POLYMERS WITH AMINE-GROUP-CONTAINING REPEATING UNITS

Abstract

The invention relates to polymers having at least one repeating unit of the following formula (I): wherein Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4, R and X, and a, b, c, d, e and f can have the meanings defined in claim 1, to processes for the preparation 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 electronic or optoelectronic devices, in particular organic electroluminescent devices, which contain said polymers.

Claims

1.-17. (canceled)

18. A polymer having at least one repeat unit of the following formula (I): ##STR00248## where X O, S, NR or CR.sub.2; Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 are the same or different at each instance and are independently a mono- or polycyclic, aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R radicals; a and b are the same or different at each instance and are independently 0 or 1; where (a+b)=1 or 2; c and d are the same or different at each instance and are independently 0 or 1; e and f are the same or different at each instance and are independently 0, 1, 2 or 3; R is the same or different at each instance and is independently 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, an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)R.sup.1, SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; or a crosslinkable group Q, where two or more R radicals together may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; R.sup.1 is the same or different at each instance and is independently H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, an aromatic or a heteroaromatic hydrocarbyl radical having 5 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; where two or more R.sup.1 substituents together may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; and the dotted lines represent bonds to adjacent repeat units in the polymer.

19. The polymer as claimed in claim 18, wherein the at least one repeat unit of the formula (I) is selected from the repeat unit of the following formula (II): ##STR00249## where Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, c and d may assume the definitions given in claim 18.

20. The polymer as claimed in claim 18, wherein the at least one repeat unit of the formula (I) is selected from the repeat unit of the following formula (III): ##STR00250## where Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4 may assume the definitions given in claim 18.

21. The polymer as claimed in claim 18, wherein the at least one repeat unit of the formula (I) is selected from the repeat unit of the following formula (IV): ##STR00251## where Ar.sup.1 and Ar.sup.2 and X may assume the definitions given in claim 18 and c=0 or 1.

22. The polymer as claimed in claim 18, wherein the at least one repeat unit of the formula (I) is selected from the repeat unit of the following formula (V): ##STR00252## where Ar.sup.1 and Ar.sup.2 may assume the definitions given in claim 18.

23. The polymer as claimed in claim 18, wherein the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar.sup.2 and Ar.sup.4 in the repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), (IIIc), (IV), (V), (Va), (Vb) and (Vc) are selected from the following units Ar1 to Ar10: ##STR00253## ##STR00254## where R may assume the definitions given in claim 18, X=CR.sup.2, NR, SiR.sup.2, O, S, C═O or P═O, p=0, 1, 2 or 3, q=0, 1, 2, 3 or 4, and r=0, 1, 2, 3, 4 or 5.

24. The polymer as claimed in claim 18, wherein the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar.sup.1 and Ar.sup.3 in the repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), (IIIc), (IV), (V), (Va), (Vb) and (Vc) are selected from the following units Ar11 to Ar18: ##STR00255## where R may assume the definitions given in claim 18, X=CR.sup.2, NR, SiR.sup.2, O, S, C═O or P═O, o=0, 1 or 2, p=0, 1, 2 or 3, and q=0, 1, 2, 3 or 4.

25. The polymer as claimed in claim 18, wherein the proportion of repeat units of the formula (I), (II), (III), (IIIa), (IIIb), (IIIc), (IV), (V), (Va), (Vb) and/or (Vc) ##STR00256## ##STR00257## in the polymer is in the range from 5 to 75 mol %, based on 100 mol % of all copolymerizable monomers present as repeat units in the polymer.

26. The polymer as claimed in claim 18, wherein the polymer, as well as one or more repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), (IIIc), (IV), (V), (Va), (Vb) and/or (Vc), also comprises further repeat units other than the repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), (IIIc), (IV), (V), (Va), (Vb) and/or (Vc).

27. The polymer as claimed in claim 18, wherein the polymer, as well as one or more repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), (IIIc), (IV), (V), (Va), (Vb) and/or (Vc) ##STR00258## ##STR00259## and optionally further repeat units, also comprises at least one repeat unit having at least one crosslinkable group Q.

28. The polymer as claimed in claim 27, wherein the repeat unit having at least one crosslinkable group is selected from the repeat unit of the formula (Ix) ##STR00260## where Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, R and X and a, b, c, d, e and f may assume the definitions given in claim 18 in relation to formula (I), but with the proviso that at least one R is a crosslinkable group Q.

