Conjugated polymers

Patent metadata

Field	Value
Publication number	US-9837613-B2
Application number	US-201514731917-A
Country	US
Kind code	B2
Filing date	Jun 5, 2015
Priority date	Sep 4, 2010
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

The invention relates to novel polymers containing repeating units based on benzo[2,1,3]thiadiazole-5,6-dicarboxylic acid bis-ester, monomers and methods for their preparation, their use as semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these polymers.

First claim

The invention claimed is:

1. A polymer according selected from the following formulae:

wherein Ar denotes a group of formula 2 or 3

X is C(R x ) or N,
Y is O, S, Se or N(R x ),
Z is C(R x ) or N,
Y 1 is O, S, Se, N(R x ), or —CH═CH—,
Z 1 is C(R x ) or N,
W is S, Se, O or NR x ,
R 1 , R 2 are, each independently of one another, an optionally substituted C 1-40 carbyl or hydrocarbyl group,
U 1 and U 2 are each, independently of one another, —C(R x )═, —C(R x R y )—, —Si(R x R y )—, —N(R x )—, —S—, —Se—, —O— or a single bond, wherein U 1 and U 2 are not both a single bond,
R x and R y are each H or 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(O)—O—, —O—C(O)—, O—C(O)—O—, —CH═CH— or —C≡C— and in which one or more H atoms are each optionally replaced by F, Cl, Br, I or CN,
u is 0 or 1, and
n is an integer >1.

2. A polymer according selected from the following formula:

wherein Ar denotes a group of formula 1, 2 or 3

X is C(R x ) or N,
Y is O, S, Se or N(R x ),
Z is C(R x ) or N,
Y 1 is O, S, Se, N(R x ), or —CH═CH—,
Z 1 is C(R x ) or N,
W is S, Se, O or NR x ,
R 1 , R 2 are, each independently of one another, an optionally substituted C 1-40 carbyl or hydrocarbyl group,
U 1 and U 2 are each, independently of one another, —C(R x )═, —C(R x R y )—, —Si(R x R y )—, —N(R x )—, —S—, —Se—, —O— or a single bond, wherein U 1 and U 2 are not both a single bond,
R x and R y are each H or 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(O)—O—, —O—C(O)—, O—C(O)—O—, —CH═CH— or —C≡C— and in which one or more H atoms are each optionally replaced by F, Cl, Br, I or CN,
u is 0 or 1, and
n is an integer >1.

3. A polymer according selected from the following formulae:

wherein Ar denotes a group of formula 1

X is C(R x ) or N,
Y is O, S, Se or N(R x ),
Z is C(R x ) or N,
Y 1 is O, S, Se, N(R x ), or —CH═CH—,
Z 1 is C(R x ) or N,
W is S, Se, O or NR x ,
R 1 , R 2 are, each independently of one another, an optionally substituted C 1-40 carbyl or hydrocarbyl group,
U 1 is —C(R x )═, —C(R x R y )—, —Si(R x R y )—, —N(R x )—, —S—, —Se—, —O— or a single bond,
U 2 is —Si(R x R y )—, —N(R x )—, —S—, —Se—, —O— or a single bond, wherein U 1 and U 2 are not both a single bond,
R x and R y are each H or 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(O)—O—, —O—C(O)—, O—C(O)—O—, —CH═CH— or —C≡C— and in which one or more H atoms are each optionally replaced by F, Cl, Br, I or CN,
u is 0 or 1, and
n is an integer >1.

4. A polymer according to claim 1 , wherein R 1 and R 2 are selected from straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—, —O—C(O)—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl having 4 to 30 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 3 , wherein
R 3 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, or 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, and
X 0 is halogen.

5. A polymer according to claim 1 , wherein
R 1 and/or R 2 are selected from primary alkyl or alkoxy with 1 to 30 C atoms, secondary alkyl or alkoxy with 3 to 30 C atoms, and tertiary alkyl or alkoxy with 4 to 30 C atoms, wherein in all these groups one or more H atoms are each optionally replaced by F, or
R 1 and/or R 2 are selected from aryl, aryloxy, heteroaryl and heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms.

6. A mixture or blend comprising one or more polymers according to claim 1 and one or more compounds or polymers having semiconducting, charge transport, hole/electron transport, hole/electron blocking, electrically conducting, photoconducting or light emitting properties.

7. A formulation comprising one or more polymers according to claim 1 , and one or more solvents.

8. A method of operating an optical, electrooptical, electronic, electroluminescent or photoluminescent component or device comprising using a charge transport, semiconducting, electrically conducting, photoconducting or light emitting material to emit light, wherein said material comprises a polymer according to claim 1 .

9. An optical, electrooptical or electronic component or device comprising one or more polymers according to claim 1 .

10. A component or device according to claim 9 , which is selected from organic field effect transistors (OFET), thin film transistors (TFT), integrated circuits (IC), logic circuits, capacitors, radio frequency identification (RFID) tags, devices or components, organic light emitting diodes (OLED), organic light emitting transistors (OLET), flat panel displays, backlights of displays, organic photovoltaic devices (OPV), solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, charge transport layers or interlayers in polymer light emitting diodes (PLEDs), Schottky diodes, planarizing layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates, conducting patterns, electrode materials in batteries, alignment layers, biosensors, biochips, security markings, security devices, and components or devices for detecting and discriminating DNA sequences.

11. A component or device according to claim 9 , which is an OFET or a bulk heterojunction OPV device.

12. A polymer according to claim 1 , wherein W is S.

13. A polymer according to claim 1 , wherein W is Se.

14. A polymer according to claim 1 , wherein W is O.

15. A polymer according to claim 1 , wherein W is or NR x .

16. A process of preparing a

Assignees

• Merck Patent Gmbh

Inventors

• Mitchell William
• Tierney Steven
• Blouin Nicolas
• Meyer Frank Egon
• Carrasco-Orozco Miguel

Classifications

• C08G2261/91

  Photovoltaic applications · CPC title

• C08G2261/3223

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

• C08G2261/3243

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

• C08G2261/3246

  containing nitrogen and sulfur as heteroatoms · CPC title

• C08G2261/124

  alternating · CPC title