Conductive polymer-based material

• US 7,204,940 B2
• Filed: 03/19/2003
• Issued: 04/17/2007
• Est. Priority Date: 03/20/2002
• Status: Expired due to Fees

• Current Assignee: The Michigan Biotechnology Institute
• Original Assignee: The Michigan Biotechnology Institute
• Inventors: Dulebohn, Joel I., McDonald, William F., Hanchar, Robert J., Koren, Amy B., Dourado, Sunil K.
• Primary Examiner(s): KOPEC, MARK T
• Application Number:
  US10/392,347
• Publication Number:
  US 20040051083A1
• Time in Patent Office: 1,490 Days
• Field of Search: 252/512, 252/513, 252/514, 528/420, 524/439, 524/440
• US Class Current: 252/512
• CPC Class Codes: C08G 69/02 Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
• CPC Class Codes: C08G 69/04 Preparatory processes
• CPC Class Codes: C08K 3/08 Metals
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 177/00 Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain based on polyhydrazides C09D179/06; based on polyamide-imides C09D179/08; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 177/06 Polyamides derived from polyamines and polycarboxylic acids C09D177/10 takes precedence
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01B 1/20 Conductive material dispersed in non-conductive organic material organic macromolecular compounds or compositions C08

Abstract

Disclosed are polymer-based coatings and materials comprising (i) a polymeric composition including a polymer having side chains along a backbone forming the polymer, at least two of the side chains being substituted with a heteroatom selected from oxygen, nitrogen, sulfur, and phosphorus and combinations thereof; and (ii) a plurality of metal species distributed within the polymer. At least a portion of the heteroatoms may form part of a chelation complex with some or all of the metal species. In many embodiments, the metal species are present in a sufficient concentration to provide a conductive material, e.g., as a conductive coating on a substrate. The conductive materials may be useful as the thin film conducting or semi-conducting layers in organic electronic devices such as organic electroluminescent devices and organic thin film transistors.

Claims

1. A conductive composition comprising:

(A) a crosslinked polymeric material formed by a process comprising reacting a polymer and a crosslinking agent, wherein the polymer has side chains along a backbone forming the polymer, at least two of the side chains being substituted with one or more heteroatoms selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus and combinations thereof, the polymer formed by reacting a mixture comprising

(i) one or more monomers selected from the group consisting of unsaturated dicarboxylic acids, esters of unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mixtures thereof; and

(ii) one or more amines selected from the group consisting of R—

NH₂, a polyalkylene polyamine, and mixtures thereof, wherein the R group contains between 1 and 50 carbon atoms and one or more of the selected amines includes at least two amino groups; and

(B) a plurality of copper species distributed within the crosslinked polymeric material,

wherein the conductive composition has a resistance of no more than about 100 ohms.

2. The conductive composition of claim 1, the one or more monomers selected from the group consisting of maleic anhydride, maleic acid esters, and mixtures thereof.

3. The conductive composition of claim 2, wherein the one or more monomers include maleic acid monoester, maleic acid diester, or mixtures thereof.

4. The conductive composition of claim 1, the one or more amines including R—

N₂, wherein the R group contains between 8 and 20 carbon atoms.

5. The conductive composition of claim 1, the one or more amines including polyalkylene polyamine.

6. The conductive composition of claim 5, wherein the polyalkylene polyamine comprises polyethyleneimine, pentaethylenehexamine, tetraethylenepentamine, or a mixture thereof.

7. The conductive composition of claim 1, the one or more amines including at least one R—

NH₂ and at least one polyalkylene polyamine.

8. The conductive composition of claim 1, wherein the crosslinking agent comprises at least two functional groups capable of reacting with an amino group.

9. The conductive composition of claim 8, wherein the one or more crosslinking agents are selected from the group consisting of aliphatic isocyanate compounds having 2 or more —

N═

C═

O groups;

aromatic isocyanate compounds having 2 or more —

N═

C═

O groups;

aliphatic aldehyde compounds having 2 or more —

CHO groups;

aromatic aldehyde compounds having 2 or more —

CHO groups;

phosphines having the general formula (A)₂P(B) wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl;

epoxy resins having end groups of the formula;

10. A conducting nanocomposite comprising the conductive composition of claim 1.

11. An OLED or LED device comprising a transparent conductive layer which comprises the conductive composition of claim 1.

12. An article comprising a conductive coating on a surface of a substrate wherein the conductive coating comprises the conductive composition of claim 1.

13. The article of claim 12, wherein the surface is an amino-functional modified surface.

14. The conductive composition of claim 1, wherein the conductive composition has a resistance of about 10–

100 ohms.

