Alkylenedioxythiophenes and poly(alkylenedioxythiophenes) containing mesogenic groups
View Patent ↗The invention relates to new 3,4-alkylenedioxythiophenes which are substituted with mesogenic groups, if desired via a bridging group, and their polymeric derivatives (poly-(3,4-alkylenedioxythiophenes)).
1. A 3,4-Alkylenedioxythiophene of the formula (I),
wherein
A is a C 1 or C 3 -C 5 -alkylene radical which is substituted at any point by a linker L and optionally bears further substituents,
L is a methylene group,
p is an integer from 1 to 6,
M is an n-functional group of the formula (II-a), (II-b) or (II-c-1) to (II-c-6),
wherein
X 1 , X 2 and X 3 are substituted or unsubstituted structures selected independently from the group consisting of
and
Z 1 and Z 2 are structures selected independently from the group consisting of
wherein
R x and R y are each, independently of one another, H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, NO 2 , a carboxyl group or a hydroxy group,
h is an integer from 1 to 10,
w is an integer from 1 to 5,
x, y and z are each, independently of one another, 0 or 1, and
n an integer from 1 to 8, where when n is an integer below 8, the group is selected from the group consisting of formulas (II-c-1), (II-c-2), (II-c-3), (II-c-4), (II-c-5) and (II-c-6) and bears a terminal group F′ on the remaining 8-n linkage points denoted by * when n is 1, the group of the formula (II-a) or (II-b) and bears a terminal group F′ at the linkage points denoted by *,
wherein
F′ is H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, a nitro (NO 2 ) group, a carboxyl group, a sulphonic acid group or sulphonate group or a hydroxy group,
B′ is a bridging group of the formula (B)
wherein
q is 0 or 1,
r and s are identical or different and each are 0 or 1, with the proviso that when r is 1, s is 0 and vice versa or both are optionally 0,
t is 0 or 1,
Sp is a spacer selected from the group consisting of substituted and unsubstituted linear or cyclic C 1 -C 20 -alkylene groups, C 5 -C 20 -arylene groups, C 2 -C 20 -heteroarylene groups in which from one to three heteroatoms selected from the group consisting of N, O and S can additionally be present in the heteroaromatic ring or ring system, C 6 -C 20 -aralkylene groups, C 2 -C 200 -oligoether and polyether groups,
m is 0 or 1, and
Q is O, S or NH.
2. The 3,4-Alkylenedioxythiophene of claim 1 , wherein
M is an n-functional group selected from the group consisting of the formulae (II-c-1) to (II-c-6),
wherein
n is at most 4, 6 or 8,
and wherein when n is an integer below 4, 6 or 8, M is selected from the group consisting of the formulae (II-c-1) to (II-c-6) bearing a terminal group F′ on the remaining 4-n, 6-n or 8-n linkage points denoted by *,
wherein
F′ is H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, a nitro (NO 2 ) group, a carboxyl group, a sulphonic acid group or sulphonic group or a hydroxy group.
3. The 3,4-Alkylenedioxythiophene of claim 1 , having the structure of the formula (I-b),
4. A 3,4-Alkylenedioxythiophene of the formula (I),
wherein
A is a C 1 -C 5 -alkylene radical which is substituted at any point by a linker L and optionally bears further substituents,
L is a methylene group,
p is 0 or an integer from 1 to 6,
M is an n-functional steroid radical or a derivative of a steroid radical,
n island
B′ is a bridging group of the formula (B)
wherein
q is 0 or 1,
r and s are each independently 0 or 1, with the proviso that when r is 1, s is 0 and vice versa or both are optionally 0,
t is 0 or 1,
Sp is a spacer selected from the group consisting of substituted and unsubstituted linear or cyclic C 1 -C 20 -alkylene groups, C 5 -C 20 -arylene groups, C 2 -C 20 -heteroarylene groups in which from one to three heteroatoms selected from the group consisting of N, O and S can additionally be present in the heteroaromatic ring or ring system, C 6 -C 20 -aralkylene groups, C 2 -C 200 -oligoether and -polyether groups,
m is 0 or 1,
Q is O, S or NH.