29. The polymer as claimed in claim 27, wherein the repeat unit having the at least one crosslinkable group is selected from the repeat units of the formulae (IIx1), (IIx2) and (IIx3) ##STR00261## where X in formula (IIx1): is NQ, CRQ or CQ.sub.2; ##STR00262## where X in formula (IIx2): is O, S, NR or CR.sub.2; and ##STR00263## where X in formula (IIx3): is O, S, NR or CR.sub.2; Q is a crosslinkable group; and Ar.sup.1, Ar.sup.2, Ar.sup.3 and Ar.sup.4, and c and d in the formulae (IIx1), (IIx2) and (IIx3) may assume the definitions given in claim 18 in relation to formula (I).

30. A process for preparing the polymer as claimed in claim 18, which comprises preparing the polymer by SUZUKI polymerization, YAMAMOTO polymerization, STILLE polymerization or HARTWIG-BUCHWALD polymerization.

31. A polymer blend comprising one or more polymers as claimed in claim 18 containing at least one repeat unit of the formula (I) and one or more further polymeric, oligomeric, dendritic and/or low molecular weight substances.

32. A solution or formulation composed of one or more polymers as claimed in claim 18 in one or more solvents.

33. A solution or formulation composed the polymer blend as claimed in claim 31 in one or more solvents.

34. An electronic or optoelectronic device comprising the polymer as claimed in claim 18.

35. An organic electroluminescent device (OLED), organic light-emitting electrochemical cell (OLEC), organic field-effect transistor (OFET), organic integrated circuit (O-IC), organic thin-film transistor (TFT), organic solar cell (O-SC), organic laser diode (O-laser), organic photovoltaic (OPV) element or device or organic photoreceptor (OPC) having one or more active layers, wherein at least one of these active layers comprises one or more polymers as claimed in claim 18.

36. An organic electroluminescent device, having one or more active layers, wherein at least one of these active layers comprises one or more polymers as claimed in claim 18.

Description

WORKING EXAMPLES

Part A: Synthesis of the Monomers

[0197] All syntheses are conducted in an argon atmosphere and in dry solvents, unless stated otherwise.

[0198] The monomers are synthesized using the following starting materials that are known from the literature:

a) Substituted 3,6-dibromocarbazoles

##STR00080## ##STR00081##

b) Substituted 3,6-dibromofluorenes

##STR00082##

c) Dibromodibenzofurans and dibromodibenzothiophenes

##STR00083##

d) Secondary Amines

[0199] ##STR00084##

Example 1

Synthesis of Monomer Mon-1

1st Step: Synthesis of the Precursor:

[0200] ##STR00085##

[0201] To a mixture of 36.7 g (150 mmol) of biphenyl-4-ylphenylamine, 30 g (74.8 mmol, 0.5 eq) of 3,6-dibromo-9-phenylcarbazole, 0.84 g of palladium acetate (3.74 mmol, 0.025 eq), 43.1 g of sodium tert-butoxide (449 mmol, 3 eq) and 7.5 ml of tri-tert-butylphosphine (7.5 mmol, 0.05 eq) is added 600 ml of dried toluene, and the mixture is inertized and boiled under reflux (110° C.) for 2 days. The reaction solution is cooled down and diluted with water, and the organic phase is separated off. The solvent is removed under a gentle vacuum, and the residue is purified by hot extraction over neutral alumina with cyclohexane as eluent. The residue is filtered off and dried under reduced pressure. 38.5 g (71% yield) of a colorless powder is obtained.

2nd Step: Synthesis of Monomer Mon-1-Br:

[0202] ##STR00086##

[0203] To an initial charge of 38.5 g (52.7 mmol) of N,N′-bis(biphenyl-4-yl)-9,N,N′-triphenyl-9H-carbazole-3,6-diamine in a 1000 ml flask is added 850 ml of dichloromethane. The solution is cooled down to internal temperature 0° C. by cooling with ice, and 18.78 g (105.5 mmol, 2 eq) of N-bromosuccinimide is added gradually. After the addition, the ice bath is removed, and the mixture is allowed to warm up to room temperature. The solvent is removed under reduced pressure, and the solids are filtered off and washed thoroughly with water. The residue is recrystallized first from ethyl acetate, then from toluene. 8.5 g (9.58 mmol, 18% yield) of a colorless powder having a purity of 99% is obtained.

