Polymer containing aldehyde groups, reaction and crosslinking of this polymer, crosslinked polymer, and electroluminescent device comprising this polymer

Patent metadata

Field	Value
Publication number	US-9728724-B2
Application number	US-201514803398-A
Country	US
Kind code	B2
Filing date	Jul 20, 2015
Priority date	Feb 27, 2009
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

The present invention relates to a polymer which comprises at least one structural unit which contains at least one aldehyde group, and to a process for the preparation of a crosslinkable or crosslinked polymer including a polymer which contains aldehyde groups. The present invention thus also relates to a crosslinkable polymer and a crosslinked polymer which is prepared by the process according to the invention, and to the use of this crosslinked polymer in electronic devices, in particular in organic electroluminescent devices, so-called OLEDs (OLED=organic light emitting device).

First claim

The invention claimed is:

1. A polymer which comprises at least one structural unit of formula (II):

where the symbols and indices used have the following meanings:
Ar 1 to Ar 6 are identical or different and represent, independently of one another, a substituted or unsubstituted, mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 25 ring atoms; and wherein Ar a and/or Ar 6 contains an aldehyde group in its para-position,
m is 0 or 1;
n is 0, 1 or 2;
the dashed lines represent bonds to the next structural unit of the polymer;
with the proviso that, if n=1, the two N atoms bond to different C atoms of the same aromatic ring system,
wherein the polymer comprises 1-30 mol % of at least one structural unit according to formula (II), and
wherein the polymer comprises at least one further structural unit which is different from the structural unit of the formula (II) which is selected from the group consisting of
structural units having hole-injection and/or hole-transport properties,
structural units having electron-injection and/or electron-transport properties,
structural units capable to emitting light from the triplet state,
structural units which are not organometallic complexes or do not influence singlet-triplet transfer selected from the group consisting of 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 and perylene derivatives, optionally substituted, or
structural units selected from the group consisting of 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, 9,9′-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydro-dibenzoxepine derivatives and cis- and trans-indenofluorene derivatives.

2. The polymer according to claim 1 , wherein Ar 3 or Ar 6 is a substituted or unsubstituted unit selected from the group consisting of phenylene, biphenylene, triphenylene, 1,1′: 3′,1″-terphenyl-2′-ylene, naphthylene, anthracene, binaphthylene, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzo[a]pyrene, fluorene, indene, indenofluorene, spirobifluorene, pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 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, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene and benzothiadiazothiophene.

3. The polymer according to claim 1 , wherein Ar 1 , Ar 2 , Ar 4 and Ar 5 in the formula (II) is (are) a substituted or unsubstituted unit selected from the group consisting of 4,5-dihydropyrene, 4,5,9,10-tetrahydrofluorene, 9,9′-spirobifluorene, fluorene, phenanthrene, 9,10-dihydrophenanthrene, 5,7-dihydrodibenzoxepine, cis-indenofluorene, trans-indenofluorene, phenylene, thiophene, benzanthracene, carbazole, benzimidazole, oxepine and triazine.

4. The polymer according to claim 1 , wherein the further structural unit is a structural unit of the formula (II) which does not contain an aldehyde group.

5. The polymer according to claim 1 , wherein the structural unit of the formula (II) is selected from the group consisting of the following structural units:

6. A mixture of one or more polymer(s) according to claim 1 with further polymeric, oligomeric, dendritic and/or low-molecular-weight substances.

7. A formulation comprising one or more polymer(s) according to claim 1 in one or more solvents.

8. A formulation comprising the mixture according to claim 7 in one or more solvents.

9. A process for the preparation of a crosslinked polymer which comprises the following steps:
(a) providing a polymer according to claim 1 which contains aldehyde groups;
(b) conversion of the aldehyde groups into vinyl groups or alkenyl groups; and
(c) crosslinking of the polymer.

10. A crosslinked polymer which is obtainable by the process according to claim 9 .

11. An organic electronic device which comprises the crosslinked polymer according to claim 10 .

12. The organic electronic device according to claim 11 , wherein the device is an organic or polymeric organic electroluminescent device (OLED, PLED), organic integrated circuit (O-IC), organic field-effect transistor (OFET), organic thin-film transistor (OTFT), organic solar cell (O-SC), organic laser diode (O-laser), organic photovoltaic (OPV) element or device or organic photoreceptor (OPC).

13. A polymer which comprises 1-30 mol % of at least one structural unit selected from the group consisting of the following structural units:

and
wherein the polymer comprises at least one further structural unit which is different from

which is selected from the group consisting of
structural units having hole-injection and/or hole-transport properties,
structural units having electron-injection and/or electron-transport properties,
structural units capable to emitting light from the triplet state,
structural units which are not organometallic complexes or do not influence singlet-triplet transfer selected from the group consisting of 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 and perylene derivatives, optionally substituted, or
structural units selected from the group consisting of 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, 9,9′-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydro-dibenzoxepine derivatives and cis- and trans-indenofluorene derivatives.

14. A process for the preparation of a crosslinked polymer which comprises t

Assignees

• Merck Patent Gmbh

Inventors

• Ludemann Aurélie
• Anémian Rémi M
• Julliart Alice

Classifications

• C08G2/30

  Chemical modification by after-treatment · CPC title

• C09D165/00 Primary

  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

• C08G2/18

  Copolymerisation of aldehydes or ketones · CPC title

• 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

• C09K11/06

  containing organic luminescent materials · CPC title