Granted Patent B2

US 8,664,339 · App. 13/128,214 · Granted Mar 4, 2014

Abstract

Claims (66)

1. A homopolymer or copolymer comprising a repeating unit M 1 selected from:

wherein:

R 1 , at each occurrence, is independently selected from H, a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, a C 1-40 haloalkyl group, -L-R a , -L-Ar 1 , -L-Ar 1 —Ar 1 , -L-Ar 1 —R a ,-L-Ar 1 —Ar 1 —R a , -L-Cy 1 , -L-Cy 1 -Cy 1 , -L-Cy 1 -R a , and -L-Cy 1 -Cy 1 -R a ;

wherein:

L, at each occurrence, is independently selected from —O—, —Y—O—Y—, —S—, —S(O)—, —Y—S—Y—, —C(O)—, —NR c C(O)—, —C(O)NR c —, —NR c —, —SiR c 2 —,

—Y—[SiR c 2 ]—Y—, a divalent C 1-20 alkyl group, a divalent C 1-20 alkenyl group, a divalent C 1-20 haloalkyl group, and a covalent bond;

Ar 1 , at each occurrence, is independently a C 6-14 aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;

Cy 1 , at each occurrence, is independently a C 3-14 cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group; and

R a , at each occurrence, is independently selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, -L′-R b , -L′-Ar 2 , -L′-Ar 2 —Ar 2 , -L′-AR 2 —R b , -L′-Ar 2 —Ar 2 —R b , -L′-Cy 2 , -L′-Cy 2 -Cy 2 , -L′-Cy 2 -R b , -L′-Cy 2 -Cy 2 -R b ;

wherein:

L′, at each occurrence, is independently selected from —O—, —Y—O—Y—, —S—, —S(O)—, —Y—S—Y—, —C(O)—, —NR c C(O)—, —C(O)NR c —, —NR c —, —SiR c 2 —, —Y—[SiR c 2 ]—Y—, a divalent C 1-20 alkyl group, a divalent C 1-20 alkenyl group, a divalent C 1-20 haloalkyl group, and a covalent bond;

Ar 2 , at each occurrence, is independently a C 6-14 aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from halogen, —CN, oxo, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;

Cy 2 , at each occurrence, is independently a C 3-14 cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, —CN, oxo, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;

R b , at each occurrence, is independently selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, a C 1-40 haloalkyl group, and a C 1-40 group;

R c , at each occurrence, is independently selected from H, a C 1-6 alkyl group, and a —Y—C 6-14 aryl group; and

Y, at each occurrence, is independently selected from a divalent C 1-6 alkyl group, a divalent C 1-6 haloalkyl group, and a covalent bond;

R d , at each occurrence, is a) halogen, b) —CN, c) —NO 2 , d) oxo, e) ═C(R e ) 2 , f) a C 1-40 alkyl group, g) a C 2-40 alkenyl group, h) a C 2-40 alkynyl group, i) a C 1-40 haloalkyl group, j) a —Y—C 3-10 cycloalkyl group, k) a —Y—C 6-14 aryl group, l) a —Y—C 6-14 haloaryl group, m) a —Y-3-12 membered cycloheteroalkyl group, or n) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-40 alkyl group, the C 2-40 alkenyl group, the C 2-40 alkynyl group, the C 3-10 cycloalkyl group, the C 6-14 aryl group, the C 6-14 haloaryl group, the 3-12 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group is optionally substituted with 1-4 R e groups;

wherein:

R e , at each occurrence, is selected from a) halogen, b) —CN, c) —NO 2 , d) oxo, e) —OH, f) —O—C 1-20 alkyl, g) —O—C 6-14 aryl, h) —NH 2 , i) —NH(C 1-20 alkyl), j) —N(C 1-20 alkyl) 2 , k) —N(C 1-20 alkyl)—C 6-14 aryl, l) —N(C 6-14 aryl) 2 , m) —S(O) m H, n) —S(O) m —C 1-20 alkyl, o) —S(O) 2 OH, p) —S(O) m —OC 1-20 alkyl, q) —S(O) m —OC 6-14 aryl, r) —CHO, s) —C(O)—C 1-20 alkyl, t) —C(O)—C 6-14 aryl, u) —C(O)OH, v) —C(O)—OC 1-20 alkyl, w) —C(O)—OC 6-14 aryl, x) —C(O)NH 2 , y) —C(O)NH—C 1-20 alkyl, z) —C(O)N(C 1-20 alkyl) 2 , aa) —C(O)NH—C 6-14 aryl, ab) —C(O)N(C 1-20 alkyl)—C 6-14 aryl, ac) —C(O)N(C 6-14 aryl) 2 , ad) —C(S)NH 2 , ae) —C(S)NH—C 1-20 alkyl, af) —C(S)N(C 1-20 alkyl) 2 , ag) —C(S)N(C 6-14 aryl) 2 , ah) —C(S)N(C 1-20 alkyl)—C 6-14 aryl, ai) —C(S)NH—C 6-14 aryl, aj) —S(O) m NH 2 , ak) —S(O) m NH(C 1-20 alkyl), al) —S(O) m N(C 1-20 alkyl) 2 , am) —S(O) m NH(C 6-14 aryl), an) —S(O) m N(C 1-20 alkyl)—C 6-14 aryl, ao) —S(O) m N(C 6-14 aryl) 2 , ap) —SiH 3 , aq) —SiH(C 1-20 alkyl) 2 , ar) —SiH 2 (C 1-20 alkyl), as) —Si(C 1-20 alkyl) 3 , at) a C 1-20 alkyl group, au) a C 2-20 alkenyl group, av) a C 2-20 alkynyl group, aw) a C 1-20 alkylthio group, ax) a C 1-20 haloalkyl group, ay) a C 3-10 cycloalkyl group, az) a C 6-14 aryl group, ba) a C 6-14 haloaryl group, bb) a 3-12 membered cycloheteroalkyl group, and bc) a 5-14 membered heteroaryl group; and

q is 0, 1, 2 or 3;

wherein the homopolymer or copolymer has a degree of polymerization (n) that is greater than 2.