3rd Step: Synthesis of Monomer Mon-1-Bo:

[0204] ##STR00087##

[0205] 50 g of N′-bis(4-bromophenyl)-9-phenyl-N,N′-diphenyl-9H-carbazole-3,6-diamine (A1:B2:Br) (65.5 mmol), 54 g of 4,4,5,5,4′,4′,5′,5′-octamethyl-[2,2′]bi[[1,3,2]dioxaborolanyl] (212.8 mmol, 3.25 eq, CAS: 73183-34-3), 1.64 g of 1,1-bis(diphenylphosphino)ferrocenedichoropalladium (II) (2.01 mmol, 0.25 eq, CAS: 72287-26-4) and 25.7 g of potassium acetate (261.9 mmol, 4 eq) are weighed out in a 2 liter 4-neck flask with reflux condenser, precision glass stirrer, argon blanketing and internal thermometer, and 1300 ml of anhydrous THE is added. After the apparatus has been fully degassed, the mixture is boiled under reflux for 3 days, and then the reaction mixture is allowed to cool down. The solvent is removed under reduced pressure, and the solids are recrystallized repeatedly from ethyl acetate and then from toluene. 43.21 g (50.38 mmol, 77% of theory) of a colorless powder is obtained.

[0206] The following monomers can be prepared analogously to example 1:

##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111##

Example 2

Synthesis of Monomer Mon-2

1 st Step: Synthesis of the Precursor:

[0207] ##STR00112##

[0208] To a mixture of 41.81 g (170 mmol) of tol-4-ylphenylamine, 30 g (85.2 mmol, 0.5 eq) of 3,6-dibromo-9,9-dimethylfluorene, 0.96 g of palladium acetate (4.26 mmol, 0.025 eq), 49.1 g of sodium tert-butoxide (511 mmol, 3 eq) and 8.5 ml of tri-tert-butylphosphine (1 M, 8.5 mmol, 0.05 eq) is added 700 ml of dried toluene, and the mixture is inertized and boiled under reflux (110° C.) for 2 days. The reaction solution is cooled down and diluted with water, and the organic phase is separated off. The solvent is removed under a gentle vacuum, and the residue is purified by hot extraction over neutral alumina with cyclohexane as eluent. The residue is filtered off and dried under reduced pressure. 46.42 g (80% yield, 85.2 mmol) of a colorless powder is obtained.

2nd Step: Synthesis of Monomer Mon-2-Br:

[0209] ##STR00113##

[0210] To an initial charge of 43 g (77.24 mmol) of 9,9-dimethyl-N3,N6-bis(4-methylphenyl)-N3,N6-diphenyl-9H-fluorene-3,6-diamine in a 1000 ml flask is added 800 ml of dichloromethane. The solution is cooled down to internal temperature 0° C. by cooling with ice, and 27.5 g (154.5 mmol, 2 eq) of N-bromosuccinimide is added gradually. After the addition, the ice bath is removed, and the mixture is allowed to warm up to room temperature. The solvent is removed under reduced pressure, and the solids are filtered off and washed thoroughly with water. The residue is recrystallized first from ethyl acetate, then from toluene. 49.12 g (68.74 mmol, 89% yield) of a colorless powder having a purity of 98% is obtained.

3rd Step: Synthesis of Monomer Mon-2-Bo

[0211] ##STR00114##

[0212] 50 g of N3,N6-bis(4-bromophenyl)-9,9-dimethyl-N3,N6-bis(4-methylphenyl)-9H-fluorene-3,6-diamine (A1:B2:Br) (70 mmol), 54 g of 4,4,5,5,4′,4′,5′,5′-octamethyl-[2,2′]bi[[1,3,2]dioxaborolanyl] (227.4 mmol, 3.25 eq, CAS: 73183-34-3), 1.28 g of 1,1-bis(diphenylphosphino)ferrocenedichoropalladium (II) (1.75 mmol, 0.025 eq, CAS: 72287-26-4) and 27.5 g of potassium acetate (279.9 mmol, 4 eq) are weighed out in a 2 liter 4-neck flask with reflux condenser, precision glass stirrer, argon blanketing and internal thermometer, and 1300 ml of anhydrous THE is added. After the apparatus has been fully degassed, the mixture is boiled under reflux for 3 days, and then the reaction mixture is allowed to cool down. The solvent is removed under reduced pressure, and the solids are recrystallized repeatedly from ethyl acetate and then from toluene. 46.4 g (57.38 mmol, 82% of theory) of a colorless powder is obtained.

