Conjugated polymers

Patent metadata

Field	Value
Publication number	US-9577197-B2
Application number	US-201214234235-A
Country	US
Kind code	B2
Filing date	Jun 21, 2012
Priority date	Jul 21, 2011
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

The invention relates to novel polymers containing one or more 3,7-dialkyl-benzo[1,2-b:4,5-b′]dithiophene repeating units, methods for their preparation and monomers used therein, blends, mixtures and formulations containing them, the use of the polymers, blends, mixtures and formulations as semiconductor in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these polymers, blends, mixtures or formulations.

First claim

The invention claimed is:

1. A conjugated polymer consisting of repeating units of formula I1 and repeating units of formula I2
—(Ar 1 ) a —B—  I1

—(Ar 2 ) b -A-  I2

wherein
B is a divalent group of the following formula

A is a divalent group of the following formula

X is O, Se, Te, NR 0 or S,
R 1 , R 2 denote independently of each other, and on each occurrence identically or differently, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms,
R 3 , R 4 denote independently of each other, and on each occurrence identically or differently, H, F, or straight-chain or branched alkyl or alkoxy with 1 to 30 C atoms,
Ar 1 , Ar 2 are, on each occurrence identically or differently, and independently of each other, of formula I1, I2, I3, I4, I5 or I6

wherein the heterocyclic rings in formulae I1, I2, I3, I4, I5 and I6 are optionally substituted by one or two groups R 1 or R 3 ,
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 , or 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 , R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
X 0 is halogen, and
a, b are on each occurrence identically or differently 1, 2 or 3.

2. The polymer according to claim 1 , which is of formula II:
—([(Ar 1 ) a —B] x —[(Ar 2 ) b -A] y ) n -,  II

wherein
B is a divalent group of the following formula

A is a divalent group of the following formula

X is O, Se, Te, NR 0 or S,
R 1 , R 2 denote independently of each other, and on each occurrence identically or differently, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms,
R 3 , R 4 denote independently of each other, and on each occurrence identically or differently, H, F, or straight-chain or branched alkyl or alkoxy with 1 to 30 C atoms,
Ar 1 , Ar 2 are, on each occurrence identically or differently, and independently of each other, of formula I1, I2, I3, I4, I5 or I6

wherein the heterocyclic rings in formulae I1, I2, I3, I4, I5 and I6 are optionally substituted by one or two groups R 1 or R 3 ,
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 , or 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 , R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
X 0 is halogen,
a, b are on each occurrence identically or differently 1, 2 or 3,
x is the mole fraction of units (Ar 1 ) a -B and is >0 and <1,
y is the mole fraction of units (Ar 2 ) b -A and is >0 and <1,
x+y is 1, and
n is an integer >1.

3. The polymer according to claim 1 , which is of formula II1 or II2
*—[Ar 1 —B—Ar 2 -A] n -*  II1

*—[(Ar 1 —B) x —(Ar 2 -A) y ] n -*  II2

wherein
B is a divalent group of the following formula

A is a divalent group of the following formula

X is O, Se, Te, NR 0 or S,
R 1 , R 2 denote independently of each other, and on each occurrence identically or differently, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms,
R 3 , R 4 denote independently of each other, and on each occurrence identically or differently, H, F, or straight-chain or branched alkyl or alkoxy with 1 to 30 C atoms,
Ar 1 , Ar 2 are, on each occurrence identically or differently, and independently of each other, of formula I1, I2, I3, I4, I5 or I6

wherein the heterocyclic rings in formulae I1, I2, I3, I4, I5 and I6 are optionally substituted by one or two groups R 1 or R 3 ,
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 , or 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 , R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
X 0 is halogen,
a, b are on each occurrence identically or differently 1, 2 or 3,
x is the mole fraction of units (Ar 1 ) a -B and is >0 and <1,
y is the mole fraction of units (Ar 2 ) b -A and is >0 and <1,
x+y is 1, and
n is an integer >1.

4. The polymer according to claim 1 , which is of formula III
R 5 -chain-R 6   III

wherein
chain is a polymer chain of formula II, II1 or II2
—([(Ar 1 ) a —B] x —[(Ar 2 ) b -A] y ) n -,  II

*—[Ar 1 —B—Ar 2 -A] n -*  II1

*—[(Ar 1 —B) x —(Ar 2 -A) y ] n -*  II2

B is a divalent group of the following formula

A is a divalent group of the following formula

X is O, Se, Te, NR 0 or S,
R 1 , R 2 denote independently of each other, and on each occurrence identically or differently, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms,
R 3 , R 4 denote independently of each other, and on each occurrence identically or differently, H, F, or straight-chain or branched alkyl or alkoxy with 1 to 30 C atoms,
Ar 1 , Ar 2 are, on each occurrence identically or differently, and independently of each other, of formula I1, I2, I3, I4, I5 or I6

wherein the heterocyclic rings in formulae I1, I2, I3, I4, I5 and I6 are optionally substituted by one or two groups R 1 or R 3 ,
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 , or 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 , R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
X 0 is halogen,
a, b are on each occurrence identi

Assignees

• Phillips Amy
• Blouin Nicolas
• Mitchell William
• Tierney Steven
• Merck Patent Gmbh

Inventors

• Phillips Amy
• Blouin Nicolas
• Mitchell William
• Tierney Steven

Classifications

• C08G2261/3245

  containing nitrogen and oxygen as heteroatoms · CPC title

• C08G61/126

  with a five-membered ring containing one sulfur atom in the ring · CPC title

• 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

• C08G2261/3246

  containing nitrogen and sulfur as heteroatoms · CPC title

• Y02E10/549

  Organic PV cells · CPC title