IP Library › Granted Patent US 8,436,127

Granted Patent B2

US 8,436,127 · App. 13/454,403 · Granted May 7, 2013

Semiconductor materials based on diketopiperidinopiperidine copolymers

Inventors: Ashok Kumar Mishra (Singapore, SG); Subramanian Vaidyanathan (Basel, CH); Hiroyoshi Noguchi (Singapore, SG); Florian Dötz (Singapore, SG); Yucui Guan (Hangzhou, CN)

Assignee: BASF SE

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Quick Facts

Patent No.: US 8,436,127
App. No.: 13/454,403
Granted: May 7, 2013
Kind: B2

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Abstract

The present invention provides a polymer comprising a unit of formula and an electronic device comprising the polymer as semiconducting material.

Claims (92)

1. A polymer comprising a unit of formula (1):

wherein:

R 1 and R 2 are independently from each other H, C 1-30 -alkyl optionally substituted with 1 to 6 substituents C 2-30 -alkenyl optionally substituted with 1 to 6 substituents R c , C 2-30 -alkynyl optionally substituted with 1 to 6 substituents R c , C 3-10 -cycloalkyl optionally substituted with 1 to 6 substituents R d , C 5-10 -cycloalkenyl optionally substituted with 1 to 6 substituents R d , monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R d , C 6-14 -aryl optionally substituted with 1 to 6 substituents R e or monovalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R e ;

R c at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 3 , —S—C 1-10 -alkyl, —NH 2 , —NHR 3 , —NR 3 R 4 , —NH—COR 3 , —COOH, —COOR 3 , —CONH 2 , —CONHR 3 , —CONR 3 R 4 , —CO—H, —COR 3 , C 3-10 -cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

R d at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 3 , —S—C 1-10 -alkyl, —NH 2 , —NHR 3 , —NR 3 R 4 , —NH—COR 3 , —COOH, —COOR 3 , —CONH 2 , —CONHR 3 , —CONR 3 R 4 , —CO—H, —COR 3 , C 1-40 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

R e at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 3 , —S—C 1-10 -alkyl, —NH 2 , —NHR 3 , —NR 3 R 4 , —NH—COR 3 , —COOH, —COOR 3 , —CONH 2 , —CONHR 3 , —CONR 3 R 4 , —CO—H, —COR 3 , C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue;

R 3 and R 4 at each occurrence are independently from each other selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

G 1 and G 2 are independently from each other C 6-14 -arylene optionally substituted with 1 to 6 substituents R a or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a ;

R a at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-30 -alkoxy, —O—CH 2 CH 2 O—C 1-30 -alkyl, —O—COR 8 , —S—C 1-30 -alkyl, —NH 2 , —NHR 8 , —NR 8 R 9 , —NH—COR 8 , —COOH, —COOR 8 , —CONH 2 , —CONHR 8 , —CONR 8 R 9 , —CO—H, —COR 8 , C 1-30 -alkyl optionally substituted with 1 to 6 substituents R f , C 2-30 -alkenyl optionally substituted with 1 to 6 substituents R f , C 2-30 -alkynyl optionally substituted with 1 to 6 substituents R f , C 3-10 -cycloalkyl optionally substituted with 1 to 6 substituents R g , C 5-10 -cycloalkenyl optionally substituted with 1 to 6 substituents R g and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R g ;

R 8 and R 9 at each occurrence are independently from each other selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

R f at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 10 , —S—C 1-10 -alkyl, —NH 2 , —NHR 10 , —NR 10 R 11 , —NH—COR 10 , —COOH, —COOR 10 , —CONH 2 , —CONHR 10 , —CONR 10 R 11 , —CO—H, —COR 10 , C 3-10 -cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

R g at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 10 , —S—C 1-10 -alkyl, —NH 2 , —NHR 10 , —NR 10 R 11 , —NH—COR 10 , —COOH, —COOR 10 , —CONH 2 , —CONHR 10 , —CONR 10 R 11 , —CO—H, —COR 10 , C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; and

