Granted Patent B2

US 9,219,233 · App. 12/865,031 · Granted Dec 22, 2015

Abstract

Claims (109)

1. A polymer represented by formula:

wherein:

M 1 is an optionally substituted aromatic imide 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 1-40 haloalkyl group, and 1-4 cyclic moieties,

wherein:

each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group can be optionally substituted with 1-10 substituents independently selected from a halogen, —CN, NO 2 , OH, —NH 2 , —NH(C 1-20 alkyl), —N(C 1-20 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)—C 1-20 alkyl, —C(O)OH, —C(O)—OC 1-20 alkyl, —C(O)NH 2 , —C(O)NH—C 1-20 alkyl, —C(O)N(C 1-20 alkyl) 2 , —OC 1-20 alkyl, —SiH 3 , —SiH(C 1-20 alkyl) 2 , —SiH 2 (C 1-20 alkyl), and —Si(C 1-20 alkyl) 3 ;

each of the C 1-40 alkyl group, the C 2-40 alkenyl group, and the C 1-40 haloalkyl group can be covalently bonded to the imide nitrogen atom via an optional linker, and

each of the 1-4 cyclic moieties can be the same or different, can be covalently bonded to each other or the imide nitrogen via an optional linker, and can be optionally substituted with 1-5 substituents independently selected from a halogen, oxo, —CN, NO 2 , OH, ═C(CN) 2 , —NH 2 , —NH(C 1-20 alkyl), —N(C 1-20 alkyl) 2 , —S(O) 2 OH, —CHO, —C(O)OH, —C(O)—C 1-20 alkyl, —C(O)—OC 1-20 alkyl, —C(O)NH 2 , —C(O)NH—C 1-20 alkyl, —C(O)N(C 1-20 alkyl) 2 , —SiH 3 , —SiH(C 1-20 alkyl) 2 ,

—SiH 2 C 1-20 alkyl), —Si(C 1-20 alkyl) 3 , —O—C 1-20 alkyl, —O—C 1-20 alkenyl, —O—C 1-20 haloalkyl, a C 1-20 alkyl group, a C 1-20 alkenyl group, and a C 1-20 haloalkyl group; and

π-1 and π-1′ are an optionally substituted fused ring moiety selected from:

wherein a° is 0 or 1;

M 2 is a repeating unit comprising one or more optionally substituted polycyclic moieties and has a formula selected from:

wherein:

π-2, at each occurrence, is independently an optionally substituted polycyclic moiety; and

Z, at each occurrence, is independently a linear conjugated linker; and

n is an integer between 2 and 5,000,

wherein π-2 has a reduction potential greater than or equal to −2.2 V;

provided that the polymer does not have a repeating unit of the formula:

2. The polymer of claim 1 , wherein M 1 is an optionally substituted aromatic imide selected from:

and R 1 is as defined in claim 1 .

3. The polymer of claim 1 , wherein each of π-1, π-1′, and π-2 independently is optionally substituted with 1-6 R a groups; wherein:

R a , at each occurrence, is a) halogen, b) —CN, c) − NO 2 , d) oxo, e) —OH, f) ═C(R b ) 2 , g) a C 1-40 alkyl group, h) a C 2-40 alkenyl group, i) a C 2-40 alkynyl group, j) a C 1-40 alkoxy group, k) a C 1-40 alkylthio group, l) a C 1-40 haloalkyl group, m) a —Y—C 3-10 cycloalkyl group, n) a —Y—C 6-14 aryl group, o) a —Y—C 6-14 haloaryl group, p) a —Y-3-12 membered cycloheteroalkyl group, or q) 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 b groups;

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

Y, at each occurrence, is a divalent C 1-20 alkyl group, a divalent C 1-20 haloalkyl group, or a covalent bond; and

m, at each occurrence, is 0, 1, or 2.

