Conjugated polymers

Patent metadata

Field	Value
Publication number	US-9590178-B2
Application number	US-201214346757-A
Country	US
Kind code	B2
Filing date	Aug 29, 2012
Priority date	Sep 28, 2011
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The invention relates to novel polymers containing one or more 4,8-dioxycarbonylalkyl-benzo[1,2-b:4,5-b′]dithiophene repeating units or their thioester derivatives, 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 polymer comprising one or more divalent units of formula I

wherein
X 1 , X 2 , X 3 , X 4 denote independently of each other, and on each occurrence identically or differently O or S,
R 1 , R 2 denote independently of each other, a straight-chain or branched alkyl with 1 to 20 C atoms, which is unsubstituted or substituted by one or more F atoms, and
R 3 , R 4 denote independently of each other, and on each occurrence identically or differently, H, halogen, or an optionally substituted carbyl or hydrocarbyl group, wherein one or more C atoms are each optionally replaced by a hetero atom.

2. The polymer according to claim 1 , wherein R 3 and R 4 are each, independently, selected from straight-chain, branched or cyclic alkyl with 1 to 30 C atoms in which one or more non-adjacent C atoms are each optionally replaced by —O—, —S—, —C(O)—, —C(S)—, —C(O)—O—, —C(S)—O—, —C(S)—S—, —C(O)—S—, —O—C(O)—, —O—C(S)—, —S—C(S)—, —S—C(O)—, —CH═CH— or —C≡C—, and which are unsubstituted or substituted by F, Cl, Br, I or CN.

3. The polymer according to claim 1 , wherein X 1 and X 2 are O or S, and X 3 and X 4 are O.

4. The polymer according to claim 1 , wherein R 1 and R 2 independently of each other are straight-chain alkyl with 1 to 20 C atoms which is unsubstituted or substituted by one or more F atoms.

5. The polymer according to claim 1 , wherein said polymer comprises one or more units of formula II
-[(Ar 1 ) a —(U) b -(Ar 2 ) c -(Ar 3 ) d ]—  II

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, 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 , —C(O)OR 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, or is P-Sp-,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
P is a polymerizable or crosslinkable group,
Sp is a spacer group or a single bond,
X 0 is halogen,
a, b, c are on each occurrence identically or differently 0, 1 or 2, and
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 II wherein b is at least 1.

6. The polymer according to claim 1 , wherein said polymer additionally comprises one or more repeating units of formula III
-[(Ar 1 ) a -(A 1 ) b -(Ar 2 ) c -(Ar 3 ) d ]—  III

wherein
U is a unit of formula I,
Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, and is optionally substituted by one or more groups R S ,
A 1 is an aryl or heteroaryl group that is different from U and Ar 2-3 , 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 , —C(O)OR 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, or is P-Sp-,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
P is a polymerizable or crosslinkable group,
Sp is a spacer group or a single bond,
X 0 is halogen,
a, b, c are on each occurrence identically or differently 0, 1 or 2, and
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 III wherein b is at least 1.

7. The polymer according to claim 1 , wherein said polymer is of formula IV:

wherein
A is a unit of formula I or is a unit of the following formula II,
-[(Ar 1 ) a —(U) b -(Ar 2 ) c -(Ar 3 ) d ]—  II

B is a unit that is different from A and comprises one or more aryl or heteroaryl groups that are optionally substituted,
x is >0 and ≦1,
y is ≧0 and <1,
x+y is 1,
n is an integer >1,
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, 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 , —C(O)OR 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, or is P-Sp-,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
P is a polymerizable or crosslinkable group,
Sp is a spacer group or a single bond,
X 0 is halogen, preferably F, Cl or Br,
a, b, c are on each occurrence identically or differently 0, 1 or 2, and
d is on each occurrence identically or differently 0 or an integer from 1 to 10.

8. The polymer according to claim 1 , wherein said polymer 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 1 ) b -(Ar 2 ) c -(Ar 3 ) d ] y ) n —*  IVe

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, 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 , —C(O)OR 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, or is P-Sp-,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
P is a polymerizable or crosslinkable group,
Sp is a spacer group or a single bond,
X 0 is halogen, preferably F, Cl or Br,
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,
x is >0 and ≦1,
y is ≧0 and <1,
x+y 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 1 ) b -(Ar 2 ) c -(Ar 3 ) d ] b is at least 1.

9. The polymer according to claim 7 , wherein said polymer is of formula V
R 5 -chain-R 6   V

wherein
“chain” is a polymer chain of formula IV as defined in claim 7 ,
R 5 and R 6 denote indepen

Assignees

• Mitchell William
• Blouin Nicolas
• Phillips Amy
• Tierney Steven
• Carrasco-Orozco Miguel
• Cull Toby
• Merck Patent Gmbh

Inventors

• Mitchell William
• Blouin Nicolas
• Phillips Amy
• Tierney Steven
• Carrasco-Orozco Miguel
• Cull Toby

Classifications

• C08G2261/91

  Photovoltaic applications · CPC title

• C08G2261/12

  Copolymers · CPC title

• C08G2261/1426

  containing carboxy groups (COOH) and/or -C(=O)O-moieties · CPC title

• C08G2261/3246

  containing nitrogen and sulfur as heteroatoms · CPC title

• C08G2261/3243

  containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene · CPC title