One-pot synthesis of highly mechanical and recoverable double-network hydrogels

Patent metadata

Field	Value
Publication number	US-10336896-B2
Application number	US-201414787041-A
Country	US
Kind code	B2
Filing date	Apr 23, 2014
Priority date	Apr 25, 2013
Publication date	Jul 2, 2019
Grant date	Jul 2, 2019

Abstract

A method of forming a hybrid physically and chemically cross-linked double-network hydrogel with highly recoverable and mechanical properties in a single-pot synthesis is provided. The method comprises the steps of combining the hydrogel precursor reactants into a single pot. The hydrogel precursor reactants include water; a polysaccharide; a methacrylate monomer; an ultraviolet initiator; and a chemical crosslinker. Next the hydrogel precursor reactants are heated to a temperature higher than the melting point of the polysaccharide and this temperature is retained until the polysaccharide is in a sol state. Then the single-pot is cooled to a temperature lower than the gelation point of the polysaccharide and this temperature is retained to form a first network. Thereafter, photo-initiated polymerization of the methacrylate monomer occurs via the ultraviolet initiator to form the second network.

First claim

What is claimed is:

1. A method of forming a hybrid physically and chemically cross-linked double-network hydrogel with highly recoverable and mechanical properties in a single-pot synthesis comprising the steps of:
combining the hydrogel precursor reactants including:
a. water,
b. a polysaccharide,
c. an acrylate monomer,
d. an ultraviolet initiator, and
e. a chemical crosslinker to form a single pot mixture;

heating the hydrogel precursor reactants to a temperature higher than the melting point of the polysaccharide and retaining this temperature until the polysaccharide is in a sol state;
cooling the single-pot to a temperature lower than the gelation point of the polysaccharide and retaining this temperature to form a first network; and
thereafter photo-initiating polymerization of the acrylate monomer via the ultraviolet initiator to form the second network, wherein the double-network hydrogel has a polysaccharide concentration of 20 mg/mL, an acrylate monomer concentration of 3.4 mol/L, a ultraviolet initiator concentration of 1 mol % of acrylate monomer, and a chemical crosslinker concentration of 0.03 mol % of acrylate monomer.

2. The method of claim 1 wherein the hydrogel precursor reactants are heated to a temperature of from 90-95° C.

3. The method of claim 1 wherein the hydrogel precursor reactants are retained at the temperature higher than the melting point of the polysaccharide for a period of 3-5 minutes.

4. The method of claim 1 wherein the single-pot is cooled to a temperature of from 30-40° C.

5. The method of claim 1 wherein the cooled single-pot is retained at a temperature lower than the gelation point of the polysaccharide for a period of 15-30 minutes.

6. The method of claim 1 wherein the polysaccharide as the first network is selected from the group consisting of agar, gelatin, sodium alginate, carrageenan, and other stimuli-responsive and reversible sol-gel systems including supermolecular hydrogels and self-healing hydrogels.

7. The method of claim 6 wherein the polysaccharide is agar.

8. The method of claim 1 wherein the acrylate monomer as the second network is selected from the group consisting of acrylamide, methylacrylamide, acrylic acid, N,N′-dimethylacrylamide, N-isopropylacrylamide, and ethylene glycol diacrylate.

9. The method of claim 8 wherein the acrylate monomer is acrylamide.

10. The method of claim 1 wherein the ultraviolet initiator is selected from the group consisting of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone and 2-oxoglutaric acid.

11. The method of claim 10 wherein the ultraviolet initiator is 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone.

12. The method of claim 1 wherein the chemical crosslinker is selected from the group consisting of N, N′-methyl-bis-acrylamide and poly(ethylene glycol) diacrylate.

13. The method of claim 12 wherein the chemical crosslinker is N, N′-methyl-bis-acrylamide.

14. The method of claim 1 wherein the forming of the hybrid physically and chemically cross-linked double-network hydrogel takes between 1 and 2 hours to complete.

Assignees

• Zheng Jie
• Chen Qiang
• Zhao Chao
• Univ Akron

Inventors

• Zheng Jie
• Chen Qiang
• Zhao Chao

Classifications

• C08B37/0039 Primary

  Agar; Agarose, i.e. D-galactose, 3,6-anhydro-D-galactose, methylated, sulfated, e.g. from the red algae Gelidium and Gracilaria; Agaropectin; Derivatives thereof, e.g. Sepharose, i.e. crosslinked agarose · CPC title

• C08L33/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title

• C08J2433/26

  Homopolymers or copolymers of acrylamide or methacrylamide · CPC title

• C08J2333/26

  Homopolymers or copolymers of acrylamide or methacrylamide · CPC title

• C08J3/075

  Macromolecular gels · CPC title