[0213] The following monomers can be prepared analogously to example 2:

##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125##

Example 3

Synthesis of Monomer Mon-3

1st Step: Synthesis of the Precursor:

[0214] ##STR00126##

[0215] To a mixture of 52.7 g (214.7 mmol) of biphenyl-4-ylphenylamine, 35 g (107.4 mmol, 0.5 eq) of 3,6-dibromodibenzofuran, 0.60 g of palladium acetate (2.68 mmol, 0.012 eq), 31 g of sodium tert-butoxide (332.1 mmol, 1.5 eq) and 5.4 ml of tri-tert-butylphosphine (5.37 mmol, 0.05 eq) is added 750 ml of dried toluene, and the mixture is inertized and boiled under reflux (110° C.) for 2 days. The reaction solution is cooled down and diluted with water, and the organic phase is separated off. The solvent is removed under a gentle vacuum, and the residue is purified by hot extraction over neutral alumina with cyclohexane as eluent. The residue is filtered off and dried under reduced pressure. 59.1 g (84% yield) of a colorless powder is obtained.

2nd Step: Synthesis of Monomer Mon-3-Br:

[0216] ##STR00127##

[0217] To an initial charge of 64 g (120.6 mmol) of N4,N12-bis(4-methylphenyl)-N4,N12-diphenyl-8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(9),2,4,6,10,12-hexaene-4,12-diamine in a 1000 ml flask is added 900 ml of dichloromethane. The solution is cooled down to internal temperature 0° C. by cooling with ice, and 42.9 g (241.2 mmol, 2 eq) of N-bromosuccinimide is added gradually. After the addition, the ice bath is removed, and the mixture is allowed to warm up to room temperature. The solvent is removed under reduced pressure, and the solids are filtered off and washed thoroughly with water. The residue is recrystallized first from ethyl acetate, then from toluene. 70.58 g (102.5 mmol, 85% yield) of a colorless powder having a purity of 98% is obtained.

3rd Step: Synthesis of Monomer Mon-3-Bo

[0218] ##STR00128##

[0219] 37 g of N4,N12-bis(4-bromophenyl)-N4,N12-bis(4-methylphenyl)-8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(9),2,4,6,10,12-hexaene-4,12-diamine (D1:B1:Br) (753.7 mmol), 44.4 g of 4,4,5,5,4′,4′,5′,5′-octamethyl-[2,2′]bi[[1,3,2]dioxaborolanyl] (174.7 mmol, 3.25 eq, CAS: 73183-34-3), 0.98 g of 1,1-bis(diphenylphosphino)ferrocenedichoropalladium (II) (1.34 mmol, 0.025 eq, CAS: 72287-26-4) and 21.1 g of potassium acetate (215 mmol, 4 eq) are weighed out in a 2 liter 4-neck flask with reflux condenser, precision glass stirrer, argon blanketing and internal thermometer, and 1300 ml of anhydrous THE is added. After the apparatus has been fully degassed, the mixture is boiled under reflux for 3 days, and then the reaction mixture is allowed to cool down. The solvent is removed under reduced pressure, and the solids are recrystallized repeatedly from ethyl acetate and then from toluene. 38.3 g (48.9 mmol, 91% of theory) of a colorless powder is obtained.

[0220] The following monomers can be prepared analogously to example 3:

##STR00129## ##STR00130## ##STR00131##

Further Monomers:

[0221] 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 the following table:

TABLE-US-00004 Monomer Structure Synthesis according to Mo1-Bo [00132] WO 99/048160 A1 Mo2-Br [00133] WO 2013/156130 A1 Mo2-Bo [00134] WO 2013/156130 A1 Mo3-Br [00135] Borylation analogous to WO 2013/156130 A1 Mo4-Br [00136] CAS 2043618-74-0 Mo5-Bo [00137] CAS 897404-05-6 Mo5-Br [00138] CAS 117635-21-9 Mo6-Br [00139] CAS 16400-51-4 Mo7-Br [00140] WO 2010/136111 A1 Mo7-Bo [00141] WO 2010/136111 A1 Mo8-Bo [00142] WO 2010/097155 A1 Mo8-Br [00143] WO 2010/097155 A1 Mo9-Br [00144] WO 2018/114882 A1 Mo9-Bo [00145] Borylation analogous to WO 2013/156130 A1 Mo10-Br [00146] WO 2018/114882 A1 Mo10-Bo [00147] Borylation analogous to WO 2013/156130 A1 Mo11-Br [00148] WO 2018/114882 A1 Mo12-Br [00149] WO 2009/102027 A1 Mo12-Bo [00150] WO 2009/102027 A1 Mo13-Br [00151] CAS 868704-91-0 Mo13-Bo [00152] Borylation analogous to WO 2013/156130 A1 Mo14-Bo [00153] WO 03/020790 A2 Mo15-Br [00154] Macromolecules 2000, 33, 2016-2020 Mo15-Bo [00155] CAS 628303-20-8 Mo16-Br [00156] CAS 2231251-18-4 Mo16-Bo [00157] CAS 2231251-19-5

