Conjugated polymers

Patent metadata

Field	Value
Publication number	US-10629815-B2
Application number	US-201515120581-A
Country	US
Kind code	B2
Filing date	Feb 10, 2015
Priority date	Feb 20, 2014
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

The invention relates to new conjugated semiconducting polymers containing thermally cleavable side groups. The thermally cleavable side groups are selected from among carbonate groups and carbamate groups. By thermally cleaving side groups, the solubility or the polymers can be reduced in a targeted manner. The polymers are used as semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, organic photodetectors (OPDs), organic light emitting diodes (OLEDs), and organic field effect transistors (OFETs).

First claim

The invention claimed is:

1. A process for partially or fully detaching the carbonate or carbamate groups in a conjugated polymer comprising heating the polymer or a layer comprising the polymer to a temperature in the range of from 150° C. to 200° C.,
wherein the conjugated polymer comprises one or more identical or different repeat units of formula (I):

wherein:
Ar is a mono- or polycyclic aryl or heteroaryl radical which is optionally substituted at one or more positions;
Sp 1 is a single bond or alkylene radical having 1 to 20 carbon atoms and is unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more nonadjacent CH 2 groups are each optionally independently replaced by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CR 0 ═CR 00 —, or —C≡C— such that no oxygen and/or sulfur atoms are directly bonded to one another;
X 1 is NR 0 or O;
wherein, if the Sp 1 -X 1 —C(O)—OR 1 radical is bonded to a nitrogen atom in the Ar radical, the Sp 1 -X 1 radical may also be a single bond,
R 0 and R 0
are each independently H or an alkyl group having 1 to 12 carbon atoms; and

R 1 is a hydrocarbyl radical having 1 to 40 carbon atoms,
with the proviso that the repeat units of the formula (I) excludes
repeat units wherein Ar is a phenylene radical that is mono-or polysubstituted by —NH—C(O)—OR 1 and wherein, in the polymer backbone, is directly adjacent to an optionally substituted benzo[lmn][3,8]phenanthroline-1,3,6,8-tetraone-4,9-diyl unit, and
repeat units wherein Ar is pyrrolo[3,4-c]pyrrole-1,4-dione-3,6-diyl, wherein both nitrogen atoms are substituted by —C(O)—OR 1 .

2. The process of claim 1 , wherein the repeat units of formula (I) are selected from the group consisting of formulae (I1) through (I11):

wherein
R 2 and R 3
are the same or different in each instance and are each independently a —Sp 1 -X 1 —C(O)—O—R 1 radical; and

R 4 is the same or different in each instance and is a straight-chain or branched alkyl radical having 1 to 25 carbon atoms.

3. The process of claim 2 , wherein the repeat units are selected from the group consisting of formulae (I4a), (I10a), and (I11a):

wherein
R 4a is a straight-chain or branched alkyl radical having 1 to 25 carbon atoms.

4. The process of claim 1 , wherein the Sp 1 radical is an alkylene radical having 1 to 20 carbon atoms.

5. The process of claim 1 , wherein the R 1 radical is a straight-chain, branched, or cyclic alkyl radical having 1 to 25 carbon atoms and is unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, and wherein one or more nonadjacent CH 2 groups are each optionally independently replaced by —O—, —S—, —C(O)—, —C(S)—, —C(O)—O—, —O—C(O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a way that no oxygen and/or sulfur atoms are joined directly to one another.

6. The process of claim 1 , wherein the X 1 radical is O or NH.

7. The process of claim 1 , wherein the -Sp 1 -X 1 —C(O)—O—R 1 radical is a radical of formula (S):

wherein
R 1a , R 1b , and R 1c
are each independently H or a straight-chain, branched, or cyclic alkyl radical having 1 to 25 carbon atoms or a straight-chain, branched, or cyclic alkenyl radical or alkynyl radical each having 2 to 25 carbon atoms, wherein two of the R 1a , R 1b , and R 1c radicals together optionally define a cyclic alkyl radical, alkenyl radical, or alkynyl radical each having 5 to 12 carbon atoms;

m is 0 or an integer from 1 to 12; and
* denotes the linkage to the Ar radical.

8. The process of claim 7 , wherein the radical of formula (S) is selected from the group consisting of formulae (S1) through (S2):

wherein
R 4 is the same or different at each instance and is 1H or a straight-chain or branched alkyl radical having 1 to 25 carbon atoms;
m is an integer from 1 to 12; and
* denotes the linkage to the Ar radical.

9. The process of claim 1 , wherein the Ar radical comprises one or more nitrogen atoms, the Sp 1 -X 1 —C(O)—O—R 1 radical is bonded to one of the nitrogen atoms in the Ar radical, and the Sp 1 -X 1 radical is a single bond.

10. The process of claim 1 , wherein the conjugated polymer comprises one or more repeat units of formulae (IIa) or (IIb):
—[(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ]—  (Ia);

—[(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar) d ]—  (Ib);

wherein
U is a unit of formula (I) or a unit selected from the group consisting of units of formulae (I1) through (I11):

wherein
R 2 and R 3
are the same or different in each instance and are each independently a -Sp 1 -X 1 —C(O)—O—R 1 radical; and

R 4 is the same or different in each instance and is a straight-chain or branched alkyl radical having 1 to 25 carbon atoms;

Ar 1 , Ar 2 , Ar 3
are each independently the same or different in each instance and are an optionally substituted aryl or heteroaryl group different than U;

R S is the same or different in each instance and is selected from the group consisting of 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 , an optionally substituted silyl or hydrocarbyl group having 1 to 40 carbon atoms and which optionally comprises one or more heteroatoms;
X 0 is halogen;
a, b, and c
are the same or different in each instance and are each independently 0, 1, or 2;

d is the same or different in each instance and is 0 or an integer from 1 to 10;

wherein the conjugated polymer comprises at least one repeat unit of formula (Ia) or (IIb) wherein b is at least 1.

11. The process of claim 10 , wherein the conjugated polymer further comprises one or more optionally substituted mono- or polycyclic aryl or heteroaryl units.

12. The process of claim 11 , wherein the optionally substituted mono- or polycyclic aryl or heteroaryl units are selected from the group consisting of formulae (ilia) and (IlIb):
—[(Ar 1 ) a —(Ar 4 ) b —(Ar 2 ) c —(Ar 3 ) d ]—  (IIIa); and

—[(Ar 4 ) b —(Ar 1 ) a —(Ar 4 ) b —(Ar 2 ) c —(Ar 3 ) d ]—  (IIIb);

wherein
Ar 4 is an optionally substituted aryl or heteroaryl group different than U and Ar 1-3 ; and
the conjugated polymer comprises at least one repeat unit of formula (IIIa) or (IIIb) wherein b is at least 1.

13. The process of claim 12 , wherein the conjugated polymer is selected from formula (IV):

Assignees

• Innovationlab Gmbh
• Karlsruher Inst Technologie
• Univ Braunschweig Tech
• Max Planck Gesellschaft

Inventors

• Kuhn Marius
• Adermann Torben
• Hamburger Manuel
• Muellen Klaus
• Schinke Janusz
• Colsmann Alexander
• Hoefle Stefan
• Lemmer Ulrich

Classifications

• C08G2261/3246

  containing nitrogen and sulfur as heteroatoms · CPC title

• C08G61/124

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

• C08G2261/412

  Yamamoto reactions · CPC title

• C08G2261/411

  Suzuki reactions · CPC title

• C08G2261/124

  alternating · CPC title