together with 28.1 g (158 mmol) of N-bromosuccinimide in 1300 ml of DCM and heated to 40 C. Subsequently, one drop of 33% HBr solution in acetic acid is added and the mixture is stirred at 40 C. for 12 hours. After cooling to room temperature, the mixture is freed of the solvent on a rotary evaporator, subjected to extractive stirring in hot ethanol and filtered. Filtration through silica gel (solvent: toluene) is followed by concentration of the solution again. The solids are taken up again in hot toluene, precipitated with ethanol, subjected to extractive stirring overnight, filtered off with suction and washed with methanol. 53.3 g (133 mmol, 85% of theory) of a solid (3) were obtained.

[0230] 9.5 g (23.5 mmol) of solid (3) are dissolved in 190 ml of dry DMSO. 13.8 g (144 mmol) of sodium t-butoxide are added to this solution at room temperature. The suspension is heated to 80 C., and 18.4 g (94 mmol) of 1-bromooct-8-ene are slowly added dropwise at this temperature. The mixture is stirred at 80 C. overnight. Subsequently, the mixture is cooled down to room temperature and quenched with 20 ml of toluene and 25 ml of water. After phase separation, the organic phase is washed three times with 500 ml each time of water, dried over sodium sulfate and freed of the solvent on a rotary evaporator. The solids are then eluted through a silica gel frit with heptane and the colorless eluate is concentrated on a rotary evaporator. Recrystallization from ethanol gave 6.5 g (10.4 mmol, 45% of theory) of Mon-6.

Examples 8 and 9

[0231] Synthesis of Monomers Mon-7 and Mon-8

[0232] Analogously to example 7, the reactants shown in table 2 below are used to obtain the monomers Mon-7 and Mon-8 in the corresponding yields.

TABLE-US-00007 TABLE 2 Product Yield Example name Reactant Product (%) 7 Mon-6 [00076] [00077] 45 8 Mon-7 [00078] [00079] 38 9 Mon-8 [00080] [00081] 63

Example 10

[0233] Synthesis of Monomer Mon-9

##STR00082##

[0234] An initial charge of 20 g (50 mmol) of solid (3) in 250 ml of THF is cooled down to 78 C. 28.7 ml (57.5 mmol) of lithium diisopropylamide (2 M in THF) are slowly added dropwise, and the mixture is warmed to room temperature and stirred for a further 15 minutes. Subsequently, the mixture is cooled back down to 78 C. and 14.2 g (100 mmol) of methyl iodide are added dropwise; the reaction comes to room temperature overnight. The reaction is quenched cautiously with a small amount of acetic acid and then water and toluene are added. After phase separation, the organic phase is washed three times with 500 ml each time of water, dried over sodium sulfate and freed of the solvent on a rotary evaporator. The remaining solids are subjected to extractive stirring in hot heptane and the suspension is filtered with suction. 18.3 g (44 mmol, 88% of theory) of a solid (4) were obtained.

[0235] An initial charge of 18.3 g (44 mmol) of solid (4) in 200 ml of THF is cooled down to 78 C. 66 ml (132 mmol) of lithium diisopropylamide (2 M in THF) are slowly added dropwise, and the mixture is warmed to room temperature and stirred for a further 15 minutes. Subsequently, the mixture is cooled back down to 78 C. and 15.8 g (66 mmol) of 3-(4-bromobutyl)bicyclo[4.2.0]octa-1(6),2,4-triene are added dropwise. The reaction comes to room temperature overnight and is then quenched cautiously with a small amount of water and acetic acid, then toluene is added. After phase separation, the organic phase is washed three times with 500 ml each time of water, dried over sodium sulfate and freed of the solvent on a rotary evaporator. The solids are then eluted through a silica gel frit with heptane and the colorless eluate is concentrated on a rotary evaporator. Recrystallization from ethanol gave 13.3 g (23.3 mmol, 53% of theory) of Mon-9.

Examples 11 to 13

[0236] Synthesis of Monomers Mon-10 to Mon-12

[0237] Analogously to example 10, the reactants shown in table 3 below are used to obtain the monomers Mon-10 to Mon-12 in the corresponding yields.

