IP Library › Granted Patent US 10,383,980
Granted Patent B2
US 10,383,980 · App. 15/172,549 · Granted Aug 20, 2019

Interpenetrating networks with covalent and ionic crosslinks

Inventors: Jeong-Yun Sun (Cambridge, MA); Xuanhe Zhao (Durham, NC); Widusha R. K. Illeperuma (Cambridge, MA); Kyu H. Oh (Seocho-gu, KR); Joost J. Vlassak (Lexington, MA); Zhigang Suo (Lexington, MA); Jianyu Li (Cambridge, MA); David J. Mooney (Sudbury, MA)
Assignees: President and Fellows of Harvard College; Seoul National University Industry Foundation
A61L27/52A61L27/16A61L27/20A61L27/26A61L27/48A61L27/50A61L27/60C08J3/075C08J3/246C08L5/04C08L33/26C08L71/02C08J2333/26C08J2405/04C08L2201/54C08L2203/02C08L2205/04
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Quick Facts
Patent No.
US 10,383,980
App. No.
15/172,549
Granted
Aug 20, 2019
Kind
B2
Abstract

The invention features a composition comprising a self-healing interpenetrating network hydrogel comprising a first network and a second network. The first network comprises covalent crosslinks and the second network comprises ionic or physical crosslinks. For example, the first network comprises a polyacrylamide polymer and second network comprises an alginate polymer.

Claims (42)

1. A composition comprising a self-healing interpenetrating networks hydrogel comprising a first network and a second network, wherein:

said first network comprises covalent crosslinks and said second network comprises ionic or physical crosslinks;

wherein said first network and said second network are covalently coupled;

said first network comprises a covalently crosslinked polymer selected from the group consisting of polyacrylamide, poly(vinyl alcohol), poly(ethylene oxide) and its copolymers, polyethylene glycol (PEG), methacrylated PEG, and polyphosphazene; and

said second network comprises an alginate polymer having a crosslinking density that is derived from a weight ratio between an ionic crosslinking agent and an alginate monomer of between about 13.28 wt. % and 19.93 wt. % based on the alginate monomer weight.

2. The composition of claim 1 , wherein said first network comprises a polyacrylamide polymer and said second network comprises an alginate polymer.

3. The composition of claim 1 , wherein said first network comprises a polyethylene glycol (PEG) polymer and said second network comprises an alginate polymer.

4. The composition of claim 1 , wherein said interpenetrating polymer networks hydrogel comprises between 30-98 wt % water.

5. The composition of claim 1 , wherein the Young's modulus of the hydrogel is about 10 kPa to about 300 kPa.

6. The composition of claim 1 , wherein the Young's modulus of the hydrogel is about 300 kPa to about 5 MPa.

7. The composition of claim 1 , wherein the fracture toughness of the hydrogel is about 3000 J/m 2 to about 9000 J/m 2 .

8. The composition of claim 1 , wherein said interpenetrating networks hydrogel is fabricated in the form of a tissue augmentation or tissue replacement composition.

9. The composition of claim 8 , wherein said tissue augmentation or tissue replacement composition comprises a synthetic joint cartilage, spin disc, tendon, blood vessel, heart valve, muscle or skin.

10. The composition of claim 1 , wherein said interpenetrating networks hydrogel is used as a shock absorber or impact protector between biological or non-biological surfaces.

11. A composition comprising a self-healing interpenetrating networks hydrogel comprising a first network and a second network, wherein:

said first network comprises covalent crosslinks and said second network comprises ionic or physical crosslinks;

said first network comprises a covalently crosslinked polymer having a crosslinking density that is derived from a weight ratio between a covalent crosslinking agent and a monomer of the covalently crosslinked polymer of between about 0.046 wt. % and 0.093 wt. % based on the monomer weight, wherein the covalently crosslinked polymer is selected from the group consisting of polyacrylamide, poly(vinyl alcohol), poly(ethylene oxide) and its copolymers, polyethylene glycol (PEG), methacrylated PEG, and polyphosphazene; and

said second network comprises an alginate polymer.

12. The composition of claim 11 , wherein said first network and said second network are covalently coupled.

13. The composition of claim 11 , wherein said first network comprises a polyacrylamide polymer and said second network comprises an alginate polymer.