5. The 3,4-Alkylenedioxythiophene as claimed in claim 4 , wherein
M is an n-functional cholesteryl radical or a derivative of the cholesteryl radical of the formula (III-a)-(III-e),
wherein R is H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 2 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, a nitro (NO 2 ) group, a carboxyl group, a sulphonic acid group or sulphonic group or a hydroxy group, and
R 1 , R 2 , R 3 and R 4 can, independently of one another, be as defined above for R.
6. A process for preparing a polythiophene comprising polymerizing the 3,4-alkylenedioxythiophene as claimed in claim 1 .
7. A process for preparing a polythiophene comprising mixing two or more of the 3,4-Alkylenedioxythiophene as claimed in claim 1 to form a mixture and polymerizing the mixture.
8. A process for preparing electrical or electronic components, light-emitting components, for antistatic coating, in optoelectronics or in solar energy technology comprising incorporating the 3,4-alkylenedioxythiophene according to claim 1 .
9. The process according to claim 7 , wherein the polymerized mixture forms a layer which further comprises heating the layer at a temperature form 80° C. to 300° C.
10. A process for preparing the polythiophene, comprising oxidatively polymerizing electro chemically the 3,4-alkylenedioxythiophene according to claim 1 .
11. A 3,4-Alkylenedioxythiophene of the formula (I),
wherein
A is a C 1 -C 5 -alkylene radical which is substituted at any point by a linker L and optionally bears further substituents,
M is an n-functional group of the formula (II-a), (II-b) or (II-c-1) to (II-c-6),
wherein
X 3 , X 2 and X 3 are substituted or unsubstituted structures selected independently from the group consisting of
and
Z 1 and Z 2 are structures selected independently from the group consisting of
wherein
R x and R y are each, independently of one another, H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, NO 2 , a carboxyl group or a hydroxy group,
h is an integer from 1 to 10,
w is an integer from 1 to 5,
x, y and z are each, independently of one another, 0 or 1, and
n an integer from 1 to 8, where when n is an integer below 8, the group is selected from the group consisting of formulas (II-c-1), (II-c-2), (II-c-3), (II-c-4), (II-c-5) and (II-c-6) and bears a terminal group F′ on the remaining 8-n linkage points denoted by * when n is 1, the group of the formula (II-a) or (II-b) and bears a terminal group F′ at the linkage points denoted by *,
wherein
F′ is substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, a nitro (NO 2 ) group, a carboxyl group, a sulphonic acid group or sulphonate group or a hydroxy group,
B′ is a bridging group of the formula (B)
wherein
q is 0 or 1,
r and s are identical or different and each are 0 or 1, with the proviso that when r is 1, s is 0 and vice versa or both are optionally 0,
t is 0 or 1,
Sp is a spacer selected from the group consisting of substituted and unsubstituted linear or cyclic C 1 -C 20 -alkylene groups, C 5 -C 20 -arylene groups, C 2 -C 20 -heteroarylene groups in which from one to three heteroatoms selected from the group consisting of N, O and S can additionally be present in the heteroaromatic ring or ring system, C 6 -C 20 -aralkylene groups, C 2 -C 200 -oligoether and polyether groups,
m is 0 or 1, and
Q is QS or NH.
12. A 3,4-Alkylenedioxythiophene of the formula (I),
wherein
A is a C 1 -C 5 -alkylene radical which is substituted at any point by a linker L and optionally bears further substituents,
M is an n-functional group of the formula (II-a), (II-b) or (II-c-1) to (II-c-6),
wherein
X 1 , X 2 and X 3 are substituted or unsubstituted structures selected independently from the group consisting of
and
Z 1 and Z 2 are structures selected independently from the group consisting of
wherein
R x and R y are each, independently of one another, H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 3 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, NO 2 , a carboxyl group or a hydroxy group,
h is an integer from 1 to 10,
w is an integer from 1 to 5,
x, y and z are each, independently of one another, 0 or 1, and
n an integer from 1 to 8, where when n is an integer below 8, the group is selected from the group consisting of formulas (II-c-1), (II-c-2), (II-c-3), (II-c-4), (II-c-5) and (II-c-6) and bears a terminal group F′ on the remaining 8-n linkage points denoted by * when n is 1, the group of the formula (II-a) or (II-b) and bears a terminal group F′ at the linkage points denoted by *,
wherein
F′ is H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, a nitro (NO 2 ) group, a carboxyl group, a sulphonic acid group or sulphonic group or a hydroxy groups
B′ is a bridging group of the formula (B)
wherein
q is 0 or 1,
r is 1,
s is 0,
t is 0 or 1,
Sp is a spacer selected from the group consisting of substituted and unsubstituted linear or cyclic C 1 -C 20 -alkylene groups, C 5 -C 20 -arylene groups, C 2 -C 20 -heteroarylene groups in which from one to three heteroatoms selected from the group consisting of N, O and S can additionally be present in the heteroaromatic ring or ring system, C 6 -C 20 -aralkylene groups, C 2 -C 200 -oligoether and polyether groups,
m is 0 or 1, and
Q is O, S or NH.