TABLE-US-00008 TABLE 3 Product Yield Example name Reactant Product (%) 10 Mon-9 [00083] [00084] 53 11 Mon-10 [00085] [00086] 48 12 Mon-11 [00087] [00088] 65 13 Mon-12 [00089] [00090] 28

Example 14

[0238] Synthesis of Monomer Mon-13

##STR00091##

[0239] 20 g (32 mmol) of monomer Mon-1, 23.6 g (96 mmol) of biphenyl-2-yl(phenyl)amine, 15.4 g (160 mmol) of sodium t-butoxide and 216 mg (0.96 mmol) of palladium acetate are dissolved in 400 ml of toluene. The mixture is saturated with argon at 45 C., then 1.92 ml (19.2 mmol) of tri-t-butylphosphine are added and the mixture is stirred under reflux for 12 hours. Subsequently, the reaction is cooled down to room temperature, water is added, and the organic phase is removed, washed three times with water, dried over sodium sulfate and freed of the solvent on a rotary evaporator. The remaining raw material is recrystallized repeatedly from a butanol/ethanol mixture. 19 g (19.8 mmol, 62% of theory) of solid (5) were obtained.

[0240] 19 g (19.8 mmol) of solid (5) are initially charged in 1000 ml of THF. The solution is cooled down to 10 C. with an ice/salt bath. Subsequently, 6.9 g (38.6 mmol) of N-bromosuccinimide are added. The mixture is stirred at 10 C. for 1.5 hours, then the mixture comes to room temperature overnight. The mixture is then freed of the solvent on a rotary evaporator, subjected to extractive stirring in hot ethanol and filtered. The remaining solids are recrystallized repeatedly in i-propanol. 17 g (15 mmol, 76% of theory) of Mon-13 were obtained.

Examples 15 and 16

[0241] Synthesis of Monomers Mon-14 and Mon-15

[0242] Analogously to example 14, the reactants shown in table 4 below are used to obtain the monomers Mon-14 and Mon-15 in the corresponding yields.

TABLE-US-00009 TABLE 4 Pro- Ex- duct Yield ample name Reactant Product (%) 14 Mon- 13 [00092] [00093] 76 15 Mon- 14 [00094] [00095] 58 16 Mon- 15 [00096] [00097] 44

Example 17

[0243] Synthesis of Monomer Mon-1-BE

##STR00098##

[0244] 10 g (16 mmol) of monomer Mon-1 are initially charged together with 10.2 g (40 mmol) of bis(pinacolato)diboron, 5.2 g (53 mmol) of potassium acetate, 0.35 g (0.48 mmol) of Pd(dppf)Cl.sub.2*CH.sub.2Cl.sub.2 in 200 ml of DMSO. The mixture is heated to 40 C. and saturated with argon for 20 minutes. Subsequently, the reaction is stirred at 80 C. overnight and cooled down to room temperature. After addition of 150 ml of water and 150 ml of ethyl acetate, the organic phase is removed, washed 3 times with water, dried over sodium sulfate and finally concentrated on a rotary evaporator. The remaining solids are repeatedly dissolved in hot heptane and precipitated again with ethanol. 8.3 g (11.5 mmol, 72% of theory) of monomer Mon-1-BE were obtained.

Examples 18 to 20

[0245] Synthesis of Monomers Mon-6-BE, Mon-9-BE and Mon-13-BE

[0246] Analogously to example 17, the reactants shown in table 5 below are used to obtain the monomers Mon-6-BE, Mon-9-BE and Mon-13-BE in the corresponding yields.

TABLE-US-00010 TABLE 5 Ex- Product Yield ample name Reactant Product (%) 17 Mon-1- BE [00099] [00100] 72 18 Mon-6- BE [00101] [00102] 83 19 Mon-9- BE [00103] [00104] 67 20 Mon-13- BE [00105] [00106] 55

[0247] Further Monomers:

[0248] Further monomers for production of the polymers of the invention are already described in the prior art, are commercially available or are prepared according to a literature method, and are summarized in table 6 below:

TABLE-US-00011 TABLE 6 Synthesis Monomer Structure according to Mon-101-BE [00107] WO 99/048160 A1 Mon-102-BE [00108] WO 2013/156130 Mon-102 [00109] WO 2013/156130 Mon-103 [00110] WO 2013/156130 Mon-103-BE [00111] WO 2013/156130 Mon-104 [00112] WO 2010/097155 A1 Mon-104-BE [00113] WO 2010/097155 A1 Mon-105 [00114] analogous to: WO 2013/156130 Mon-106-BE [00115] WO 2009/102027 Mon-107 [00116] WO 2010/136111 Mon-107-BE [00117] WO 2010/136111 Mon-108 [00118] WO 2003/020790 Mon-109-BE [00119] WO 2005/104264 Mon-110 [00120] Macromolecules 2000, 33, 2016-2020 Mon-110-Be [00121] Macromolecules 2000, 33, 2016-2020 Mon-111 [00122] CAS 16400-51-4 Mon-112 [00123] WO 2013/156125 A1

[0249] Part B: Synthesis of the Polymers

Examples 21 to 41

[0250] Preparation of comparative polymers V1, V2, V3 and V4 and of inventive polymers Po1 to Po17

[0251] The comparative polymers V1, V2, V3 and V4 and the inventive polymers Po1 to Po17 are prepared by SUZUKI coupling by the process described in WO 03/048225 from the monomers disclosed in Part A.