R 10 and R 11 at each occurrence are independently from each other selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,

wherein:

G 1 and G 2 are independently from each other:

R 5 and R 6 are independently from each other H or C 1-30 -alkyl;

L is C 6-24 -arylene optionally substituted with 1 to 6 substituents R b or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R b ;

R b at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-30 -alkoxy, —O—CH 2 CH 2 O—C 1-30 -alkyl, —O—COR 12 , —S—C 1-30 -alkyl, —NH 2 , —NHR 12 , —NR 12 R 13 , —NH—COR 12 , —COOH, —COOR 12 , —CONH 2 , —CONHR 12 , —CONR 12 R 13 , —CO—H, —COR 12 , C 1-30 -alkyl optionally substituted with 1 to 6 substituents R h , C 2-30 -alkenyl optionally substituted with 1 to 6 substituents R h , C 2-30 -alkynyl optionally substituted with 1 to 6 substituents R h , C 3-10 -cycloalkyl optionally substituted with 1 to 6 substituents R i , C 5-10 -cycloalkenyl optionally substituted with 1 to 6 substituents R i and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R i ;

R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

R h at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 14 , —S—C 1-10 -alkyl, —NH 2 , —NHR 14 , —NR 14 R 15 , —NH—COR 14 , —COOH, —COOR 14 , —CONH 2 , —CONHR 14 , —CONR 14 R 15 , —CO—H, —COR 14 , C 3-10 -cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

R i at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 14 , —S—C 1-10 -alkyl, —NH 2 , —NHR 14 , —NR 14 R 15 , —NH—COR 14 , —COOH, —COOR 14 , —CONH 2 , —CONHR 14 , —CONR 14 R 15 , —CO—H, —COR 14 , C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; and

R 14 and R 15 at each occurrence are independently from each other selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 3-10 -cycloalkyl, C 5-10 -cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,

wherein:

L is:

R 16 and R 17 are independently from each other H, C 1-30 -alkyl, —CN or halogen;

q and s are independently from each other 0, 1, 2, 3, 4 or 5;

r is 0, 1 or 2; and

n is an integer from 2 to 10,000.

2. The polymer of claim 1 , wherein:

R 1 and R 2 are independently from each other H, C 1-30 -alkyl optionally substituted with 1 to 6 substituents R c , C 2-30 -alkenyl optionally substituted with 1 to 6 substituents R c , C 2-30 -alkynyl optionally substituted with 1 to 6 substituents R c , C 3-10 -cycloalkyl optionally substituted with 1 to 6 substituents R d , C 5-10 -cycloalkenyl or C 6-14 -aryl optionally substituted with 1 to 6 substituents R e ;

R d at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 3 , —S—C 1-10 -alkyl, —NH 2 , —NHR 3 , —NR 3 R 4 , —NH—COR 3 , —COOH, —COOR 3 , —CONH 2 , —CONHR 3 , —CONR 3 R 4 , —CO—H, —COR 3 , C 1-10 -alkyl, C 2-40 -alkenyl, C 2-10 -alkynyl, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;

3. The polymer of claim 1 , wherein:

R 1 and R 2 are independently from each other C 1-30 -alkyl optionally substituted with 1 to 6 substituents R c ;

4. The polymer of claim 1 , wherein R 1 and R 2 are independently from each other C 1-16 -alkyl.

5. The polymer of any one of claims 1 to 4 , wherein:

G 1 and G 2 are independently from each other bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a ;

