Polymers with amine-group-containing repeating units

Patent metadata

Field	Value
Publication number	US-12065536-B2
Application number	US-201917292338-A
Country	US
Kind code	B2
Filing date	Nov 4, 2019
Priority date	Nov 7, 2018
Publication date	Aug 20, 2024
Grant date	Aug 20, 2024

Abstract

The invention relates to polymers having at least one repeating unit of the following formula (I): wherein Ar 1 , Ar 2 , Ar 3 and Ar 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.

First claim

The invention claimed is:

1. A polymer having at least one repeat unit of the following formula (I):

wherein
X is selected from O, S, NR or CR 2 ;
Ar 1 , Ar 2 , Ar 3 and Ar 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 optionally substituted by one R radical;
a and b are the same at each instance and are 1; where (a+b)=2;
c and d are the same at each instance and are 1;
e and f are the same at each instance and are independently 0, 1, 2 or 3;
R is the same at each instance and is independently H, D, F, Cl, Br, I, N(R 1 ) 2 , CN, NO 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R 1 , P(═O)(R 1 ) 2 , S(═O)R 1 , S(═O) 2 R 1 , OSO 2 R 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 optionally substituted by one or more R 1 radicals, where one or more nonadjacent CH 2 groups optionally replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, C═S, C═NR 1 , P(═O)R 1 , SO, SO 2 , NR 1 , O, S or CONR 1 and where one or more hydrogen atoms optionally 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 optionally substituted in each case by one or more R 1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and optionally substituted by one or more R 1 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and optionally substituted by one or more R 1 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and optionally substituted by one or more R 1 radicals; or a crosslinkable group Q, where two or more R radicals together optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
is the same 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 optionally be replaced by F; where two or more R 1 substituents together optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; and the dotted lines represent bonds to adjacent repeat units in the polymer,
and wherein the polymer contains from 5 to 75 mol %, based on 100 mol % of all copolymerizable monomers present as repeat units in the polymer, of the at least one repeat unit of the formula (I).

2. The polymer as claimed in claim 1 , wherein the at least one repeat unit of the formula (I) is selected from the repeat unit of the following formula (II):

where Ar 1 , Ar 2 , Ar 3 , Ar 4 , c and d may assume the definitions given in claim 1 .

3. The polymer as claimed in claim 1 , wherein the at least one repeat unit of the formula (I) is selected from the repeat unit of the following formula (III):

where Ar 1 , Ar 2 , Ar 3 and Ar 4 assume the definitions given in claim 1 .

4. The polymer as claimed in claim 1 , wherein the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar 2 and Ar 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:

where R assume the definitions given in claim 1 ,
X═CR 2 , NR, SiR 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.

5. The polymer as claimed in claim 1 , wherein the mono- or polycyclic, aromatic or heteroaromatic ring systems Ar 1 and Ar 3 in the of repeat units of the formula (I), (II), (III), (IIIa), (IIIb), (IIIc), (IV), (V), (Va), (Vb) and (Vc) are selected from the following units Ar11 to Ar18:

where R assume the definitions given in claim 1 ,
X═CR 2 , NR, SiR 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.

6. The polymer as claimed in claim 1 , wherein the proportion of repeat units of the formula (I), (II), (III), (IIIa), (IIIb), and/or (IIIc)

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.

7. The polymer as claimed in claim 1 , wherein the polymer comprises one or more repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), and/or (IIIc),

and comprises further repeat units other than the repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), and/or (IIIc).

8. The polymer as claimed in claim 1 , wherein the polymer comprises one or more repeat units of the formulae (I), (II), (III), (IIIa), (IIIb), and/or (IIIc)

and optionally further repeat units, and further comprises at least one repeat unit having at least one crosslinkable group Q.

9. The polymer as claimed in claim 8 , wherein the repeat unit having at least one crosslinkable group is selected from the repeat unit of the formula (Ix)

where Ar 1 , Ar 2 , Ar 3 , Ar 4 , R and X and a, b, c, d, e and f assume the definitions given in claim 1 in relation to formula (I), but with the proviso that at least one R is a crosslinkable group Q.

10. The polymer as claimed in claim 8 , wherein the repeat unit having the at least one crosslinkable group is selected from the repeat units of the formulae (IIx1), (IIx2) and (IIx3)

where X in formula (IIx1): is NQ, CRQ or CQ 2 ;

where X in formula (IIx2): is O, S, NR or CR 2 ; and

where X in formula (IIx3): is O, S, NR or CR 2 ;
Q is a crosslinkable group;
and Ar 1 , Ar 2 , Ar 3 and Ar 4 , and c and d in the formulae (IIx1), (IIx2) and (IIx3) assume the definitions given in claim 1 in relation to formula (I).

11. A process for preparing the polymer as claimed in claim 1 , which comprises preparing the polymer by SUZUKI polymerization, YAMAMOTO polymerization, STILLE polymerization or HARTWIG-BUCHWALD polymerization.

12. A polymer blend comprising one or more polymers as claimed in claim 1

Assignees

• Merck Patent Gmbh

Inventors

• Koenen Nils
• Joosten Dominik
• Burkhart Beate
• Scheible Katja
• Engel Miriam
• Heil Holger

Classifications

• C09B57/008

  Triarylamine dyes containing no other chromophores · CPC title

• H10K50/15

  Hole transporting layers · CPC title

• H10K85/111

  comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene · CPC title

• C08G2261/95

  Use in organic luminescent diodes · CPC title

• C08G2261/76

  crosslinking · CPC title