Conjugated polymers

Patent metadata

Field	Value
Publication number	US-10053542-B2
Application number	US-201314423496-A
Country	US
Kind code	B2
Filing date	Jul 10, 2013
Priority date	Aug 24, 2012
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

The invention relates to novel conjugated polymers containing one or more polycyclic repeating units, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these polymers, polymer blends, mixtures or formulations.

First claim

The invention claimed is:

1. A polymer comprising one or more units of formula I

wherein the individual radicals have the following meanings:
X and Y independently of each other, and on each occurrence identically or differently, C(R 1 R 2 ), C═C(R 1 R 2 ), Si(R 1 R 2 ), Ge(R 1 R 2 ), C(═O) or NR 1 ,
A 1 ,

A 2 on each occurrence identically or differently

A 3 on each occurrence identically or differently

provided that A 1 , A 2 and A 3 do not at the same time denote a benzene ring,
V CR 1 or N,
W O, S or Se,
R 1 and R 2 independently of each other H, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted,
Y 1 and Y 2 independently of each other H, F, Cl or CN,
R 0 and R 00 independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl.

2. The polymer according to claim 1 , characterized in that V in formula I denotes CH.

3. The polymer according to claim 1 , characterized in that W in formula I denotes S.

4. The polymer according to claim 1 , characterized in that A 1 in formula I is selected from the following groups

5. The polymer according to claim 1 , characterized in A 2 in formula I is selected from the following groups

6. The polymer according to claim 1 , characterized in A 3 in formula I is selected from the following groups

7. The polymer according to claim 1 , characterized in the units of formula I are selected from the following subformulae

wherein X and Y have the meanings given in formula I.

8. A polymer according to claim 7 , wherein X and Y independently denote CR 1 R 2 .

9. The polymer according to claim 1 , characterized in that in the units of formula I, R 1 and R 2 denote straight-chain, branched or cyclic alkyl with 1 to 30 C atoms which is unsubstituted or substituted by one or more F atoms, or R 1 and R 2 denote aryl, heteroaryl, aryloxy or heteroaryloxy, each of which is optionally fluorinated, alkylated or alkoxylated and has 4 to 30 ring atoms.

10. The polymer according to claim 1 , characterized in that it comprises one or more units of formula IIa or IIb
—[(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIa

-[(U) b -(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIb

wherein
U is a unit of formula I,
Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,
R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
X 0 is halogen,
a, b, c are on each occurrence identically or differently 0, 1 or 2,
d is on each occurrence identically or differently 0 or an integer from 1 to 10,
wherein the polymer comprises at least one repeating unit of formula IIa or IIb wherein b is at least 1.

11. A polymer according to claim 10 , wherein X 0 is F, Cl or Br.

12. The polymer according to claim 10 , characterized in that it additionally comprises one or more repeating units selected of formula IIIa or IIIb
—[(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIIa

-[(A c ) b -(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]-  IIIb

wherein Ar 1 , Ar 2 , Ar 3 , a, b, c and d are as defined in claim 10 , and A c is an aryl or heteroaryl group that is different from U and Ar 1-3 , has 5 to 30 ring atoms, is optionally substituted by one or more groups R S as defined in claim 10 , and is selected from aryl or heteroaryl groups having electron acceptor properties, wherein the polymer comprises at least one repeating unit of formula IIIa or IIIb wherein b is at least 1.

13. The polymer according to claim 12 , wherein A c and/or Ar 3 denotes aryl or heteroaryl selected from the group consisting of the following formulae

wherein one of X 11 and X 12 is S and the other is Se, and R 11 , R 12 , R 13 , R 14 and R 15 independently of each other denote H or have one of the meanings of R S .

14. The polymer according to claim 1 , characterized in that it is selected of formula IV:
* (A) x -(B) y -(C) z n *  IV

wherein
A, B, C independently of each other denote a distinct unit of formula I,
x is >0 and ≤1,
y is ≥0 and <1,
z is ≥0 and <1,
x+y+z is 1, and
n is an integer >1.

15. The polymer according to claim 14 , characterized in that it is selected of formula V
R 5 -chain-R 6   V

wherein “chain” is a polymer chain selected of formulae IV as defined in claim 14 , R 5 and R 6 are independently of each other H, F, Br, Cl, I, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more h

Assignees

• Merck Patent Gmbh

Inventors

• Mitchell William
• Wang Changsheng
• Blouin Nicolas
• D'Lavari Mansoor
• Song Jingyao

Classifications

• C07D519/00

  Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00 · CPC title

• C07D513/22

  in which the condensed system contains four or more hetero rings · CPC title

• C08G2261/51

  Charge transport · CPC title

• C08G2261/1336

  Ladder-type, e.g. ladder-poly-p-phenylenes · CPC title

• C08L81/02

  Polythioethers; Polythioether-ethers · CPC title