Electroluminescent polymers, process for the preparation thereof, and use thereof

Patent metadata

Field	Value
Publication number	US-9534077-B2
Application number	US-201113578439-A
Country	US
Kind code	B2
Filing date	Jan 18, 2011
Priority date	Feb 12, 2010
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

The present invention relates to electroluminescent polymers which comprise indenofluorenarylamine derivatives as recurring units, to a process for the preparation thereof, to blends and formulations comprising these polymers, and to the use of these polymers or blends in electronic devices, in particular in organic light-emitting diodes, so-called OLEDs.

First claim

The invention claimed is:

1. A polymer comprising 0.01 to 100 mol % of one or more structural units of the formula (7c) or (7d),

where the symbols and indices used have the following meanings:
R 1 is on each occurrence, identically or differently, H, F, Cl, Br, I, CN, NO 2 , Si(R 2 ) 3 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more non-adjacent CH 2 groups is optionally replaced by —R 2 C═CR 2 —, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , —O—, —S— or —CONR 2 — and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems; two or more substituents R 1 here optionally also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
R 2 is on each occurrence, identically or differently, H, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic hydrocarbon radical having 6 to 20 C atoms;
X 1 is on each occurrence, identically or differently, selected from B(R 1 ), C(R 1 ) 2 , Si(R 1 ) 2 , C═O, C═NR 1 , C═C(R 1 ) 2 , O, S, S═O, SO 2 , N(R 1 ), P(R 1 ), P(═O)R 1 , P(═S)R 1 or a combination of two, three or four of these groups;
X 2 is on each occurrence, identically or differently, selected from B(R 1 ), C(R 1 ) 2 , Si(R 1 ) 2 , C═O, C═NR 1 , C═C(R 1 ) 2 , O, S, S═O, SO 2 , N(R 1 ), P(R 1 ), P(═O)R 1 , P(═S)R 1 or a combination of two, three or four of these groups; and

wherein the dashed lines denote the links in the polymer and the polymer has 10 to 10,000 recurring units.

2. The polymer according to claim 1 , wherein the polymer comprises further structural units besides the units of the formula (7c) or (7d).

3. The polymer according to claim 2 , wherein the further structural units, which have hole-injection and/or hole-transport properties, are triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiyne, carbazole, azulene, thiophene, pyrrole or furan derivatives or further O-, S- or N-containing heterocycles having a high HOMO.

4. The polymer according to claim 2 , wherein the further structural units, which have electron-injection and/or electron-transport properties, are pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide or phenazine derivative, triarylborane or further O-, S- or N-containing heterocycles having a low LUMO.

5. The polymer according to claim 2 , wherein the further structural elements modify the emission characteristics to such an extent that electrophosphorescence can be obtained instead of electrofluorescence.

6. The polymer according to claim 2 , wherein the further structural elements, which improve the transfer from the singlet state to the triplet state, are selected from the classes of the carbazole and bridged carbazole dimer units, ketones, phosphine oxides, sulfoxides, sulfones and silane derivatives.

7. The polymer according to claim 2 , wherein the further structural elements, which influence the emission colour of the polymers, are 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-anthrylene, 1,6-, 2,7- or 4,9-pyrenylene, 3,9- or 3,10-perylenylene, 4,4′-biphenylylene, 4,4″-terphenylylene, 4,4′-bi-1,1′-naphthylylene, 4,4′-tolanylene, 4,4′-stilbenylene, 4,4″-bisstyrylarylene, benzothiadiazole and corresponding oxygen derivatives, quinoxaline, phenothiazine, phenoxazine, dihydrophenazine, bis(thiophenyl)arylene, oligo(thiophenylene), phenazine, rubrene, pentacene or perylene derivatives.

8. The polymer according to claim 2 , wherein the further structural elements, which are typically used as backbone, are selected from the classes of the 4,5-dihydropyrene, 4,5,9,10-tetrahydropyrene, fluorene, 9,9′-spirobifluorene, phenanthrene, 9,10-dihydrophenanthrene, 5,7-dihydrodibenzoxepine and cis- or trans-indenofluorene derivatives.

9. A process for the preparation of the polymer according to claim 1 , which comprises preparing the polymer according to claim 1 by SUZUKI polymerisation, YAMAMOTO polymerisation, STILLE polymerisation or HARTWIG-BUCHWALD polymerisation.

10. A mixture of one or more polymers according to claim 1 with further polymeric, oligomeric, dendritic and/or low-molecular-weight substances.

11. A solution or formulation comprising the mixture according to claim 10 in one or more solvents.

12. An organic electronic device comprising one or more active layers, wherein at least one of said active layers comprises the mixture according to claim 10 .

13. A solution or formulation comprising one or more polymers according to claim 1 in one or more solvents.

14. An organic electronic device comprising one or more active layers, wherein at least one of said active layers comprises one or more polymers according to claim 1 .

15. The organic electronic device according to claim 14 , wherein the organic device is an organic or polymeric organic light-emitting diode, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic solar cell, an organic laser diode, an organic photovoltaic element or device or an organic photoreceptor.

16. The polymer according to claim 1 , wherein the polymer has 20 to 5,000 recurring units.

17. The polymer according to claim 1 , wherein the polymer has 50 to 2,000 recurring units.

18. A polymer comprising 0.01 to 100 mol % of one or more structural units of the formula (7),

where the symbols and indices used have the following meanings:
Y is on each occurrence N, P, P═O, PF 2 , P═S, As, As═O, As═S, Sb, Sb═O or Sb═S;
Ar 4 and Ar y is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
R 1 is on each occurrence, identically or differently, F, Cl, Br, I, CN, NO 2 , Si(R 2 ) 3 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more non-adjacent CH 2 groups is optionally replaced by —R 2 C═CR 2 —, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , —O—, —S— or —CONR 2 — and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems; two or more substituents R 1 here optionally also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring

Assignees

• Anémian Rémi Manouk
• Ludemann Aurélie
• Pan Junyou
• Merck Patent Gmbh

Inventors

• Anémian Rémi Manouk
• Ludemann Aurélie
• Pan Junyou

Classifications

• C09K2211/1416

  Condensed systems · CPC title

• C08G2261/18

  conjugated · CPC title

• H05B33/14

  characterised by the chemical or physical composition or the arrangement of the electroluminescent material {, or by the simultaneous addition of the electroluminescent material in or onto the light source} · CPC title

• C08G2261/411

  Suzuki reactions · CPC title

• C08G61/12 Primary

  Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule · CPC title