Conjugated polymers

Patent metadata

Field	Value
Publication number	US-10059796-B2
Application number	US-201414909036-A
Country	US
Kind code	B2
Filing date	Jul 28, 2014
Priority date	Jul 30, 2013
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

The present invention comprises a conjugated polymer for optoelectronic devices, comprising a structural unit of formula (I) or formula (II):

-[A-D1-A-D2]n-  (I)

-[A1-D1-A2-D2]n-  (II)

wherein A is an acceptor group; A1 and A2 are acceptor M groups which differ from one another; D1 and D2 are donor groups which differ from one another; and n is an integer between 30 and 1000.

First claim

The invention claimed is:

1. A regioregular conjugated polymer for optoelectronic devices, comprising a structural unit of formula (I) or formula (II):
-[A-D1-A-D2] n -  (I)

-[A1-D1-A2-D2] n -  (II)

wherein
A is an acceptor group;
A1 and A2 are acceptor groups which differ from one another;
D1 and D2 are donor groups which differ from one another; and
n is an integer between 30 and 1000,
wherein the acceptor is an asymmetric group and the acceptor groups A are disposed with mutual symmetry about the donor group D1.

2. The polymer according to claim 1 , wherein the structural unit is of formula (I) and the acceptor group, A, is selected from the group consisting of:

wherein
R is alkyl or aryl;
X is S or O;
Y and Z are independently selected from the group consisting of C—H, C—R, C—F, C—Cl, C—CF 3 , C—CN, N, C—COOH, C—COOR and C—CONHR.

3. The polymer according to claim 1 , wherein the acceptor group A at each occurrence is of formula (4):

4. The polymer according to claim 1 , wherein D1 and D2 are independently selected from the group consisting of:

wherein
R 1 to R 4 are independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted aryl, and optionally substituted heterocyclyl; and
p is an integer from 1 to 3.

5. The polymer according to claim 4 , wherein D1 and D2 are different monomer units independently selected from structural units of formula (Xa)

wherein
R 1 to R 4 are independently selected from hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted carbocyclyl, optionally substituted aryl, and optionally substituted heterocyclyl.

6. The polymer according to claim 5 , wherein R 3 or R 4 are hydrogen.

7. The polymer according to claim 6 , wherein the substituents R 1 or R 2 are independently selected from hydrogen or an optionally substituted alkyl chain and at least one of R 1 or R 2 is optionally substituted alkyl.

8. The polymer according to claim 1 , wherein the polymer has a number average molar mass in the range of 40,000 to 100,000 Daltons.

9. The polymer according to claim 1 , wherein the polymer comprises thiophene or phenyl endcaps.

10. The polymer according to claim 1 , which is a polymer of a macromonomer comprising a structural unit of formula (XI) and a donor monomer, D2:
A-D1-A  (XI).

11. The polymer according to claim 1 , which is a polymer of a macromonomer comprising formula (Xla) with a donor monomer of formula (XIII):
P-A-D1-A-P  (Xla)

Q-D2-Q  (XIII)

wherein P and Q are reactive coupling partners; and
wherein the acceptor groups, A, are disposed with mutual symmetry about donor group D1.

12. The polymer according to claim 11 , wherein the macromonomer is of formula (Xlb):

13. The polymer according to claim 11 ,
wherein either
(a) P is selected from the group consisting of bromine, iodine and pseudo-halides; and
Q is selected from the group consisting of alkenyl, —B(R 5 ) 2 ,—BF 3 K, —SiR 6 3 , —SnR 3 , —MgX, —ZnCI, —ZnBr, —Znl;
wherein
R is alkyl or aryl;
R 5 is selected from the group consisting of R and (OR); and
R 6 is chlorine, fluorine or alkyl; and
X is selected from the group consisting of bromine, iodine and pseudo-halides; or

(b) P is selected from the group consisting of alkenyl, —B(R 5 ) 2 , —BF 3 K, —SiR 6 3 , —SnR 3 , —MgX, —ZnCI, —ZnBr, —Znl;
Q is selected from the group consisting of bromine, iodine and pseudo-halides;
R is alkyl;
R 5 is selected from the group consisting of R and (OR);
R 6 is chlorine, fluorine or alkyl; and
X is selected from the group consisting of bromine, iodine and pseudo-halides.

14. A method of preparing a polymer according to claim 1 , comprising polymerising a macromonomer of formula (Xla) with a donor monomer of formula (XIII)
P-A-D1-A-P  (Xla)

Q-D 2 -Q  (XIII)

wherein P and Q are reactive coupling partners; and
wherein acceptor groups, A, are disposed with mutual symmetry about donor group D1.

15. The method according to claim 14 , wherein the macromonomer of formula (XI) or (Xla) is prepared by reaction of D1 with an acceptor of any one of formulae shown in claim 2 to provide selective coupling of the acceptor, one unit of acceptor on each side of the donor wherein said acceptor is coupled with mutual symmetry about donor D1.

16. A photosensitive optoelectronic device comprising one or more polymers according to claim 1 .

17. The device according to claim 16 , wherein the device is a photovoltaic device, a photoconductive device or a photodetector.

18. A solar cell device fabricated using one or more polymers according to claim 1 and an electron acceptor polymer or molecule.

19. The solar cell device according to claim 18 , wherein the electron acceptor polymer or molecule is one or more fullerene derivatives.

Assignees

• Commw Scient Ind Res Org

Inventors

• Qin Tianshi
• Watkins Scott Edward

Classifications

• C08G2261/3247

  containing combinations of different heteroatoms other than nitrogen and oxygen or nitrogen and sulfur · CPC title

• C08G2261/3246

  containing nitrogen and sulfur as heteroatoms · CPC title

• H01L51/0036

  Electricity · mapped topic

• C08G61/126 Primary

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

• Y02E10/549

  Organic PV cells · CPC title