15. A conductive material comprising:

(A) a polymeric material comprising a polymer having side chains along a backbone forming the polymer, at least two of the side chains being substituted with one or more heteroatoms selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus and combinations thereof, wherein the polymer is synthesized by a process that includes reacting a mixture comprising;

(i) one or more monomers selected from the group consisting of unsaturated dicarboxylic acids, esters of unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mixtures thereof; and

(ii) one or more amines selected from the group consisting of R—

NH₂, polyalkylene polyamines, and mixtures thereof, wherein the R group contains between 1 and 50 carbon atoms and one or more of the selected amines includes at least two amino groups; and

(B) one or more copper species distributed within the polymeric material,

wherein the conductive material has a resistance of no more than about 100 ohms.

16. The conductive material of claim 15, the one or more monomers selected from the group consisting of maleic anhydride, maleic acid esters, and mixtures thereof.

17. The conductive material of claim 16, wherein the one or more monomers include maleic acid monoester, maleic acid diester, or mixtures thereof.

18. The conductive material of claim 15, the one or more amines including R—

NH₂, wherein the R group contains between 8 and 20 carbon atoms.

19. The conductive material of claim 15, the one or more amines including polyalkylene polyamine.

20. The conductive material of claim 19, wherein the polyalkylene polyamine comprises polyethyleneimine, pentaethylenehexamine, tetraethylenepentamine, or a mixture thereof.

21. The conductive material of claim 15, the one or more amines including at least one R—

NH₂ and at least one polyalkylene polyamine.

22. The conductive material of claim 15, wherein the polymer is crosslinked by a process that includes reacting the polymer with one or more crosslinking agents comprising at least two functional groups capable of reacting with an amino group.

23. The conductive material of claim 22, wherein the one or more crosslinking agents are selected from the group consisting of aliphatic isocyanate compounds having 2 or more —

N═

C═

O groups;

aromatic isocyanate compounds having 2 or more —

N═

C═

O groups;

aliphatic aldehyde compounds having 2 or more —

CHO groups;

aromatic aldehyde compounds having 2 or more —

CHO groups;

phosphines having the general formula (A)₂P(B) wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl;

epoxy resins having end groups of the formula;

24. A conducting nanocomposite comprising the conductive material of claim 15.

25. An OLED or LED device comprising a transparent conductive layer which comprises the conductive material of claim 15.

26. An article comprising a conductive coating on a surface of a substrate wherein the conductive coating comprises the conductive material of claim 15.

27. The article of claim 26, wherein the surface is an amino-functional modified surface.

28. The conductive material of claim 15, wherein the conductive material has a resistance of about 10–

100 ohms.

29. A conductive composition comprising:

(A) a crosslinked polymeric material formed by a process comprising reacting a polymer and a crosslinking agent, wherein the polymer has side chains along a backbone forming the polymer, at least two of the side chains being substituted with one or more heteroatoms selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus and combinations thereof, the polymer formed by reacting a mixture comprising

(i) one or more monomers selected from the group consisting of unsaturated dicarboxylic acids, esters of unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mixtures thereof; and

(ii) one or more amines selected from the group consisting of R—

NH₂, a polyalkylene polyamine, and mixtures thereof, wherein the R group contains between 1 and 50 carbon atoms and one or more of the selected amines includes at least two amino groups; and

(B) a plurality of silver species distributed within the crosslinked polymeric material,

wherein the conductive composition has a resistance of no more than about 100 ohms.

30. The conductive composition of claim 29, wherein the conductive composition has a resistance of about 10–

100 ohms.

31. A conductive material comprising:

(A) a polymeric material comprising a polymer having side chains along a backbone forming the polymer, at least two of the side chains being substituted with one or more heteroatoms selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus and combinations thereof, wherein the polymer is synthesized by a process that includes reacting a mixture comprising;

(i) one or more monomers selected from the group consisting of unsaturated dicarboxylic acids, esters of unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mixtures thereof; and

(ii) one or more amines selected from the group consisting of R—

NH₂, polyalkylene polyamines, and mixtures thereof, wherein the R group contains between 1 and 50 carbon atoms and one or more of the selected amines includes at least two amino groups; and

(B) one or more silver species distributed within the polymeric material,

wherein the conductive material has a resistance of no more than about 100 ohms.

32. The conductive material of claim 31, wherein the conductive material has a resistance of about 10–

100 ohms.

33. A conductive material formed from a coating composition comprising:

(A) a polymer-based material which includes a polyamide having two or more amino functionalized side chains; and

(B) copper species or silver species distributed within the polyamide;

the polymer-based material is formed by a process which comprises adding an organic soluble metal salt of copper or silver to a solution of the polyamide in an organic solvent; and

the polyamide is formed by reacting a mixture comprising;

(i) one or more monomers selected from the group consisting of unsaturated dicarboxylic acids, esters of unsaturateddicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mixtures thereof; and

(ii) one or more amines selected from the group consisting of R—

NH₂, polyalkylene polyamines, and mixtures thereof, wherein the R group contains between 1 and 50 carbon atoms and one or more of the selected amines includes at least two amino groups;

wherein the copper species or silver species is present at a sufficient concentration in the coating composition such that the resistance of the conductive material is no more than about 100 ohms.

34. The conductive material of claim 33, wherein the conductive material has a resistance of about 10–

100 ohms.