[0252] The polymers V1 to V4 and Po1 to Po17 prepared in this way contain the structural units, after elimination of the leaving groups, in the percentages reported in table 7 below (percent figures=mol %). 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. The polymers listed correspondingly in Table 7 and used in Part C thus have crosslinkable vinyl groups rather than the aldehyde groups originally present.

[0253] The palladium and bromine contents of the polymers are determined by ICP-MS. The values determined are below 10 ppm.

[0254] 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.

TABLE-US-00012 Molecular Exam- Poly- weight Polydisp. ple mer Inventive monomers Further monomers M.sub.w (g/mol) D 21 V1 Mon-110 50% Mon- 50% 145 000 2.5 101-BE 22 V2 Mon-110 50% Mon- 40% Mon- 10% 125 000 2.9 101-BE 104-BE 23 V3 Mon- 25% Mon- 25% Mon-111 50% 85 000 5.3 110-BE 102-BE 24 V4 Mon-112 50% Mon- 50% 160 000 2.3 101-BE 25 Po1 Mon-1 50% Mon- 50% 123 000 2.6 101-BE 26 Po2 Mon-4 50% Mon- 50% 153 000 3.2 103-BE 27 Po3 Mon-1 50% Mon- 40% Mon- 10% 98 000 3.5 101-BE 104-BE 28 Po4 Mon-3 50% Mon- 30% Mon- 20% 180 000 2.8 102-BE 106-BE 29 Po5 Mon- 50% Mon-9 10% Mon-103 40% 135 000 3.2 1-BE 30 Po6 Mon-5 30% Mon-6 10% Mon-8 10% Mon- 50% 155 000 2.9 103-BE 31 Po7 Mon-7 10% Mon-101 40% Mon- 50% 189 000 1.9 110-BE 32 Po8 Mon-10 10% Mon-11 10% Mon- 30% Mon- 20% Mon-102 30% 220 000 2.7 109-BE 102-BE 33 Po9 Mon-4 50% Mon- 50% 138 000 2.1 9-BE 34 Po10 Mon- 50% Mon-102 30% Mon-105 20% 114 000 2.5 13-BE 35 Po11 Mon-14 30% Mon-15 20% Mon- 50% 136 000 2.4 108-BE 36 Po12 Mon-2 30% Mon- 50% Mon-105 20% 163 000 2.6 103-BE 37 Po13 Mon- 25% Mon- 25% Mon-111 50% 74 000 4.8 1-BE 102-BE 38 Po14 Mon-15 25% Mon-3 25% Mon- 50% 185 000 1.8 107-BE 39 Po15 Mon-13 20% Mon-12 25% Mon- 50% 155 000 3.1 107-BE 40 Po16 Mon-13 50% Mon- 50% 195 000 2.7 101-BE 41 Po17 Mon-16 50% Mon- 50% 68 000 3.2 103-BE

Part C: Production of the OLEDs

Examples 21 to 41

[0255] The comparative polymers and the inventive polymers are processed from solution.

[0256] Whether the crosslinkable variants of the polymers after crosslinking give rise to a completely insoluble layer is tested analogously to WO 2010/097155.

[0257] Table 8 lists the remaining layer thickness of the original 100 nm after the washing operation described in WO 2010/097155. If there is no decrease in the layer thickness, the polymer is insoluble and hence the crosslinking is sufficient.

TABLE-US-00013 TABLE 8 Check of the residual layer thickness of the original 100 nm after the wash test Residual layer thickness after wash test [in nm] Polymer Crosslinking at 220 C. for 30 minutes V1 22.5 V2 99 Po3 99.5 Po5 98 Po10 98.5 Po12 99

[0258] As can be inferred from Table 8, comparative polymer V1 which does not bear any crosslinking group hardly crosslinks at all on baking at 220 C. for 30 minutes. Comparative polymer V2 and inventive polymers Po3, Po5, Po10 and Po12 crosslink fully at 220 C.

[0259] There are already many descriptions of the production of 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).

[0260] The inventive polymers are used in two different layer sequences:

[0261] Structure A is as follows: [0262] substrate, [0263] ITO (50 nm), [0264] PEDOT:PSS (20 nm), [0265] hole transport layer (HTL) (20 nm), [0266] emission layer (EML) (60 nm), [0267] hole blocker layer (HBL) (10 nm), [0268] electron transport layer (ETL) (40 nm), [0269] cathode.