13. A polythiophene which comprise recurring units of the formula (IV),
wherein
A is a C 1 or C 3 -C 5 -alkylene radical which is substituted at any point by a linker L and optionally bears further substituents,
L is a methylene group,
p is an integer from 1 to 6,
M is an n-functional group of the formula (II-a), (II-b) or (II-c-1) to (II-c-6),
wherein
X 1 , X 2 and X 3 are substituted or unsubstituted structures selected independently from the group consisting of
and
Z 1 and Z 2 are structures selected independently from the group consisting of
wherein
R x and R y are each, independently of one another, H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, NO 2 , a carboxyl group or a hydroxy group,
h is an integer from 1 to 10,
w is an integer from 1 to 5,
x, y and z are each, independently of one another, 0 or 1, and
n an integer from 1 to 8, where when n is an integer below 8, the group is selected from the group consisting of formulas (II-c-1), (II-c-2), (II-c-3), (II-c-4), (II-c-5) and (II-c-6) and bears a terminal group F′ on the remaining 8-n linkage points denoted by * when n is 1, the group of the formula (II-a) or (II-b) and bears a terminal group F′ at the linkage points denoted by *,
wherein
F′ is H, substituted or unsubstituted C 1 -C 22 -alkyl, C 1 -C 22 -haloalkyl, C 1 -C 22 -alkenyl, C 1 -C 22 -alkoxy, C 1 -C 22 -thioalkyl, C 1 -C 22 -iminoalkyl, C 1 -C 22 -alkoxycarbonyl, C 1 -C 22 -alkoxycarbonyloxy, a radical of an aliphatic C 1 -C 22 -alkanecarboxylic acid or of acrylic acid, halogen, pseudohalogen, a nitro (NO 2 ) group, a carboxyl group, a sulphonic acid group or sulphonic group or a hydroxy group,
B′ is a bridging group of the formula (B)
wherein
q is 0 or 1,
r and s are identical or different and each are 0 or 1, with the proviso that when r is 1, s is 0 and vice versa or both are optionally 0,
t is 0 or 1,
Sp is a spacer selected from the group consisting of substituted and unsubstituted linear or cyclic C 1 -C 20 -alkylene groups, C 5 -C 20 -arylene groups, C 2 -C 20 -heteroarylene groups in which from one to three heteroatoms selected from the group consisting of N, O and S can additionally be present in the heteroaromatic ring or ring system, C 6 -C 20 -aralkylene groups, C 2 -C 200 -oligoether and polyether groups,
m is 0 or 1, and
Q is O, S or NH.
14. A process for preparing electrical or electronic components, light-emitting components, for antistatic coating, in optoelectronics or in solar energy technology comprising incorporating the polythiophene of claim 13 .
15. A process for preparing conductive layers comprising incorporating the polythiophene according to claim 13 .
16. The process according to claim 15 , which further comprises heating the layer at a temperature form 80° C. to 300° C.
17. The polythiophene of claim 13 , wherein they are cationically and electrically conductive and contain bound anions as counterions to balance the positive charge.
18. The polythiophene of claim 17 , wherein the counterions are polyanions of polymeric carboxylic acids or polymeric sulphonic acids.
19. The polythiophene according to claim 13 , wherein they are uncharged and semiconducting.