Part B: Synthesis of the Polymers

Examples 1 to 36

Preparation of Inventive Polymers P1 to P35 and of Comparative Polymer V1

[0222] Inventive polymers P1 to P35 and comparative polymer V1 are prepared by SUZUKI coupling by the method described in WO 03/048225 from the monomers disclosed in part A.

[0223] The polymers P1 to P35 and V1 that have been prepared in this way contain the repeat units, after elimination of the leaving groups, in the percentages specified in the table below (percentages=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 correspondingly listed in the table below and used in part C thus have crosslinkable vinyl groups in place of the aldehyde groups originally present.

[0224] The palladium and bromine contents of the polymers are determined by ICP-MS. The values determined are below 10 ppm.

[0225] The molecular weights M.sub.w and the polydispersities D ascertained by means of gel permeation chromatography (GPC) (model: Agilent HPLC System Series 1100) (column: PL-RapidH from Polymer Laboratories; solvent: THE with 0.12% by volume of o-dichlorobenzene; detection: UV and refractive index; temperature: 40° C.). Calibration is effected with polystyrene standards.

TABLE-US-00005 (Mw) Poly- [g/mol]/ mer Inventive monomers Further monomers D P1  [00158] [00159] 77.000 4.3 A1:B1:Br Mo1-Bo 50% 50% P2  [00160] [00161] 85.000 5.2 A1:B1:Br Mo2-Bo 50% 50% P3  [00162] [00163] 53.000 6.3 A1:B1:Br Mo5-Bo 50% 50% P4  [00164] [00165] 55.000 6.3 A1:B1:Br Mo7-Bo 50% 50% P5  [00166] [00167] 90.000 5.4 A1:B1:Br Mo8-Bo 50% 50% P6  [00168] [00169] 89.000 5.3 A1:B1:Br Mo9-Bo 50% 50% P7  [00170] [00171] 92.000 5.5 A1:B1:Br Mo12-Bo 50% 50% P8  [00172] [00173] 105.000 4.2 A1:B1:Br Mo14-Bo 50% 50% P9  [00174] [00175] 97.000 4.5 A1:B1:Br Mo15-Bo 50% 50% P10 [00176] [00177] 78.000 5.3 A1:B5:Br Mo2-Bo 50% 50% P11 [00178] [00179] 108.000 3.3 A1:B14:Br Mo15-Bo 40% 50% [00180] Mo8-Br 10% P12 [00181] [00182] 60.000 3.0 A1:B14:Br Mo13-Br 40% 50% [00183] Mo8-Br 10% P13 [00184] [00185] 85.000 2.5 A1:B14:Br Mo2-Bo 50% 30% [00186] Mo8-Br 20% P14 [00187] [00188] 96.000 2.7 A1:B5:Br Mo5-Bo 30% 50% [00189] Mo8-Br 20% P15 [00190] [00191] 120.000 2.9 A1:B5:Br Mo8-Bo 50% 50% P16 [00192] [00193] 75.000 5.4 A9:B9:Br Mo2-Bo 50% 50% P17 [00194] [00195] 67.000 6.6 A9:B14:Br Mo2-Bo 50% 50% P18 [00196] [00197] 78.000 5.2 A21:B2:Br Mo2-Bo 50% 50% P19 [00198] [00199] 64.000 5.3 A1:B14:BOR Mo2-Br 50% 50% P20 [00200] [00201] 74.000 5.1 A8:B9:BOR Mo2-Br 50% 50% P21 [00202] [00203] 83.000 5.7 A16:B13:BOR Mo2-Br 50% 50% P22 [00204] [00205] 68.000 6.2 C1:B14:Br Mo2-Bo 50% 50% P23 [00206] [00207] 107.000 5.9 C3:B9:Br Mo2-Bo 50% 50% P24 [00208] [00209] 77.000 5.3 C4:B14:BOR Mo2-Br 50% 50% P25 [00210] [00211] 61.000 4.8 D1:B14:BOR Mo2-Br 50% 50% P26 [00212] [00213] 55.000 6.0 A1:B5:Br Mo5-Bo 50% 50% P27 [00214] [00215] 68.000 5.1 A1:B5:Br Mo8-Bo 50% 50% P28 [00216] [00217] 88.000 5.0 A1:B5:Br Mo15-Bo 50% 50% P29 [00218] [00219] 93.000 5.6 A1:B5:Br Mo2-Bo 25% 50% [00220] Mo8-Bo 25% P30 [00221] [00222] 55.000 6.8 A1:B5:Br Mo5-Bo 40% 50% [00223] Mo8-Br 10% P31 [00224] [00225] 74.000 5.7 A1:B5:Br Mo15-Bo 50% 30% [00226] Mo8-Bo 20% P32 [00227] [00228] 80.000 A1:B14:Br Mo13-Bo 20% 50% [00229] Mo14-Br 20% [00230] Mo8-Br 10% P33 [00231] [00232] 68.000 A1:B5:Br Mo16-Bo 50% 30% [00233] Mo8-Br 20% P34 [00234] [00235] 86.000 A1:B5:Br Mo5-Bo 40% 50% [00236] Mo8-Br 10% P35 [00237] [00238] 76.000 A1:B5:Br Mo5-Bo 20% 50% [00239] Mo8-Br 30%

