Conductive self-healing network

Patent metadata

Field	Value
Publication number	US-10669399-B2
Application number	US-201715484597-A
Country	US
Kind code	B2
Filing date	Apr 11, 2017
Priority date	Apr 11, 2016
Publication date	Jun 2, 2020
Grant date	Jun 2, 2020

Abstract

Disclosed herein are self-healing conductive network compositions. The networks can contain one or more conductive polymers and one or more supramolecular complexes. The supramolecular complex can be introduced into conductive polymer matrix, resulting in a network of the two components. In this network, the nanostructured conductive polymer gel constructs a 3D network to promote the transport of electrons and mechanically reinforce the network while the supramolecular complex contributes to self-healing property and also conductivity. The networks disclosed herein are useful for various applications such as self-healing electronics, artificial skins, soft robotics and biomimetic prostheses.

First claim

What is claimed is:

1. A self-healing, conductive network composition comprising:
a conductive polymer; and
an organometallic supramolecular complex, having a cubic architecture.

2. The network composition according to claim 1 , in the state of a gel.

3. The network composition according to claim 2 , further comprising a solvent.

4. The network composition according to claim 1 , wherein the ratio (w/w) of conductive polymer and supramolecular complex is from about 25:1 to 1:25.

5. The network composition according to claim 1 , wherein the conductive polymer comprises a polyaniline, a polypyrrole, a polythiophene, a polystyrene sulfonic acid, or a combination thereof.

6. The network composition according to claim 1 , wherein the conductive polymer comprises a compound of the formula:

wherein R is C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkyl, C 1-6 haloalkoxy, F, Cl, Br, I, CN, NO 2 , n is 0, 1, 2, 3 or 4, m is 0, 1 or 2, X is NH, O, S, Se, or a mixture thereof.

7. The network composition according to claim 1 , wherein the conductive polymer comprises a dopant.

8. The network composition according to claim 1 , wherein the conductive polymer comprises a dopant comprising a polybasic compound.

9. The network composition of claim 1 , wherein the organometallic supramolecular complex, in the absence of the conductive polymer, is characterized by a sol-gel transition temperature no greater than about 75° C.

10. The network composition according to claim 1 , wherein the organometallic supramolecular complex is represented by the formula M 12 L 8 , wherein M represents a transition metal and L represents a tritopic ligand.

11. The network composition according to claim 10 , wherein M is selected from the group consisting of Zn, Cd, Ni, Co, Fe, Ru, Mn and combinations thereof.

12. The network composition according to claim 10 , wherein the organometallic supramolecular complex comprises a tritopic ligand having the formula:

wherein:
Z is a group of the formula:

wherein each represents a bond to a B 3 yyy group, Φ represents a 1,4 phenylene, z is either 0 or 1, and R z is selected from hydrogen, C 1-12 alkyl, C 3-12 cycloalkyl, C 1-12 alkoxy, C 2-12 heterocyclyl, C 6-12 aryl, C 3-12 heteroaryl, poly(alkylene glycol), crown ethers, and pillarene;
x, xx, and xxx are each independently 0 or 1, and A 1 , A 2 and A 3 are independently selected from:

y, yy, and yyy are each independently 0, 1 or 2, and B 1 , B 2 and B 3 are independently selected from

wherein R is in each case independently selected from hydrogen, F, Cl, Br, I, OH, COOH, NO 2 , C 1-6 alkyl, C 1-6 haloalkyl, C 3-6 cycloalkyl, C 1-6 alkoxy, C 2-12 heterocyclyl, C 6-12 aryl, and C 3-12 heteroaryl, and wherein any two or more R groups may together form a ring;
with the proviso that the sum of x, xx, xxx, y, yy, and yyy is not 0;
R b and R d are independently selected hydrogen, halogen (e.g., F, C 1 , Br, I), OH, COOH, NO 2 , C 1-6 alkyl, C 1-6 haloalkyl, C 3-6 cycloalkyl, C 1-6 alkoxy, C 2-12 heterocyclyl, C 6-12 aryl, and C 3-12 heteroaryl;
R a and R c are independently selected from:

or wherein either R a and R b or R c and R d , together form a group having the structure:

wherein R 1 is in each case independently selected from hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, and C 1 -C 6 haloalkyl, R 2 is in each case independently selected from C 1 -C 6 alkyl, and wherein any two or more of R 1 or R 2 may together form a ring.

13. The network composition according to claim 12 , wherein Z has the formula:

14. The network composition according to claim 12 , wherein R b and R d are both hydrogen, and R a and R c each have the formula:

15. The network composition according to claim 14 , wherein R 1 is in each case tert-butyl.

16. A method of making the self-healing, conductive network composition of claim 1 , comprising the step of combining a dry conductive polymer, an organometallic supramolecular complex having a cubic architecture, and a solvent, and partially evaporating the mixture to give a self-healing, conductive network.

17. The method of claim 16 , wherein the solvent comprises water, acetonitrile, THF, DMF, DMSO, or a mixture thereof.

18. The method of claim 16 , wherein the network composition, after partial evaporation, comprises from about 40-60% by weight of the solvent.

Assignees

• Univ Texas
• Texas State Univ

Inventors

• Yu Guihua
• Shi Ye
• Li Xiaopeng

Classifications

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• C08G2261/3221

  containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole · CPC title

• C08K5/5442

  Chemistry & Metallurgy · mapped topic

• C08K5/3432 Primary

  Six-membered rings · CPC title

• H01B1/127

  comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes · CPC title