Conjugated polymers

Patent metadata

Field	Value
Publication number	US-9178166-B2
Application number	US-201414452713-A
Country	US
Kind code	B2
Filing date	Aug 6, 2014
Priority date	Feb 15, 2012
Publication date	Nov 3, 2015
Grant date	Nov 3, 2015

Abstract

The invention relates to novel conjugated polymers containing repeating units comprising a halogenated benzene ring, a silolobithiophene moiety, and a benzofused heteroaromatic moiety, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in 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 polymer comprising:
at least one unit of formula I

 wherein
A is an optionally substituted, benzofused heteroaryl moiety comprising 1-6 heteroatoms selected from the group consisting of N, O, S, P, Si, Se, As, Te, and Ge, wherein the benzofused heteroaryl moiety is selected from the group consisting of
formula B1a, formula B1b, formula B1c, formula B2a, formula B2b, and formula B3a,

 R 1 and R 2 are the same or different, and are independently selected from H or halogen,
R 3 , R 4 , R 5 , R 6 , R 7 are the same or different, and are independently selected from H, halogen, C 1 -C 30 straight-chain, branched or cyclic alkyl moieties, in which one or more non-adjacent CH 2 groups are optionally 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— so that O and/or S atoms are not linked directly to one another, and one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms that are optionally substituted by halogen or substituted or unsubstituted C 1 -C 30 straight-chain, branched or cyclic alkyl moieties,
Y 1 and Y 2 are the same or different, and are independently selected from H, F, Cl or CN,
R 0 and R 00 are the same or different, and are independently selected from H or optionally substituted C 1 -C 40 carbyl or hydrocarbyl moieties.

2. The polymer according to claim 1 , wherein A is a moiety selected from the group consisting of formula B1a, formula B2b and formula B3a.

3. The polymer according to claim 1 , wherein the at least one unit of formula I is selected from the group consisting of formula Ia, formula Ib, formula Ic, formula Id, formula Ie, formula If, formula Ig, formula Ih, formula Ii, formula Ij, formula Ik, formula Il, formula Im, formula In, formula Io, formula Ip, formula Iq, and formula Ir,

wherein R 3 , R 5 and R 6 are the same or different, and are independently selected from H, halogen, C 1 -C 30 straight-chain, branched or cyclic alkyl moieties, in which one or more non-adjacent CH 2 groups are optionally 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— so that O and/or S atoms are not linked directly to one another, and one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms that are optionally substituted by halogen or substituted or unsubstituted C 1 -C 30 straight-chain, branched or cyclic alkyl moieties.

4. The polymer according to claim 1 of formula II

wherein
A is at least one unit selected from the group consisting of formula I, formula Ia, formula Ib, formula Ic, formula Id, formula Ie, formula If, formula Ig, formula Ih, formula Ii, formula Ij, formula Ik, formula Il, formula Im, formula In, formula Io, formula Ip, formula Iq, and formula Ir,
B is at least one unit that is different from A and is selected from the group consisting of formula I, formula Ia, formula Ib, formula Ic, formula Id, formula Ie, formula If, formula Ig, formula Ih, formula Ii, formula Ij, formula Ik, formula Il, formula Im, formula In, formula Io, formula Ip, formula Iq, and formula Ir,
wherein R 3 , R 5 and R 6 are the same or different, and are independently selected from H, halogen, C 1 -C 30 straight-chain, branched or cyclic alkyl moieties, in which one or more non-adjacent CH 2 groups are optionally 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— so that O and/or S atoms are not linked directly to one another, and one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms that are optionally substituted by halogen or substituted or unsubstituted C 1 -C 30 straight-chain, branched or cyclic alkyl moieties;
x is >0 and ≦1,
Y is ≧0 and <1,
x+y is 1, and
n is an integer >1.

5. The polymer according to claim 4 selected from the group consisting of formula IIa, formula IIb, formula IIc, formula IId, formula IIe, formula IIf, formula IIg, formula IIh, formula IIi, formula Ilk, formula IIm, formula IIn, formula IIo, formula IIp, formula IIq, and formula IIr,

wherein R 3 , R 5 and R 6 are the same or different, and are independently selected from H, halogen, C 1 -C 30 straight-chain, branched or cyclic alkyl moieties, in which one or more non-adjacent CH 2 groups are optionally 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— so that O and/or S atoms are not linked directly to one another, and one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms that are optionally substituted by halogen or substituted or unsubstituted C 1 -C 30 straight-chain, branched or cyclic alkyl moieties, n is an integer >1, 0<x<1 and 0<y<1.

6. A polymer of formula III
R 8 -chain-R 9   III

wherein “chain” is the polymer of claim 4 , R 8 and R 9 are the same or different, and are selected independently from the group consisting of H, halogen, C 1 -C 30 straight-chain, branched or cyclic alkyl moieties, in which one or more non-adjacent CH 2 groups are optionally 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— so that O and/or S atoms are not linked directly to one another, and one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms that are optionally substituted by halogen or substituted or unsubstituted C 1 -C 30 straight-chain, branched or cyclic alkyl moieties, or are selected independently from the group consisting of H, F, Br, Cl, I, —CH 2 Cl, —CHO, —CR a ═CR b 2 , —SiR a R b R c , —SiR a X a X b , —SiR a R b X a , —SnR a R b R c , —BR a R b , —B(OR a )(OR b ), —B(OH) 2 , —O—SO 2 —R a , —C≡CH, —C≡—SiR a 3 , —ZnX a or an endcap group, X a and X b are halogen, R a , R b and R c are the same or different, and are selected independently from the group consisting of H or optionally substituted C 1 -C 40 carbyl or hydrocarbyl moieties, and wherein two of R a , R b and R c may also form a ring together with the hetero atom to which they are attached.

7. A mixture or polymer blend comprising:
at least one polymer according to claim 1 , and
at least one compound or polymer having semiconducting, charge transport, hole/electron transport, hole/electron blocking, electricall

Assignees

• Merck Patent Gmbh

Inventors

• Waller David P
• Cheon Kap-Soo

Classifications

• C08G2261/3223

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

• C08G2261/411

  Suzuki reactions · CPC title

• C08G2261/1414

  Unsaturated aliphatic units · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title