[0226] Polymer V1 is synthesized as comparative polymer:

TABLE-US-00006 (Mw) Poly- [g/mol]/ mer Further monomers D V1 [00240] 98.000 Mo15-Br 40% [00241] Mo2-Bo 50% [00242] Mo8-Br 10%

Part C: Production of the OLEDs

[0227] 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).

[0228] The polymers of the invention are used in the following layer sequence: [0229] substrate, [0230] ITO (50 nm), [0231] PEDOT:PSS (20 nm), [0232] hole transport layer (HTL) (20 nm), [0233] emission layer (EML) (60 nm), [0234] hole blocker layer (HBL) (10 nm), [0235] electron transport layer (ETL) (40 nm), [0236] cathode.

[0237] The 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.

[0238] 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/I when, as here, the layer thicknesses of 20 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.

[0239] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). It is also possible for there to be mixtures of multiple matrix materials and co-dopants. What is meant here by details given in such a form as H1 30%; H2 55%; TEG 15% is that material H1 is present in the emission layer in a proportion by weight of 30%, the co-dopant in a proportion by weight of 55%, and the dopant in a proportion by weight of 8%. The mixture for the emission layer is dissolved in toluene. The typical solids content of such solutions is about 18 g/I 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.

[0240] The materials used in the present case are shown in table 1.

TABLE-US-00007 TABLE 1 Structural formulae of the materials used in the emission layer [00243] H1 [00244] H2 [00245] TEG

[0241] 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 2. 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-00008 TABLE 2 HBL and ETL materials used [00246] ETM1 [00247] ETM2

[0242] The cathode is formed by the thermal evaporation of an aluminum layer of thickness 100 nm.

[0243] The exact structure of the OLEDs can be found in table 3.

TABLE-US-00009 TABLE 3 Structure of the OLEDs Example HTL polymer EML composition Ph1  V1 H1 30%; H2 55%; TEG 15% Ph2 P11 H1 30%; H2 55%; TEG 15%

[0244] 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. LT80 @ 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.

[0245] The properties of the various LEDs are compiled in table 4. Example Ph1 shows the comparative component; example Ph2 shows the properties of the OLEDs of the invention.

TABLE-US-00010 TABLE 4 Properties of the OLEDs Efficiency Voltage LT80 LT80 LT90 at 1000 at 1000 at 10000 at 8000 at 8000 cd/m.sup.2 cd/m.sup.2 cd/m.sup.2 cd/m.sup.2 cd/m.sup.2 Example % EQE [V] [h] [h] [h] Ph1 16.6 5.0 134 512 156 Ph2 17.6 4.5 121 487 153

[0246] As table 4 shows, the polymer of the invention, when used as hole transport layer in OLEDs, results in improvements over the prior art. Its higher triplet level improves the efficiencies in particular of the green-emitting OLEDs produced.

[0247] The fact that the polymers of the invention have a higher triplet level T1 than their direct comparative polymers is shown by quantum-mechanical calculations using some selected polymers. The results are shown in table 5.

TABLE-US-00011 TABLE 5 Comparison of the calculated T1 level Polymer V1 P13 P11 P32 P33 P34 T1 (eV) 2.38 2.44 2.41 2.51 2.44 2.57