Polyurethane-grafted hydrogels

• US 8,853,294 B2
• Filed: 05/29/2013
• Issued: 10/07/2014
• Est. Priority Date: 08/05/2008
• Status: Expired due to Fees

• Current Assignee: Biomimedica, Inc, Emergence Venture Partners, LLC
• Original Assignee: Biomimedica, Inc, Emergence Venture Partners, LLC
• Inventors: Myung, David, Kourtis, Lampros, Ward, Robert, Jaasma, Michael J., McCrea, Keith
• Primary Examiner(s): Tran, Thao T.
• Application Number:
  US13/905,028
• Publication Number:
  US 20130261212A1
• Time in Patent Office: 496 Days
• Field of Search: 522/86, 524/115, 514/16.7, 514/17.1, 514/17.2, 623/23.58
• US Class Current: 522/86
• CPC Class Codes: A61K 6/893 Polyurethanes
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/26 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 27/48 with macromolecular fillers
• CPC Class Codes: A61L 27/52 Hydrogels or hydrocolloids
• CPC Class Codes: A61L 27/54 Biologically active materials, e.g. therapeutic substances A61L27/227 takes precedence
• CPC Class Codes: A61L 27/56 Porous materials, e.g. foams or sponges
• CPC Class Codes: A61P 19/08 for bone diseases, e.g. rachitism, Paget's disease
• CPC Class Codes: B32B 2037/243 Coating
• CPC Class Codes: B32B 2375/00 Polyureas; Polyurethanes
• CPC Class Codes: B32B 2535/00 Medical equipment, e.g. bandage, prostheses, catheter medical patches B32B2556/00
• CPC Class Codes: C08F 283/02 on to polycarbonates or saturated polyesters C08F283/004 takes precedence
• CPC Class Codes: C08G 18/44 Polycarbonates
• CPC Class Codes: C08G 18/664 with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 2270/00 Compositions for creating interpenetrating networks
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 9/36 After-treatment C08J9/22 takes precedence
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 75/02 : Polyureas
• CPC Class Codes: C08L 75/16 : having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31583 : Nitrile monomer type [polyacrylonitrile, etc.]

Abstract

An article comprising two chemically grafted polymer layers comprising a hydrogel layer and an end-functionalized polyurethane layer. The invention also includes methods of making and using the article.

Claims

1. A method of grafting a polyurethane layer to a hydrogel layer the method comprising the steps of:

providing a first solution comprising either reactive hydrogel or end-functionalized polyurethane precursors;

applying a second solution to the first solution wherein the second solution comprises end-functionalized polyurethane precursors if the first solution comprises hydrogel precursors and wherein the second solution comprises reactive hydrogel precursors if the first solution comprises polyurethane precursors; and

polymerizing and crosslinking the solutions to form a laminated graft polymer comprising a polyurethane layer and a hydrogel layer.

2. The method of claim 1 further comprising freezing the first solution to form a solidified layer.

3. The method of claim 1 further comprising drying the first solution to form a solidified layer.

4. The method of claim 1 wherein the polymerizing step comprises exposing the first and second solutions to UV light or heat.

5. The method of claim 1 further comprising:

swelling the hydrogel layer with a third solution comprising hydrogel precursors different from the precursors in the first or second solutions; and

polymerizing the third solution to create a graft polymer comprising an IPN layer Comprising a second hydrogel network intertwined with a first hydrogel network and a polyurethane layer.

6. The method of claim 5 wherein the third solution comprises a partial solvent for the first hydrogel and is able to swell the first hydrogel network.

7. The method of claim 1 wherein the hydrogel solution comprises telechelic molecules.

8. The method of claim 7 wherein the telechelic molecules are poly(ethylene glycol) with one or more endgroups selected from the group consisting of acrylate, methacrylate, acrylamide, vinyl, and allyl ether.

9. The method of claim 1 wherein the polyurethane solution comprises one or more of vinyl terminated polyurethane, polycarbonate urethane, polyether urethane, polycarbonate urethane urea, polyester urethane, polyurethane urea and silicon derivatives of these.

10. The method of claim 1, further comprising covalently linking the hydrogel layer to the polyurethane layer at an interface between the two layers.

11. The method of claim 5, further comprising covalently linking the IPN layer to the polyurethane layer at an interface between the two layers.

12. A method of forming a laminated graft polymer having an end-fonetionalized polyurethane layer and a hydrogel layer comprising:

contacting a polyurethane precursor solution with a hydrogel precursor solution;

graft polymerizing the polyurethane precursor solution and the hydrogel precursor to form a laminated graft polymer having the end,funetionalized polyurethane layer covalently linked to the hydrogel layer at an interface between the two layers.

13. The method of claim 12, further comprising solidifying the polyurethane precursor solution.

14. The method of claim 13, wherein the polymerizing step generates heat to melt a portion of the solidified precursor solution.

15. The method of claim 12, further comprising solidifying the hydrogel precursor solution.

16. The method of claim 15, wherein the contacting step comprises casting the polyurethane precursor solution over a surface of the solidified hydrogel precursor solution.

17. The method of claim 15, wherein solidifying comprises flash freezing the hydrogel precursor solution.

18. The method of claim 12, further comprising crosslinking at least one of the hydrogel or polyurethane layers.

19. The method of claim 12, further comprising:

swelling the hydrogel layer with another hydrogel precursor solution; and

polymerizing the another hydrogel precursor solution inside the hydrogel layer to form a hydrogel IPN inside the hydrogel layer.

20. The method of claim 12, wherein the polyurethane precursor solution comprises one or more of vinyl terminated polyurethane, polycarbonate urethane, polyether urethane, polycarbonate urethane urea, polyester urethane, polyurethane urea and silicon derivatives of these.