[0270] Structure B is as follows: [0271] substrate, [0272] ITO (50 nm), [0273] PEDOT:PSS (20 nm), [0274] hole transport layer (HTL) (40 nm), [0275] emission layer (EML) (30 nm), [0276] electron transport layer (ETL) (20 nm), [0277] cathode.

[0278] Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. These are coated with PEDOT:PSS. Spin-coating is effected under air from water. The layer is baked at 180 C. for 10 minutes. PEDOT:PSS is sourced from Heraeus Precious Metals GmbH & Co. KG, Germany. The hole transport layer and the emission layer are applied to these coated glass plates.

[0279] The hole transport layers used are the compounds of the invention and comparative compounds, each dissolved in toluene. The typical solids content of such solutions is about 5 g/l when, as here, the layer thicknesses of 20 nm or 40 nm which are typical of a device are to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 220 C. for 30 minutes in the case of the crosslinked polymers (structure A) and at 180 C. for 10 minutes in the case of the uncrosslinked polymers (structure B).

[0280] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). In addition, mixtures of a plurality of matrix materials and co-dopants may occur. Details given in such a form as H1 (92%):dopant (8%) mean here that the material H1 is present in the emission layer in a proportion by weight of 92% and the dopant in a proportion by weight of 8%. The mixture for the emission layer is dissolved in toluene for structure A. The typical solids content of such solutions is about 18 g/l when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The layers are spun on in inert gas atmosphere, argon in the present case, and baked at 150 C. for 10 minutes.

[0281] In structure B, the emission layer is formed by thermal evaporation in a vacuum chamber. This layer may consist of more than one material, the materials being added to one another by co-evaporation in a particular proportion by volume.

[0282] Details given in such a form as H3:dopant (95%:5%) mean here that the H3 and dopant materials are present in the layer in a proportion by volume of 95%:5%.

[0283] The materials used in the present case are shown in table 9.

TABLE-US-00014 TABLE 9 Structural formulae of the materials used in the emission layer [00124] H1 [00125] H2 [00126] H3 [00127] TEG [00128] SEB

[0284] The materials for the hole blocker layer and electron transport layer are likewise applied by thermal vapor deposition in a vacuum chamber and are shown in Table 10. The hole blocker layer consists of ETM1. The electron transport layer consists of the two materials ETM1 and ETM2, which are added to one another by co-evaporation in a proportion by volume of 50% each.

TABLE-US-00015 TABLE 10 HBL and ETL materials used [00129] ETM1 [00130] ETM2

[0285] The cathode is formed by the thermal evaporation of an aluminum layer of thickness 100 nm.

[0286] The exact structure of the OLEDs can be found in Table 11.

TABLE-US-00016 TABLE 11 Structure of the OLEDs Example HTL polymer Structure EML composition 42 V1 B H3 95%; SEB 5% 43 V2 A H1 30%; H2 55%; TEG 15% 44 V3 B H3 95%; SEB 5% 45 Po3 A H1 30%; H2 55%; TEG 15% 46 Po5 A H1 30%; H2 55%; TEG 15% 47 Po10 A H1 30%; H2 55%; TEG 15% 48 Po12 A H1 30%; H2 55%; TEG 15% 49 Po13 B H3 95%; SEB 5%

[0287] 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 such as the operating voltage (in V) and 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.

[0288] The properties of the different OLEDs are summarized in tables 12a and 12b. Examples 42 and 44 show comparative components; all the other examples show properties of inventive OLEDs.

[0289] Tables 12a and 12b:

[0290] Properties of the OLEDs

TABLE-US-00017 TABLE 12a Efficiency at Voltage at LT80 at 1000 cd/m.sup.2 1000 cd/m.sup.2 10 000 cd/m.sup.2 Example % EQE [V] [h] 42 4.9 4.5 120 44 8.0 4.6 160 49 9.7 4.8 160

TABLE-US-00018 TABLE 12b Efficiency at Voltage at LT80 at 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Example % EQE [V] [h] 43 17.0 4.2 110 45 18.8 4.3 125 46 18.9 4.2 130 47 17.9 3.9 260 48 18.1 3.8 230

[0291] As shown in tables 12a and 12b, the polymers of the invention, when used as hole transport layer in OLEDs, show improvements over the prior art. By virtue of their higher triplet level and the larger bandgap, the efficiencies in particular of the green- and blue-emitting OLEDs produced are improved.

[0292] The fact that the polymers of the invention have a higher triplet level than their direct comparative polymers is shown by quantum-mechanical calculations using some selected polymers. The results are shown in table 13.

TABLE-US-00019 TABLE 13 Comparison of the calculated T1 level Polymer V1 Po1 Po2 V2 Po3 V3 Po13 V4 Po16 T1 (eV) 2.31 2.43 2.49 2.31 2.45 2.38 2.52 2.31 2.45