Conjugated polymers

Patent metadata

Field	Value
Publication number	US-9806263-B2
Application number	US-201415031537-A
Country	US
Kind code	B2
Filing date	Sep 26, 2014
Priority date	Oct 22, 2013
Publication date	Oct 31, 2017
Grant date	Oct 31, 2017

Abstract

The invention relates to novel conjugated polymers containing one or more diindeno-thieno[3,2-b]thiophene based 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 R on each occurrence identically or differently denotes straight-chain or branched alkyl with 16 to 24 C atoms, which is optionally fluorinated.

2. 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 as defined in claim 1 ,
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.

3. The polymer according to claim 2 , 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 2 , 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 2 , 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.

4. The polymer according to claim 1 , characterized in that it is selected of formula IV:

wherein
A, B, C independently of each other denote a distinct unit of formula I, as defined in claim 1 ,
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.

5. The polymer according to claim 2 , characterized in that it is selected from the following formulae
*—[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ] n —*  IVa

*—[(Ar 1 —U—Ar 2 ) x —(Ar 3 —Ar 3 ) y ] n —*  IVb

*—[(Ar 1 —U—Ar 2 ) x —(Ar 3 —Ar 3 —Ar 3 ) y ] n —*  IVc

*—[(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] n —*  IVd

*—([(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] x —[(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ] y ) n —*  IVe

*—[(U—Ar 1 —U) x —(Ar 2 —Ar 3 ) y ] n —*  IVf

*—[(U—Ar 1 —U) x —(Ar 2 —Ar 3 —Ar 2 ) y ] n —*  IVg

*—[(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) c ] n —*  IVh

*—([(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) c ] x —[(A c ) b -(Ar 1 ) a -(A c ) b -(Ar 2 ) d ] y ) n *  IVi

*—[(U—Ar 1 ) x —(U—Ar 2 ) y —(U—Ar 3 ) z ] n —*  IVk

wherein U, Ar 1 , Ar 2 , Ar 3 , a, b, c and d have in each occurrence identically or differently one of the meanings given in claim 2 ,
A c is on each occurrence identically or differently, 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 2 , and is selected from aryl or heteroaryl groups having electron acceptor properties,

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,
wherein these polymers can be alternating or random copolymers, and wherein in formula IVd and IVe in at least one of the repeating units [(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] and in at least one of the repeating units [(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ], b is at least 1 and wherein in formula IVh and IVi in at least one of the repeating units [(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) d ] and in at least one of the repeating units [(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) d ], b is at least 1.

6. The polymer according to claim 1 , characterized in that it is selected of formula IV1

wherein
R has the meaning given in claim 1 ,
D a , D b , D c , D d , D e and D f are independently of each other aryl or heteroaryl that has electron donor properties and is different from formula I, has 5 to 30 ring atoms, and is optionally substituted, by one or more groups R S ,
wherein 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,

i is >0 and <1, and
m, o, p, q, r and s are independently of each other ≧0 and <1,
with at least one of m, o, p, q, r and s being >0.

7. The polymer according to claim 2 , wherein one or more of Ar 1 , Ar 2 , and Ar 3 , denote aryl or heteroaryl selected from the group consisting of the following formulae

wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other denote H or have one of the meanings of R S as defined in claim 2 .

8. The polymer accordi

Assignees

• Merck Patent Gmbh

Inventors

• Mitchell William
• D'Lavari Mansoor
• Wang Changsheng
• Sparrowe David

Classifications

• C07D495/04

  Ortho-condensed systems · CPC title

• C08G2261/51

  Charge transport · CPC title

• C08G2261/94

  Applications in sensors, e.g. biosensors · CPC title

• C08G2261/92

  TFT applications · CPC title

• C08G2261/364

  containing hetero atoms · CPC title