Crosslinkable and crosslinked polymers, method for the production thereof, and use thereof

Patent metadata

Field	Value
Publication number	US-9315617-B2
Application number	US-201013203567-A
Country	US
Kind code	B2
Filing date	Feb 1, 2010
Priority date	Feb 27, 2009
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

Abstract

The present invention relates to cross-linkable and cross-linked polymers and to a method for the production thereof. The invention further relates to the use of said polymers in electronic devices and to the corresponding electronic devices themselves.

First claim

The invention claimed is:

1. Polymer containing at least one structural unit of the general formula I,

wherein
Z is an aromatic or an heteroaromatic ring system, optionally substituted by one or more radical R, wherein the aromatic or heteroaromatic ring system is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, benzothiadiazole, benzanthrene, benzanthracene, rubicene and triphenylene,
R is selected on each occurrence, independently of one another, from F, Cl, Br, I, N(Ar) 2 , N(R 2 ) 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)Ar, C(═O)R 2 , P(═O)(Ar) 2 , P(═O)(R 2 ) 2 , S(═O)Ar, S(═O)R 2 , S(═O) 2 Ar, S(═O) 2 R 2 , CR 2 ═CR 2 Ar, OSO 2 R 2 , 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 optionally substituted by one or more radicals R 2 , where in the straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or in the branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms one or more non-adjacent CH 2 groups optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , P(═O)(R 2 ), SO, SO 2 , NR 2 , O, S or CONR 2 and where in the straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or in the branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms one or more H atoms optionally replaced by F, Cl, Br, I, CN or NO 2 , where two or more substituents R optionally form a mono- or polycyclic, or aromatic ring system with one another, where R 2 is in each case, independently of one another, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms,
X is selected from a direct bond, a linear or branched alkylene group having 1 to 20 C atoms, in which one or more non-adjacent CH 2 groups are optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —N—CO—, —N—CO—O—, —N—CO—, N, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —CH(CN)—, —CH═CH— or —C≡C—, or a cyclic alkyl group,
Ar 1 and Ar 2
are an optionally substituted aryl or an optionally substituted heteroaryl group, which are optionally linked to one another,

Q is a crosslinkable group,
R 1 is 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 or a silyl group or substituted keto group having 1 to 40 C atoms, or an optionally substituted aromatic or heteroaromatic ring system having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems, or Ar 2 , where one or more H atoms is optionally replaced by fluorine,
n is 1, 2, 3 or 4, and
the dashed lines represent the linking in the polymer,
wherein if n=1 or if Z=fluorene and n=2, X is not a direct bond.

2. The polymer of claim 1 , wherein Q is a vinyl or alkenyl group.

3. The polymer of claim 1 , wherein Z is selected from the group consisting of fluorene, spirobifluorene, indenofluorene, anthracene, phenanthrene, and dihydrophenanthrene.

4. The polymer of claim 1 , wherein Ar 1 and Ar 2 are each, independently of one another, an optionally substituted aryl or heteroaryl group having 5 to 60 ring atoms.

5. The polymer of claim 1 , wherein Ar 1 is an optionally substituted 1,4-linked aryl or heteroaryl group.

6. The polymer of claim 1 , wherein the polymer contains further structural units which are different from the general formula I.

7. A formulation comprising the polymer of claim 1 in one or more solvents.

8. An electronic device comprising the polymer of claim 1 .

9. The electronic device of claim 8 , wherein said polymer is crosslinked.

10. The electronic device of claim 8 , wherein said polymer is present in said electronic device as a hole-transport, a hole-injection, an emitter, an electron-transport, an electron-injection, a charge-blocking, and/or a charge-generation layer.

11. The electronic device of claim 8 , wherein said electronic device is an organic electroluminescent device, a polymeric electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell or an organic laser diode.

12. A compound of formula II,

wherein
Z is an aromatic or an heteroaromatic ring system, optionally substituted by one or more radical R, wherein the aromatic or heteroaromatic ring system is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,

Assignees

• Meyer Frank Egon
• Schulte Niels
• Scheurich René Peter
• Anémian Rémi Manouk
• Ludemann Aurélie
• Julliart Alice
• Merck Patent Gmbh

Inventors

• Meyer Frank Egon
• Schulte Niels
• Scheurich René Peter
• Anémian Rémi Manouk
• Ludemann Aurélie
• Julliart Alice

Classifications

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• C08G61/12 Primary

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

• C09D165/00

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• C09K11/06

  containing organic luminescent materials · CPC title

• C07C211/56

  the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups · CPC title