Cross-linkable and cross-linked polymers, process for the preparation thereof, and the use thereof

Patent metadata

Field	Value
Publication number	US-9644070-B2
Application number	US-201314391409-A
Country	US
Kind code	B2
Filing date	Apr 12, 2013
Priority date	Apr 17, 2012
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

The present invention relates to cross-linkable and cross-linked polymers, methods for the production thereof, the use of said cross-linked polymers in electronic devices, especially in OLEDs (OLED=Organic Light Emitting Diode), and to electronic devices, especially organic electroluminescent devices which contain the cross-linked polymers.

First claim

The invention claimed is:

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

at least one structural unit of the following formula (II):

and at least one further structural unit of the following formula (III) which is different from structural units (I) and (II):
—Ar 9 —  (III)

where
Ar 1 to Ar 8 is on each occurrence, in each case identically or differently, a mono- or polycyclic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;
Ar 9 in formula (III) is selected from:

where,
X is CR 2 , SiR 2 , O or S,
and
the indices used have the following meaning:
k=0 or 1;
m=0, 1 or 2;
n=0, 1, 2 or 3; and
o=0, 1, 2, 3 or 4;

i and j is each 0 or 1, where the sum (i+j) =1;
R is on each occurrence, identically or differently, 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 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 1 , where one or more non-adjacent CH 2 groups may be 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 H atoms may be replaced by D, F, Cl , Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may in each be substituted by one or more radicals R 1 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 1 ; where two or more radicals R may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another;
R 1 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; where two or more substituents R 1 may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; and
the dashed lines represent bonds to adjacent structural units in the polymer and the dashed lines which are located in brackets represent possible bonds to adjacent structural units in the polymer;
characterised in that at least one of the structural units of the formula (I) and/or (II) contains at least one crosslinkable group Q.

2. The polymer according to claim 1 , wherein the structural unit of the formula (II) corresponds either to the structural unit of the following formula (IIa):

or to the structural unit of the following formula (IIb):

3. The polymer according to claim 1 , wherein the proportion of structural units of the formulae (I) and (II) in the polymer is 100 mol %.

4. The polymer according to claim 1 , wherein the proportion of structural units of the formulae (I) and (II) in the polymer is in the range from 25 to 75 mol %.

5. The polymer according to claim 1 , wherein the polymer, besides structural units of the formulae (I), (II) and (III), also contains further structural units which are different from the structural units of the formulae (I), (II) and (III).

6. The polymer according to claim 1 , wherein the mono- or polycyclic, aromatic or heteroaromatic groups Ar1 in formula (I), Ar4 and Ar6 in formula (IIa) and Ar6 and Ar7 in formula (IIb) are selected from:

where
X is CR 2 , SiR 2 , NR, O or S, and
the indices used have the following meaning:
m=0, 1 or 2;
n=0, 1, 2 or3;
o=0, 1, 2, 3 or 4; and
p=0, 1, 2, 3, 4 or 5.

7. The polymer according to claim 1 , wherein the mono- or polycyclic, aromatic or heteroaromatic groups Ar2 and Ar3 in formula (I), Ar5, Ar7 and Ar8 in formula (IIa), Ar4, Ar5 and Ar8 in formula (IIb), are selected from:

where,
X is CR 2 , SiR 2 , O or S,
Y is CR 2 , SiR 2 , O, S or a straight-chain or branched alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, each of which may be substituted by one or more radicals R 1 , where one or more non-adjacent CH 2 groups, CH groups or C atoms of the alkyl, alkenyl or alkynyl groups may be replaced by Si(R 1 ) 2 , C═O, C═S, C═NR 1 , P(═O)(R 1 ), SO, SO 2 , NR 1 , O, S, CONR 1 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 1 , where here too the radicals R and R 1 can adopt the same meanings as the radicals R and R 1 in the formulae (I) and (II), and the indices used have the following meaning:
k=0 or 1;
m=0, 1 or 2;
n=0, 1, 2 or 3;
o=0, 1, 2, 3 or 4; and
q=0, 1, 2, 3, 4, 5 or 6.

8. The polymer according to claim 1 , wherein the crosslinkable group Q is selected from:
terminal or cyclic alkenyl or terminal dienyl and alkynyl groups,
alkenyloxy, dienyloxy or alkynyloxy groups,
acrylic acid groups,
oxetane and oxirane groups,
silane groups, and
cyclobutane groups.

9. The polymer according to claim 8 , wherein the crosslinkable group Q is selected from:

where
the radicals R 11 , R 12 and R 13 in the formulae Q1 to Q8, Q11, Q13 to Q20 and Q23 are on each occurrence, i

Assignees

• Merck Patent Gmbh

Inventors

• Eckes Fabrice
• Gerhard Anja
• Hayer Anna
• Heil Holger
• Joosten Dominik

Classifications

• C08G2261/411

  Suzuki reactions · CPC title

• C08G2261/135

  Cross-linked structures · CPC title

• C08G2261/12

  Copolymers · CPC title

• C08G2261/3142

  fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title