Electrically conducting dendrimers

• US 6,043,336 A
• Filed: 01/26/1998
• Issued: 03/28/2000
• Est. Priority Date: 07/25/1996
• Status: Expired due to Term

• Current Assignee: Sumitomo Chemical Company Limited, University of Minnesota
• Original Assignee: Dendritech Inc.
• Inventors: Miller, Larry L., Duan, Robert G., Tomalia, Donald A.
• Primary Examiner(s): HAMPTON HIGHTOWER, PATRICIA
• Application Number:
  US09/000,311
• Time in Patent Office: 792 Days
• Field of Search: 528/310, 528/363, 528/328, 528/331, 528/332, 528/422, 528/322
• US Class Current: 528/310
• CPC Class Codes: C08G 73/0688 with only one nitrogen atom in the ring, e.g. polyquinolines
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: Y10S 424/16 Dendrimers and dendritic polymers

Abstract

An electrically conductive polymer is comprised of the reaction product of a dendrimer and an electrophoric compound which exhibits π-stacking upon reduction. The reaction product which is a peripherally modified dendrimer is formed and reduced, either chemically or electrochemically, in a polar solvent. The reduced electrophoric moieties aggregate (form π-stacks) to form electrically conductive pathways. The reduced peripherally modified dendrimers of the invention can be cast into films and other solid forms to provide flexible electrical conductors and semiconductors. The conductive polymers of the invention exhibit electrical conductivities comparable to that of doped polyacetalene, but are oxygen and moisture stable.

Claims

1. A polymeric composition comprising the reaction product of a dendrimer and a compound which exhibits π

-stacking upon reduction.

2. The composition of claim 1, wherein said compound is a mono-anhydride mono-imide compound.

3. The composition of claim 1, wherein said dendrimer is a poly(amidoamine).

4. The composition of claim 1, wherein said reaction product includes terminal moieties, and wherein the terminal moieties are reduced to form anion radical groups which aggregate to form electrically conductive pathways.

5. The composition of claim 1, wherein said dendrimer and said electrophoric compound are reacted in a polar solvent.

6. A polymeric composition comprising the reaction product of a dendrimer and a compound represented by the formula:

##STR8## wherein R is as follows;

##STR9## wherein R'"'"' is an alkyl and said reaction product is a peripherally modified dendrimer represented by the formula ##STR10## wherein D represents a dendrimer and n represents the number of molecules of said compound bonded to the dendrimer.

7. The composition of claim 6, wherein at least a portion of said molecules of said compound bonded to the dendrimer are reduced to form anionic radical groups which aggregate to form electrically conductive pathways.

8. The composition of claim 7, wherein said dendrimer and said compound are reacted in a polar solvent.

9. The composition of claim 8, wherein said dendrimer is a poly(amidoamine).

10. The composition of claim 6, wherein at least a portion of said molecules of said compound are reduced in polar solvent utilizing a chemical reducing agent.

11. An electrically conductive polymer comprising the chemically or electrochemically reduced product of a dendrimer and a compound which exhibits π

-stacking upon reduction.

12. The electrically conductive polymer of claim 11, wherein said compound is a mono-anhydride mono-imide compound.

13. The electrically conductive polymer of 12, wherein said dendrimer is a poly(amidoamine).

14. An electrically conductive polymer comprising the chemically or electrochemically reduced product of a dendrimer and a compound represented by the formula ##STR11## wherein R is as follows:

##STR12## wherein R'"'"' is an alkyl and said reaction product is a peripherally modified dendrimer represented by the formula ##STR13## wherein D represents a dendrimer and n represents the number of molecules of said compound bonded to said dendrimer.

15. The electrically conductive polymer of claim 14, wherein said dendrimer and said compound are reacted in a polar solvent.

16. The electrically conductive polymer of claim 15, wherein said dendrimer is a poly(amidoamine).

17. An electrically conductive polymer comprising the chemically or electrochemically reduced product of a dendrimer having reactive terminal groups and a compound which exhibits π

-stacking upon reduction.

18. The electrically conductive solid polymer of claim 17, wherein said product is formed and at least partially reduced in a polar solvent, and said solid polymer is formed by evaporation of a polar solvent containing said reduced product.

19. The electrically conductive solid polymer of claim 18, wherein said compound is a mono-anhydride mono-imide compound and said dendrimer is a poly(amidoamine).

21. The electrically conductive solid polymer of claim 17, wherein at least 50% of the reactive terminal groups on the dendrimer are reacted with said compound.

22. The electrically conductive solid polymer of claim 17, wherein at least 70% of the reactive terminal groups of the dendimer are reacted with said compound.

23. The electrically conductive solid polymer of claim 21, wherein less than all reducible terminal moieties are reduced.

24. The electrically conductive solid polymer of claim 23, wherein about 50% of the terminal moieties are reduced.

25. The electrically conductive solid polymer of claim 24, which is formed by solvent casting a temperature below about 100°

C.

26. The electrically conductive solid polymer of claim 24, which is formed by solvent casting a temperature below about 60°

C.

20. An electrically conductive solid polymer comprising the chemically or electrochemically reduced product of a dendrimer having reactive terminal groups and a compound represented by the formula:

##STR14## wherein R is as follows;

##STR15## wherein R'"'"' is an alkyl and said reaction product having reducible terminal moieties and being represented by the formula;

##STR16## wherein D represents a dendrimer and n represents the number of molecules of said compound bonded to said dendrimer.

27. An electrically conductive material comprising a polymeric film which is the reaction product of a dendrimer and a compound which exhibits π

-stacking upon reduction.

28. The material of claim 27, wherein the electrical conductivity of the film increases with increasing humidity.

29. The material of claim 27, wherein the film exhibits reversible humidity dependant electrical conductivity.

30. The material of claim 27, wherein said compound is a mono-anhydride mono-imide compound.

31. The material of claim 30, wherein said dendrimer is a poly(amidoamine).

32. An electrically conductive material comprising a polymeric film which is the reaction product of a dendrimer and a compound represented by the formula:

##STR17## wherein R is as follows;

##STR18## wherein R'"'"' is an alkyl and said reaction product is a peripherally modified dendrimer represented by the formula ##STR19## wherein D represents a dendrimer and n represents the number of molecules of said compound bonded to said dendrimer.

33. A method of forming an electrically conductive solid material, comprising:

reacting a dendrimer with a compound which exhibits π

-stacking upon reduction to form a reaction product having reducible terminal moieties;

reducing at least a portion of said reducible terminal moieties of the reaction product to form anion radical groups; and

solvent casting the reaction product to form an electrically conductive solid.

34. The method of claim 33, wherein the step of reacting the dendrimer with a compound which exhibits π

-stacking upon reduction is conducted in a solvent.

35. The method of claim 34, wherein the solvent is a polar solvent.

36. The method of claim 33, wherein said compound is a mono-anhydride mono-imide compound.

37. The method of claim 36, wherein said dendrimer is a poly(amidoamine).

38. A method of forming an electrically conductive solid material, comprising:

reacting a dendrimer with a compound represented by the formula;

##STR20## wherein R is as follows;

##STR21## wherein R'"'"' is an alkyl and said reaction product is a peripherally modified dendrimer represented by the formula ##STR22## wherein D represents a dendrimer and n represents the number of molecules of said compound bonded to said dendrimer.