Thermally healable and reshapable conductive hydrogel composite

• US 9,757,496 B2
• Filed: 08/20/2014
• Issued: 09/12/2017
• Est. Priority Date: 08/26/2013
• Status: Active Grant

• Current Assignee: Korea Advanced Institute of Science and Technology, Samsung Electronics Co. Ltd.
• Original Assignee: Korea Advanced Institute of Science and Technology, Samsung Electronics Co. Ltd.
• Inventors: Hur, Jae-hyun, Park, No-kyoung, Im, Kyu-hyun, Kim, Sang-won, Hwang, Sung-woo, Choi, Jang-wook
• Primary Examiner(s): Hammer, Katie L
• Application Number:
  US14/463,884
• Publication Number:
  US 20150053896A1
• Time in Patent Office: 1,119 Days
• Field of Search: None
• CPC Class Codes: A61L 27/20 Polysaccharides
• CPC Class Codes: A61L 27/443 with carbon fillers
• CPC Class Codes: A61L 27/446 with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
• CPC Class Codes: A61L 27/48 with macromolecular fillers
• CPC Class Codes: A61L 27/50 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: A61L 27/52 Hydrogels or hydrocolloids
• CPC Class Codes: A61L 27/60 Materials for use in artificial skin
• CPC Class Codes: B82Y 5/00 Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• CPC Class Codes: C08J 3/075 Macromolecular gels
• CPC Class Codes: C08J 3/247 Heating methods
• CPC Class Codes: C08L 5/12 Agar or agar-agar , i.e. mixture of agarose and agaropectin; Derivatives thereof
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys

Abstract

An electro-conductive hydrogel composite material that may be suitable as an artificial skin satisfies all four requirements of artificial skin, namely, flexibility, electrical conductivity, healing property, and biocompatibility. The electro-conductive hydrogel composite material includes a hydrogel composition including water and a cross-linkable polymer which reversibly forms cross-linkage by hydrogen bonding; and an electro-conductive material dispersed in the hydrogen bond-based hydrogel.

Claims

1. An electro-conductive hydrogel composite material comprising:

a hydrogel composition comprising (a) water and (b) a cross-linkable polymer, said polymer reversibly forming a cross-linkage by hydrogen bonding; and

an electro-conductive material dispersed in the hydrogel composition,

wherein the electro-conductive hydrogel composite material is a thermally healable skin.

2. The electro-conductive hydrogel composite material of claim 1, wherein the cross-linkable polymer is agarose.

3. The electro-conductive hydrogel composite material of claim 1, wherein an amount of the water in the hydrogel composition is about 0.5 parts by weight to about 5.0 parts by weight based on 100 parts by weight of the cross-linkable polymer.

4. The electro-conductive hydrogel composite material of claim 1, wherein the electro-conductive material is a metal particle, a conductive carbon material, a conductive polymer, or a combination thereof.

5. The electro-conductive hydrogel composite material of claim 4, wherein the metal is a metal element or a metal compound wherein the metal is selected from the group consisting of gold, silver, platinum, titanium, iron, and a combination thereof.

6. The electro-conductive hydrogel composite material of claim 4, wherein the conductive carbon material is carbon black, carbon nanotubes, graphene, or a combination thereof.

7. The electro-conductive hydrogel composite material of claim 4, wherein the conductive polymer is polypyrroles, poly(3,4-ethylenedioxythiophenes), poly(styrenesulfonates), poly(3,4-ethylenedioxythiophenes):

poly(styrenesulfonates), polyanilines, or a combination thereof.

8. The electro-conductive hydrogel composite material of claim 1, wherein the electro-conductive material has an average particle size of about 100 nm to about 1 μ

m.

9. The electro-conductive hydrogel composite material of claim 1, wherein an amount of the electro-conductive material in the hydrogel composition is about 10 parts by weight to about 300 parts by weight based on 100 parts by weight of the cross-linkable polymer.

10. The electro-conductive hydrogel composite material of claim 1, wherein the water further comprises an electrolyte.

11. The electro-conductive hydrogel composite material of claim 10, wherein the electrolyte is NaCl, KCl, Na₂HPO₄, KH₂PO₄, Na₂SO₄, Li₂SO₄, MgSO₄, phosphate-buffered saline buffer, Tris-HCl buffer, or a combination thereof.

12. The electro-conductive hydrogel composite material of claim 10, wherein an amount of the electrolyte is about 0.1 parts by weight to about 5.0 parts by weight based on 100 parts by weight of the water in the hydrogel composition.

13. The electro-conductive hydrogel composite material of claim 10, wherein the water which comprises an electrolyte is phosphate-buffered saline.

14. The electro-conductive hydrogel composite material of claim 1, wherein the electro-conductive material is polypyrrole, and an amount of the polypyrrole is greater than 0 parts by weight and equal to or less than about 300 parts by weight based on 100 parts by weight of the cross-linkable polymer.

15. A method of preparing an electro-conductive hydrogel composite material, comprising

providing a heated dispersion comprising a cross-linkable polymer which reversibly forms cross linkages by hydrogen bonding, water, and an electro-conductive material;

and

cooling the dispersion to a temperature such that the dispersion forms a hydrogel in which the conductive material is dispersed,

wherein the electro-conductive hydrogel composite material is a thermally healable skin.

16. A method of preparing an electro-conductive hydrogel composite material comprising (i) a hydrogel comprising water and a cross-linkable polymer which reversibly forms cross linkages by hydrogen bonding;

and (ii) an electro-conductive polymer dispersed in the hydrogel, the method comprising;

providing a heated mixture comprising the cross-linkable polymer;

water;

a monomer for forming an electro-conductive polymer; and

an oxidizing agent; and

cooling the mixture to a temperature such that the dispersion forms a hydrogel,

wherein the electro-conductive hydrogel composite material is a thermally healable skin.

17. The method of claim 16, wherein the oxidizing agent is FeCl₃, CuCl₂, K₂S₂O₈, or a combination thereof.

18. The method of claim 16, wherein an amount of the oxidizing agent in the reaction mixture is about 50 parts by weight to about 1500 parts by weight based on 100 parts by weight of the cross-linkable polymer capable of being cross-linked by hydrogen bonding.

19. An electro-conductive hydrogel composite material comprising:

a hydrogel composition comprising (a) an aqueous base and (b) agarose; and

a polypyrrole dispersed in the hydrogel composition,

wherein the electro-conductive hydrogel composite material is a thermally healable skin.

20. The electro-conductive hydrogel composite material of claim 19, wherein the aqueous base is water or a phosphate-buffered saline.