2. A copolymer according to claim 1 having the formula:

wherein M 2 has a formula selected from:

wherein:

π-2 is an optionally substituted fused ring moiety;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated linear linker; and

m, m′ and m″ independently are 0, 1, 2, 3, 4, 5 or 6; and

M 1 and n are as defined in claim 1 .

3. The homopolymer or copolymer of claim 1 , wherein M 1 is

wherein R 1 is as defined in claim 1 .

4. The hompolymer or copolymer of claim 1 , wherein M 1 is selected from:

wherein:

R 1 , R d , and q are as defined in claim 1 .

5. A copolymer according to claim 2 , wherein Z is selected from:

6. A copolymer according to claim 2 , wherein π-2 is an optionally substituted C 8-22 aryl group or 8-22 membered heteroaryl group selected from:

wherein:

k, k′, l and l′ independently can be selected from —CR 2 ═, ═CR 2 —, —C(O)—, and —C(C(CN) 2 )—;

p, p′, q and q′ independently can be selected from —CR 2 ═, ═CR 2 —, —C(O)—, —C(C(CN) 2 )—, —O—, —S—, —N═, ═N—, —N(R 2 )—, —SiR 2 ═, ═SiR 2 —, and —SiR 2 R 2 —;

r and s independently can be —CR 2 R 2 — or —C(C(CN) 2 )—;

u, u′, v and v′ independently can be selected from —CR 2 ═, ═CR 2 —, —C(O)—, —C(C(CN) 2 )—, —S—, —S(O)—, —S(O) 2 —, —O—, —N═, ═N—, —SiR 2 ═, ═SiR 2 —, —SiR 2 R 2 —, —CR 2 R 2 —CR 2 R 2 —, and —CR 2 ═CR 2 —; and

R 2 , at each occurrence, independently can be H or R e , wherein R e is as defined in claim 1 .

7. A copolymer according to claim 2 , wherein Ar, at each occurrence, is independently selected from:

wherein:

a, b, c and d independently are selected from —S—, —O—, —CH═, ═CH—, —CR 3 ═, ═CR 3 —, —C(O)—, —C(C(CN) 2 )—, —N═, ═N—, —NH— and —NR 3 —;

R 3 , at each occurrence, is independently selected from a) halogen, b) —CN, c) —NO 2 , d) —N(R c ) 2 , e) —OR c , f) —C(O)R c , g) —C(O)OR c , h) —C(O)N(R c ) 2 , i) a C 1-40 alkyl group, j) a C 2-40 alkenyl group, k) a C 2-40 alkynyl group, l) a C 1-40 alkoxy group, m) a C 1-40 alkylthio group, n) a C 1-40 haloalkyl group, o) a —Y—C 3-14 cycloalkyl group, p) a —Y—C 6-14 aryl group, q) a —Y-3-14 membered cycloheteroalkyl group, and

r) a —Y-5-14 membered heteroaryl group, wherein each of the C 1-40 alkyl group, the C 2-40 alkenyl group, the C 2-40 alkynyl group, the C 3-14 cycloalkyl group, the C 6-14 aryl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group optionally is substituted with 1-5 R e groups;

wherein R c , R e and Y are as defined in claim 1 .

8. A copolymer according to claim 1 , wherein (Ar) m , (Ar) m′ , and (Ar) m″ are selected from:

wherein R 4 , at each occurrence, independently is H or R 3 , and R 3 is as defined in claim 7 .

9. A copolymer according to claim 2 , wherein π-2 is selected from:

wherein R 2 is selected from a C 1-20 alkyl group, a C 1-20 alkoxy group, and a C 1-20 haloalkyl group.

10. A copolymer according to claim 2 , wherein M 2 is selected from:

wherein R 3 and R 4 are as defined in claim 8 .

11. A copolymer according to claim 2 , wherein M 2 is selected from:

wherein R 2 is selected from a C 1-20 alkyl group, a C 1-20 alkoxy group, and a C 1-20 haloalkyl group.

12. A copolymer according to claim 2 , wherein M 2 is selected from:

wherein R 2 is selected from a C 1-20 alkyl group, a C 1-20 alkoxy group, and a C 1-20 haloalkyl group; R c is a C 1-6 alkyl group; and R 3 and R 4 are as defined in claim 8 .

13. A homopolymer or copolymer according to claim 1 , wherein R 1 , at each occurrence, is independently selected from:

14. A homopolymer or copolymer according to claim 1 , wherein R 1 is independently selected from a branched C 3-40 alkyl group or a branched C 3-40 alkenyl group.

15. A homopolymer or copolymer according to claim 1 , wherein R 1 is independently selected from an n-hexyl group, a 1-methylhexyl group, a 2-ethylhexyl group, and a 2-octyldodecyl group.

16. A homopolymer or copolymer according to claim 1 , wherein R 1 is a -L-C 3-14 cycloalkyl group optionally substituted with 1-4 C 1-6 alkyl groups, wherein L is as defined in claim 1 .

17. A homopolymer or copolymer according to claim 1 , wherein n is an integer between 4 and 1,000.

18. An article of manufacture comprising a thin film semiconductor comprising one or more homopolymers or copolymers of claim 1 .

19. The article of manufacture of claim 18 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device.

20. The article of manufacture of claim 18 , wherein the article of manufacture is selected from an organic field effect transistor device, an organic photovoltaic device, and an organic light emitting device.

Assignments (8)