R a at each occurrence are independently from each other selected from the group consisting of ═O, ═C(CN) 2 , —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-30 -alkoxy, —O—CH 2 CH 2 O—C 1-30 -alkyl, —O—COR 8 , —S—C 1-30 -alkyl, —NH 2 , —NHR 8 , —NR 8 R 9 , —NH—COR 8 , —COOH, —COOR 3 , —CONH 2 , —CONHR 8 , —CONR 8 R 9 , —CO—H, —COR 8 , C 1-30 -alkyl optionally substituted with 1 to 6 substituents R f , C 2-30 -alkenyl optionally substituted with 1 to 6 substituents R f , C 2-30 -alkynyl optionally substituted with 1 to 6 substituents R f , C 3-10 -cycloalkyl optionally substituted with 1 to 6 substituents R g , C 5-10 -cycloalkenyl optionally substituted with 1 to 6 substituents R g and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R g ;

wherein:

G 1 and G 2 are independently from each other:

R 5 and R 6 are independently from each other H or C 1-30 -alkyl.

6. The polymer of any one of claims 1 to 4 , wherein:

G 1 and G 2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents R a ;

R a at each occurrence are independently from each other C 1-30 -alkyl optionally substituted with 1 to 4 substituents R f ; and

7. The polymer of any one of claims 1 to 4 , wherein:

G 1 and G 2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, such that G 1 and G 2 are substituted with 1 to 2 substituents R a ; and

R a at each occurrence are independently from each other C 6-20 -alkyl.

8. The polymer of any one of claims 1 to 4 , wherein:

L is bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R b ;

wherein:

L is:

R 16 and R 17 are independently from each other H, C 1-30 -alkyl, —CN or halogen.

9. The polymer of any one of claims 1 to 4 , wherein:

L is bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents R b ;

R b at each occurrence are independently from each other C 1-30 -alkyl optionally substituted with 1 to 4 substituents R h ; and

R h at each occurrence are independently from each other selected from the group consisting of ═O, —O—C 2-6 -alkylene-O—, halogen, —CN, —NO 2 , —OH, C 1-10 -alkoxy, —O—CH 2 CH 2 O—C 1-10 -alkyl, —O—COR 14 , —S—C 1-10 -alkyl, —NH 2 , —NHR 14 , —NR 14 R 15 , —NH—COR 14 , —COOH, —COOR 14 , —CONH 2 , —CONHR 14 , —CONR 14 R 15 , —CO—H, —COR 14 , C 3-10 -cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C 6-14 -aryl and monovalent 5 to 14 membered aromatic heterocyclic residue.

10. The polymer of any one of claims 1 to 4 , wherein:

L is bivalent 5 to 14 membered aromatic heterocyclic residue, such that L is substituted with 1 to 2 substituents R b ; and

R b at each occurrence are independently from each other C 6-20 -alkyl.

11. The polymer of any one of claims 1 to 4 , wherein:

q and s are independently from each other 1, 2 or 3;

r is 1 or 2; and

n is an integer from 5 to 10,000.

12. The polymer of claim 11 , wherein:

q and s are both 1;

r is 1; and

n is an integer from 5 to 10,000.

13. The polymer of claim 1 , wherein the unit of formula (1) is a unit of formula:

14. The polymer of claim 13 , wherein L is:

15. The polymer of any one of claims 1 to 4 or 13 to 14 , wherein n is an integer from 5 to 5,000.

16. An electronic device, comprising the polymer of any one of claims 1 to 4 or 13 to 14 .

17. The electronic device of claim 16 , which is an organic field effect transistor (OFET).

18. The electronic device of claim 16 , which is an organic photovoltaic device (OPV).

19. A semiconducting material, comprising the polymer of any one of claims 1 to 4 or 13 to 14 .

Assignments (2)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 22, 2020

From: BASF SE

To: CLAP CO., LTD.

Reel/Frame 052459/0201 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2012

From: MISHRA, ASHOK KUMAR; VAIDYANATHAN, SUBRAMANIAN; NOGUCHI, HIROYOSHI; DOETZ, FLORIAN; GUAN, YUCUI

To: BASF SE

Reel/Frame 028500/0031 →

Continuity (2)

Provisional Application 61479872 · Apr 28, 2011

Related Publication 20120277404A1 · Nov 1, 2012