4. The polymer of claim 1 , 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 1-40 haloalkyl group, -L-Ar 1 , -L-Ar 1 —Ar 1 , -L-Ar 1 —R 2 , -L-Ar 1 —Ar 1 —R 2 , -L-Cy 1 , -L-Cy 1 -Cy 1 , -L-Cy 1 -R 2 , and -L-Cy 1 -Cy 1 -R 2 ;

wherein:

L, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —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;

wherein:

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

Ar 1 , at each occurrence, is independently a monovalent or divalent 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; and

Cy 1 , at each occurrence, is independently a monovalent or divalent 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 2 , at each occurrence, is independently selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, -L′-Ar 2 , -L′-Ar 2 —Ar 2 , -L′-Ar′—R 3 , -L′-Ar 2 —Ar 2 —R 3 , -L′-Cy 2 , -L′-Cy 2 -Cy 2 , -L′-Cy 2 -R 3 , -L′-Cy 2 -Cy 2 -R 3 ;

wherein:

L′, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]-Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —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 monovalent or divalent C 6-14 aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from halogen, oxo, —CN, ═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 monovalent or divalent C 3-14 cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, oxo, —CN, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;

R 3 , at each occurrence, is a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 1-40 haloalkyl group, or a C 1-40 alkoxy group;

Y, at each occurrence, is a divalent C 1-20 alkyl group, a divalent C 1-20 haloalkyl group, or a covalent bond; and

m, at each occurrence, is 0, 1, or 2.

5. The polymer of claim 1 , represented by formula:

wherein n is an integer between 5 and 1,000; x is a real number and 0<x≦1; and π-2 and R 1 are as defined in claim 1 .

6. The polymer of claim 1 , wherein R 1 is a linear or branched C 3-40 alkyl group selected from an n-hexyl group, a 1-methylpropyl group, a 1-methylbutyl group, a 1-methylpentyl group, a 1-methylhexyl group, a 1-ethylpropyl group, a 1-ethylbutyl group, a 1-3,dimethylbutyl group, and a 2-octyldodecyl group.

7. The polymer of claim 1 , wherein R 1 is selected from:

8. The polymer of claim 3 , wherein π-2 is selected from:

wherein:

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

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

r and s independently are —CR d R d — or —C(C(CN) 2 )—;

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

R d , at each occurrence, independently is H or R a ; and

R a is as defined in claim 3 .

9. The polymer of claim 3 , wherein π-2 is selected from:

wherein R d , at each occurrence, independently is H or R a ; and R a is as defined in claim 3 .

10. The polymer of claim 1 , wherein π-2 is a polycyclic moiety comprising a Spiro atom or substituted with 1-4 groups selected from an oxo group and a dicyanovinylidenyl group.

11. The polymer of claim 1 , wherein the polymer is

or wherein R 1 and n are as defined in claim 1 .

12. The polymer of claim 1 , wherein the polymer is

wherein R 1 and n are as defined in claim 1 .

13. The polymer of claim 1 , wherein the polymer is selected from:

wherein R 1 and n are as defined in claim 1 .

14. The polymer of claim 1 , wherein the polymer is selected from:

wherein R 1 and n are as defined in claim 1 .

15. A polymer represented by formula I or formula I′:

wherein:

π-1 and π-1′ independently are a cyclic moiety optionally substituted with 1-4 R a groups;

π-2 is a 7-conjugated moiety having a reduction potential greater than about −2.6 V and optionally substituted with 1-6 R a groups;

wherein:

R a , at each occurrence, is a) halogen, b) —CN, c) —NO 2 , d) oxo, e) —OH, f) ═C(R b ) 2 , g) a C 1-40 alkyl group, h) a C 2-40 alkenyl group, i) a C 2-40 alkynyl group, j) a C 1-40 alkoxy group, k) a C 1-40 alkylthio group, l) a C 1-40 haloalkyl group, m) a —Y—C 3-10 cycloalkyl group, n) a —Y—C 6-14 aryl group, o) a —Y—C 6-14 haloaryl group, p) a —Y-3-12 membered cycloheteroalkyl group, or q) 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 b groups;

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

Y, at each occurrence, is a divalent C 1-20 alkyl group, a divalent C 1-20 haloalkyl group, or a covalent bond; and

m, at each occurrence, is 0, 1, or 2;