14. The composition of claim 11 , wherein said first network comprises a polyethylene glycol (PEG) polymer and said second network comprises an alginate polymer.

15. The composition of claim 11 , wherein said interpenetrating polymer networks hydrogel comprises between 30-98 wt % water.

16. The composition of claim 11 , wherein the fracture toughness of the hydrogel is about 1000 J/m 2 to about 9000 J/m 2 .

17. The composition of claim 11 , wherein said interpenetrating networks hydrogel is fabricated in the form of a tissue augmentation or tissue replacement composition.

18. The composition of claim 17 , wherein said tissue augmentation or tissue replacement composition comprises a synthetic joint cartilage, spin disc, tendon, blood vessel, heart valve, muscle or skin.

19. The composition of claim 11 , wherein said interpenetrating networks hydrogel is used as a shock absorber or impact protector between biological or non-biological surfaces.

20. A composition comprising a self-healing interpenetrating networks hydrogel comprising a first network and a second network, wherein:

said first network comprises covalent crosslinks and said second network comprises ionic or physical crosslinks;

wherein said first network and said second network are covalently coupled;

said first network comprises a covalently crosslinked polymer selected from the group consisting of polyacrylamide, poly(vinyl alcohol), poly(ethylene oxide) and its copolymers, polyethylene glycol (PEG), and polyphosphazene;

said first network comprises a covalent crosslinking agent selected from the group consisting of N,N-methylenebisacrylamide (MBAA), a methacrylate crosslinker, N,N′-dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (ECC), N-hydroxysuccinimide, N-hydroxysulfosuccinimide, glutaraldehyde, and a transglutaminase;

said second network comprises an alginate polymer; and

said composition has a covalently crosslinked polymer/(covalently crosslinked polymer and alginate polymer) ratio of between about 66.67 wt. % and 94.12 wt. % based on monomer weights.

21. The composition of claim 1 , wherein said alginate polymer has a crosslinking density of about 13.28 wt. % alginate monomer weight.

22. The composition of claim 1 , wherein said first network further comprises a covalent crosslinking agent.

23. The composition of claim 22 , wherein said covalent crosslinking agent is selected from the group consisting of N,N-methylenebisacrylamide (MBAA), a methacrylate crosslinker, N,N′-dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (ECC), N-hydroxysuccinimide, N-hydroxysulfosuccinimide, glutaraldehyde, and a transglutaminase.

24. The composition of claim 11 , wherein the Young's modulus of the hydrogel is at least 10 kPa.

25. The composition of claim 11 , wherein said covalently crosslinked polymer has a crosslinking density of about 0.06 wt. % based on monomer weight.

26. The composition of claim 20 , wherein the Young's modulus of the hydrogel is about 300 kPa to about 5 MPa.

27. The composition of claim 20 , wherein said composition has a covalently crosslinked polymer/(covalently crosslinked polymer and alginate polymer) ratio of between about 66.67 wt. % and 88.89 wt. % based on monomer weights.

28. The composition of claim 20 , wherein said composition has a covalently crosslinked polymer/(covalently crosslinked polymer and alginate polymer) ratio of about 88.89 wt. % based on monomer weights.

29. The composition of claim 20 , wherein said composition has a covalently crosslinked polymer/(covalently crosslinked polymer and alginate polymer) ratio of about 85.71 wt. % based on monomer weights.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 3, 2016
From: SEOUL NATIONAL UNIVERSITY INDUSTRY FOUNDATION
To: SEOUL NATIONAL UNIVERSITY R&DB FOUNDATION
Reel/Frame 040562/0385 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 20, 2016
From: ILLEPERUMA, WIDUSHA; LI, JIANYU; MOONEY, DAVID J.; SUN, JEONG-YUN; SUO, ZHIGANG; VLASSAK, JOOST J.; ZHAO, XUANHE
To: PRESIDENT AND FELLOWS OF HARVARD COLLEGE
Reel/Frame 040088/0247 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 31, 2016
From: OH, KYU HWAN
To: SEOUL NATIONAL UNIVERSITY INDUSTRY FOUNDATION
Reel/Frame 039600/0759 →
Continuity (4)
Continuation 14370451
Provisional Application 61694039 · Aug 28, 2012
Provisional Application 61583586 · Jan 5, 2012
Related Publication 20160354520A1 · Dec 8, 2016
Cited By (1)
US 12,605,480