Conjugated polymers

Patent metadata

Field	Value
Publication number	US-9559305-B2
Application number	US-201314385609-A
Country	US
Kind code	B2
Filing date	Feb 15, 2013
Priority date	Mar 16, 2012
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

The invention relates to novel conjugated polymers comprising in their backbone one or more divalent donor units, like for example benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl (BDT), that are linked on both sides to an acceptor unit, to methods of preparing the polymers and educts or intermediates used in such preparation, to polymer blends, mixtures and formulations containing the polymers, to the use of the polymers, polymer blends, mixtures and formulations as semiconductors organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these polymers, polymer blends, mixtures or formulations.

First claim

The invention claimed is:

1. A conjugated polymer that comprises in its backbone one or more electron donor units D i and one or more electron acceptor units A i , and optionally one or two terminal or endcap units T, wherein each donor unit D i in the polymer backbone is flanked by two acceptor units A i to form a triad A i -D i -A i , except for D i units adjacent to a terminal or endcap group T, which polymer fulfils the condition f≦s/2+2, wherein f is the total number of units D i in the polymer backbone, s is the total number of units A i in the polymer backbone and s is at least 2, and excluding polymers comprising repeating units [A-D-A] wherein A is optionally substituted pyrazolone and D is optionally substituted benzo[1,2-b:4,5-b′]dithiophene.

2. The conjugated polymer according to claim 1 , which comprises in its backbone one or more spacer units Sp i linking the triads A i -D i -A i , wherein said one or more spacer units Sp i are different from D i and are selected such that they do not act as electron acceptor towards the donor unit D i .

3. The conjugated polymer according to claim 1 , which comprises in its backbone one or more repeating units, sequences, segments or blocks selected from the group consisting of the formulae -[A 1 -D 1 ] x -[A 2 -Sp 1 ] y - and -[A 1 -D 1 -A 2 -Sp 1 ]- wherein A 1 and A 2 denote independently of each other an acceptor unit, D 1 denotes a donor unit, and Sp 1 denotes a spacer unit which is not acting as electron acceptor towards D 1 and is different from D 1 .

4. The conjugated polymer according to claim 3 , wherein 0<x<1, 0<y<1, x+y=1, wherein x is the molar ratio of the segments A 1 -D 1 and y is the molar ratio of the segments A 2 -Sp 1 .

5. The conjugated polymer according to claim 1 , wherein the donor units D i are selected from the group consisting of
benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl,
7H-3,4-dithia-7-sila-cyclopenta[a]pentalene-di-2,5-diyl, and
4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2,6-diyl.

6. The conjugated polymer according to claim 1 , wherein the donor units D i and the acceptor units A i are selected from the group consisting of arylene and heteroarylene units, which are monocyclic or polycyclic and are unsubstituted or substituted.

7. The conjugated polymer according to claim 6 , wherein the donor units D i are selected from the group consisting of the following formulae:

wherein
Ar denotes a carbocyclic, heterocyclic, aromatic or heteroaromatic group, which comprises one or more saturated or unsaturated rings that are covalently linked or fused, which is fused to the terminal five-membered rings in formula Ia or Ib to form a conjugated system, and which is unsubstituted or substituted,
Ar 1 denotes a carbocyclic, heterocyclic, aromatic or heteroaromatic group, which comprises one or more saturated or unsaturated rings that are covalently linked or fused, which is fused to the divalent five-membered ring in formula Ig, and which is unsubstituted or substituted,
X 1 and X 2 denote independently of each other O, S, Se, Si or NR 1 ,
Y 1-4 denote independently of each other CR 1 or N,
R 1 denotes H, halogen, or an optionally substituted carbyl or hydrocarbyl group, wherein one or more C atoms are optionally replaced by a hetero atom, and
R 11 and R 12 independently of each other have one of the meanings of R 1 .

8. The conjugated polymer according to claim 7 , wherein Ar and Ar 1 in formula Ia, Ib and Ig are selected from the group consisting of benzene, pyrazine, 2H-pyran, 1,4-dioxane, naphthalene, anthracene, cyclopentadiene, thiophene, pyrrole, furan, 1H-silole, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, 1,5-dihydro-s-indacene, 1,7-dihydro-s-indacene, 1,5-disila-s-indacene, 1,7-disila-s-indacene, pyrrolo[3,2-f]indole, and pyrrolo[2,3-f]indole, all of which are unsubstituted or substituted by one or more groups R 1 , which denotes H, halogen, or an optionally substituted carbyl or hydrocarbyl group wherein one or more C atoms are optionally replaced by a hetero atom.

9. The conjugated polymer according to claim 1 , wherein the donor units D i are selected from the group consisting of the following formulae and their mirror images:

wherein one of X 11 and X 12 is S and the other is Se, and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 16 , R 17 and R 18 independently of each other denote H, halogen, or an optionally substituted carbyl or hydrocarbyl group wherein one or more C atoms are optionally replaced by a hetero atom.

10. The conjugated polymer according to claim 1 , wherein the donor units D i are selected from the group consisting of the following formulae

wherein R 1-4 independently of each other denote H, halogen, or an optionally substituted carbyl or hydrocarbyl group wherein one or more C atoms are optionally replaced by a hetero atom.

11. The conjugated polymer according to claim 1 , wherein the donor units D i are selected from the group consisting of the following formulae

wherein R 1-4 independently of each other denote H, halogen, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent CH 2 groups are optionally replaced by —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—, —O—C(O)—O—, —SO 2 —, —SO 3 —, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CHR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl or heteroaryl that is optionally substituted and has 4 to 30 ring atoms, wherein R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl, and Y 1 and Y 2 denote H, F or CN.

12. The conjugated polymer according to claim 1 , wherein the acceptor units A i are selected from the group consisting of the following formulae and their mirror images:

Assignees

• Merck Patent Gmbh

Inventors

• Blouin Nicolas
• Phillips Amy
• Nanson Lana
• Tierney Steven
• Cull Toby
• Tiwana Priti
• Berny Stephane
• Carrasco-Orozco Miguel
• Meyer Frank Egon

Classifications

• C08G75/32

  Polythiazoles; Polythiadiazoles · CPC title

• C07F5/04

  Esters of boric acids · CPC title

• C08G2261/51

  Charge transport · CPC title

• C07D495/04

  Ortho-condensed systems · CPC title

• C08G2261/3245

  containing nitrogen and oxygen as heteroatoms · CPC title