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

wherein:

L, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]—Y—, —Y—C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —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;

wherein:

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

Ar 1 , at each occurrence, is independently a monovalent or divalent 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; and

Cy 1 , at each occurrence, is independently a monovalent or divalent 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 2 , at each occurrence, is independently selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, -L′-Ar 2 , -L′-Ar c —Ar 2 , -L′-Ar 2 —R 3 , -L′-Ar 2 —Ar 2 —R 3 , -L′-Cy 2 , -L′-Cy 2 -Cy 2 , -L′-Cy 2 -R 3 , -L′-Cy 2 -Cy 2 -R 3 ;

wherein:

L′, at each occurrence, is independently selected from —Y—O—Y—, —Y—[S(O) m ]—Y—, —Y—[C(O)—Y—, —Y—[NR c C(O)]—Y—, —Y—[C(O)NR c ]—, —Y—NR c —, —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 c , at each occurrence, is independently a monovalent or divalent C 6-14 aryl group or a 5-14 membered heteroaryl group, each optionally substituted with 1-5 substituents independently selected from halogen, oxo, —CN, ═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 monovalent or divalent C 3-14 cycloalkyl group or a 3-14 membered cycloheteroalkyl group, each optionally substituted with 1-5 substituents independently selected from a halogen, oxo, —CN, ═C(CN) 2 , a C 1-6 alkyl group, a C 1-6 alkoxy group, and a C 1-6 haloalkyl group;

R 3 , at each occurrence, is a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 1-40 haloalkyl group, or a C 1-40 alkoxy group; and

n is an integer in the range from 2 to 5,000.

16. The polymer of claim 15 , wherein 7-2 has a reduction potential greater than or equal to about −1.2 V.

17. The polymer of claim 15 , wherein π-2 is a polycyclic moiety optionally substituted with 1-6 R a groups.

18. A composition comprising the polymer of claim 1 dissolved or dispersed in a liquid medium.

19. The composition of claim 18 , wherein the liquid medium comprises water or an organic solvent.

20. The composition of claim 18 , the composition further comprising at least one additive.

21. The composition of claim 20 , wherein the additive is independently selected from the group consisting of a detergent, a dispersant, a binding agent, a compatiblizing agent, a curing agent, an initiator, a humectant, an antifoaming agent, a wetting agent, a pH modifier, a biocide, and a bactereriostat.

22. An article of manufacture comprising the polymer of claim 1 .

23. The article of manufacture of claim 22 , wherein the article of manufacture is an electronic device, an optical device, or an optoelectronic device.

24. A thin film semiconductor comprising the polymer of claim 1 .

25. A composite comprising a substrate and the thin film semiconductor of claim 24 deposited on the substrate.

26. A field effect transistor device comprising the thin film semiconductor of claim 24 .

27. A field effect transistor device comprising the composite of claim 25 .

28. The field effect transistor device of claim 26 , wherein the field effect transistor has a structure selected from top-gate bottom-contact structure, bottom-gate top-contact structure, top-gate top-contact structure, and bottom-gate bottom-contact structure.

29. The field effect transistor device of claim 26 comprising a dielectric material, wherein the dielectric material comprises an organic dielectric material, an inorganic dielectric material, or a hybrid organic/inorganic dielectric material.

30. A photovoltaic device comprising the thin film semiconductor of claim 24 .

31. A photovoltaic device comprising the composite of claim 25 .

32. The photovoltaic device of claim 30 comprising a p-type semiconducting material adjacent to the polymer.

33. An organic light emitting device comprising the thin film semiconductor of claim 24 .

34. An organic light emitting device comprising the composite of claim 25 .

35. A method of making an article of manufacture comprising depositing a composition of claim 26 onto a substrate.

36. The method of claim 35 , wherein depositing the composition comprises at least one of printing, spin coating, drop-casting, zone casting, dip coating, blade coating, and spraying.

37. The method of claim 36 , wherein printing is selected from gravure printing, inkjet printing, flexographic printing, screen printing, pad printing, offset printing, and lithographic printing.

Assignments (10)