Electrically conductive polymers with enhanced conductivity
View Patent ↗An electrically conductive polymer linked to conductive nanoparticle is provided. The conductive polymer can include conductive monomers and one or more monomers in the conductive polymer can be linked to a conductive nanoparticle and can include a polymerizable moiety so that it can be incorporated into a polymer chain. The electrically conductive monomer can include a 3,4-ethylenedioxythiophene as a conductive monomer. The electrically conductive polymer having the conductive nanoparticle can be prepared into an electrically conductive layer or film for use in electronic devices.
1. A polymer and nanoparticle combination comprising:
a conductive copolymer having one or more first conductive monomers and one or more second conductive monomers, wherein the one or more first conductive monomers and the one or more second conductive monomers are copolymerized to form the conductive copolymer; a conductive nanoparticle covalently bound to a first end of a linker and a second end of the linker being covalently bound to the conductive copolymer, the linker including at least one member selected from the group consisting of an alkylthio, an alkenylthio, and an alkynylthio;
wherein the one or more first conductive monomers have a structure Formula 4 or an analog or derivative thereof:
where:
X 2 is S; and
R 3 and R 3 ′ are substituents and represent 3,4-propylenedioxythiophene; and
wherein the one or more second conductive monomers have a structure of Formula 1:
where:
A is thienylene vinylene, which is unsubstituted or substituted with one or more substituents,
wherein the substituents are independently selected from the group of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl, alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl, haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl, cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy, cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl, heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl, heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl, heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy, heteroaryloxy, aryloxycarbonyl, heteroaryloxycarbonyl, arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl, arylthio, arylsulfonyl and arylsulfinyl, or the substituents together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring having 0 or more divalent nitrogen, sulfur or oxygen atoms; and the substituents being substituted or unsubstituted.
2. The polymer and nanoparticle combination of claim 1 , wherein the conductive nanoparticle is linked to one or more of the first conductive monomers, and/or one or more of the second conductive monomers.
3. The polymer and nanoparticle combination of claim 1 , wherein the polymer has a degree of polymerization in a range from 100 to 1,000.
4. The polymer and nanoparticle combination as in claim 1 , wherein the conductive nanoparticle has one or more solvent compatible groups.
5. The polymer and nanoparticle combination as in claim 4 , wherein the solvent compatible groups are hydrophilic moieties.
6. The polymer and nanoparticle combination of claim 1 , wherein the linker is unsubstituted or substituted.
7. The polymer and nanoparticle combination of claim 1 , wherein the conductive polymer includes one or more cationic or anionic monomers.
8. The polymer and nanoparticle combination of claim 1 , comprising one or more styrene sulfonate monomers.
9. A polymer and nanoparticle combination comprising:
the polymer having one or more first conductive monomers and one or more second conductive monomers that are copolymerized to form the copolymer;
wherein the one or more first conductive monomers have a structure of Formula 4 or an analog or derivative thereof:
where:
X 2 is S; and
R 3 and R 3 ′ are substituents and represent 3,4-propylenedioxythiophene; and
a conductive nanoparticle linked to the one or more conductive monomers through the R 3 , or R 3 ′ substituent, the one or more conductive monomers covalently bound to a first end of a linker and a second end of the linker being covalently bound to the conductive nanoparticle, the linker including at least one member selected from the group consisting of an alkylthio, an alkenylthio, and an alkynylthio;
the one or more second conductive monomers have a structure of Formula 1:
where:
A is thienylene vinylene, which is unsubstituted or substituted with one or more substituents,
wherein the substituents are independently selected from the group of hydroxyl, alkyl, alkenyl, alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl, alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl, haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl, cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy, cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl, heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl, heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl, heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy, heteroaryloxy, aryloxycarbonyl, heteroaryloxycarbonyl, arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl, arylthio, arylsulfonyl and arylsulfinyl, or the substituents together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring having 0 or more divalent nitrogen, sulfur or oxygen atoms; and the substituents being substituted or unsubstituted.
10. The polymer and nanoparticle combination of claim 9 , wherein the polymer has a degree of polymerization in a range from 100 to 1,000.
11. An electronic device comprising the polymer and nanoparticle combination of claim 9 .
12. The polymer and nanoparticle combination of claim 9 , wherein the linker is unsubstituted or substituted.
13. The polymer and nanoparticle combination of claim 9 , wherein the polymer includes one or more cationic or anionic monomers.
14. The polymer and nanoparticle combination of claim 9 , wherein the polymer includes one or more styrene sulfonate monomers.
15. A composition comprising the polymer and nanoparticle combination of claim 1 and a polymeric acid doped into the polymer.
16. An electronic device comprising the polymer and nanoparticle combination of claim 1 .
17. A polymer and nanoparticle combination comprising:
a conductive copolymer having one or more first conductive monomers and one or more second monomers, wherein the one or more first conductive monomers and the one or more second monomers are copolymerized to form the conductive copolymer; a conductive nanoparticle covalently bound to a first end of a linker and a second end of the linker being covalently bound to the conductive copolymer, so that the nanoparticle is indirectly linked to the conductive polymer through the linker, the linker including at least one member selected from the group consisting of an alkylthio, an alkenylthio, and an alkynylthio;
wherein the conductive nanoparticle is selected from the group consisting of gold, silver, copper, platinum, and palladium;
wherein the one or more first conductive monomers have a structure of Formula 4 or an analog or derivative thereof:
where:
X 2 is S; and
R 3 and R 3 ′ are substituents and represent 3,4-propylenedioxythiophene; and
wherein the one or more second monomers have a structure of Formula 1:
where:
A is thienylene vinylene, which is unsubstituted or substituted with one or more substituents,
wherein the substituents are independently selected from the group of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, alkanoyl, alkanoylamino, alkenoyl, alkynoyl, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, alkylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylsulfonyl, alkylsulfinyl, sulfonylaminoalkyl, alkylsulfonylaminocarbonyl, aminoalkyl, cyanoalkyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloalkanoyl, haloalkenoyl, haloalkynoyl, haloalkoxy, haloalkoxycarbonyl, hydroxyalkyl, oxoalkyl, cycloalkyl, cycloalkenyl, cycloalkanoyl, cycloalkenoyl, cycloalkoxy, cycloalkoxycarbonyl, aryl, arylene, heterocycle, heterocyclyl, heteroaryl, heteroarylene, arylalkyl, heteroarylalkyl, arylalkanoyl, heteroarylalkanoyl, arylalkenoyl, heteroarylalkenoyl, arylalkynoyl, heteroarylalkynoyl, arylalkoxy, heteroarylalkoxy, aryloxy, heteroaryloxy, aryloxycarbonyl, heteroaryloxycarbonyl, arylalkoxycarbonyl, heteroarylalkoxycarbonyl, alkylthio, alkylthioalkyl, arylthio, arylsulfonyl and arylsulfinyl, or the substituents together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring having 0 or more divalent nitrogen, sulfur or oxygen atoms; and the substituents being substituted or unsubstituted.
18. A composition comprising the polymer and nanoparticle combination of claim 17 , wherein the conductive nanoparticle is surrounded by hydrophilic moieties bonded thereto to increase solubility of the polymer and nanoparticle combination in water.