Multi-polymer hydrogels

• US 7,731,988 B2
• Filed: 08/03/2007
• Issued: 06/08/2010
• Est. Priority Date: 08/03/2007
• Status: Expired due to Fees

• Current Assignee: Zimmer Incorporated (Zimmer Biomet Holdings, Inc.)
• Original Assignee: Zimmer Incorporated (Zimmer Biomet Holdings, Inc.)
• Inventors: Zhang, Kai, Thomas, Brian
• Primary Examiner(s): Wax; Robert A
• Assistant Examiner(s): AL-AWADI, DANAH J
• Application Number:
  US11/833,549
• Publication Number:
  US 20090035344A1
• Time in Patent Office: 1,040 Days
• Field of Search: None
• US Class Current: 424/423
• CPC Class Codes: A61L 27/52 Hydrogels or hydrocolloids
• CPC Class Codes: C08J 2300/00 Characterised by the use of unspecified polymers
• CPC Class Codes: C08J 2329/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: C08J 3/075 Macromolecular gels

Abstract

The invention provides a multi-polymer hydrogel article having a first polymeric, water-swellable material and a second polymeric material, organized such that a first region substantially comprises the first polymeric, water-swellable material, a second region adjacent the first region comprises a mixture of the first polymeric, water-swellable material and the second polymeric material, and a third region adjacent the second region substantially comprises the second polymeric material. The article exhibits an increasing concentration gradient of the second polymeric material moving from the first region, through the second region, to the third region. The invention also provides methods for forming a multi-polymer hydrogel article by (a) forming a hydrogel structure using a first polymeric, water-swellable material, (b) creating an aerogel structure having a plurality of open pores by dehydrating the hydrogel structure, (c) contacting the aerogel structure with a second polymeric material to incorporate the second polymeric material into at least a portion of the plurality of open pores to form the multi-polymer hydrogel article, and (d) rehydrating the multi-polymer hydrogel article.

Claims

1. A method of forming a multi-polymer hydrogel article comprising:

(a) forming a hydrogel structure comprising a first polymeric, water-swellable material,

(b) creating an aerogel structure comprising a plurality of open pores by dehydrating the hydrogel structure,

(c) contacting the aerogel structure with a second polymeric material to incorporate the second polymeric material into at least a portion of the plurality of open pores to form the multi-polymer hydrogel article, and

(d) rehydrating the multi-polymer hydrogel article.

2. The method of claim 1, wherein forming the hydrogel structure comprises dip coating, casting, injection molding, or compression molding the first polymeric, water-swellable material into a shape.

3. The method of claim 2, wherein forming the hydrogel structure further comprises dip coating, casting or molding the first polymeric, water-swellable material at least partially encompassing a third sacrificial material.

4. The method of claim 3, wherein the third sacrificial material is soluble in an aqueous solution.

5. The method of claim 3, wherein the third sacrificial material is selected from the group consisting of sugars, waxes, gelatins, salts, low molecular weight water-soluble polymers, ice, and biodegradable polymers, and combinations thereof.

6. The method of claim 3, further comprising dissolving the third sacrificial material to form a void at least partially encompassed by the first polymeric, water-swellable material.

7. The method of claim 6, wherein the void is limited at its periphery by the first polymeric, water-swellable material such that the first polymeric, water-swellable material substantially surrounds the void.

8. The method of claim 6, wherein dissolving the third sacrificial material occurs in vivo.

9. The method of claim 1, further comprising, prior to forming the hydrogel structure, introducing a third sacrificial material into the first polymeric, water-swellable material, and wherein creating the aerogel structure further includes dissolving the third sacrificial material to thereby form additional open pores.

10. The method of claim 9, wherein the third sacrificial material is soluble in an aqueous solution.

11. The method of claim 9, wherein the third sacrificial material is selected from the group consisting of sugars, waxes, gelatins, salts, low molecular weight water-soluble polymers, ice, and biodegradable polymers, and combinations thereof.

12. The method of claim 1, wherein forming the hydrogel structure further comprises using a surfactant or rapid agitation to create spheres, rods, globules, ellipsoidal shapes, cylindrical shapes, or disc shapes.

13. The method of claim 12, further comprising polymerizing the surfactant in the case of a self emulsifying polymerization to create hydrogel beads.

14. The method of claim 1, wherein dehydrating the hydrogel structure includes removing water and/or plasticizers from the hydrogel structure by heating, subjecting to a vacuum, solvent exchange, or freeze-drying, or combinations thereof.

15. The method of claim 1, wherein creating the aerogel structure further comprises forming the aerogel structure following dehydrating the hydrogel structure, wherein forming comprises cutting, molding, and/or shaping the aerogel structure.

16. The method of claim 1, wherein the contacting results in a first region substantially comprising the first polymeric, water-swellable material, a second region adjacent the first region comprising a mixture of the first polymeric, water-swellable material and the second polymeric material, and a third region adjacent the second region substantially comprising the second polymeric material, wherein the second polymeric material exhibits an increasing concentration gradient moving from the first region, through the second region, to the third region.

17. The method of claim 16 wherein the first region extends from a first point to a first interface with the second region, the second region extends from the first interface to a second interface with the third region and includes therein a second point, and the third region extends from the second interface to a third point;

wherein a percent volume ratio of the first polymeric, water-swellable material to the second polymeric material continuously changes from about 100;

0 at the first point, to about 50;

50 at the second point, to about 0;

100 at the third point; and

wherein the presence of pore blockers moves the second point towards the third point.

18. The method of claim 17 wherein the pore blockers are selected from the group consisting of sugars, salts, low molecular weight water-soluble polymers, and biodegradable polymers, and combinations thereof.

19. The method of claim 1, wherein contacting the aerogel structure with the second polymeric material further comprises introducing the second polymeric material into a void created by dissolving a third sacrificial material.

20. The method of claim 19, further comprising introducing a material into the void created by dissolving the third sacrificial material.

21. The method of claim 1, wherein contacting the aerogel structure with the second polymeric material occurs under a pressure.

22. The method of claim 21 wherein a first region extends from a first point to a first interface with a second region, the second region extends from the first interface to a second interface with a third region and includes therein a second point, and the third region extends from the second interface to a third point;

wherein a percent volume ratio of the first polymeric, water-swellable material to the second polymeric material continuously changes from about 100;

0 at the first point, to about 50;

50 at the second point, to about 0;

100 at the third point; and

wherein the extent of the pressure of the second polymeric material moves the second point towards the first point.

23. The method of claim 1 wherein at least two of the steps (a)-(d) are repeated to produce a multilayered, multi-polymer hydrogel article.

24. The method of claim 1 further comprising crosslinking the multi-polymer hydrogel article.

25. The method of claim 24 wherein crosslinking occurs by radiation crosslinking, physical crosslinking, or chemical crosslinking, or combinations thereof.

26. The method of claim 25 wherein radiation crosslinking comprises exposing the multi-polymer hydrogel article to at least one of visible light radiation, ultraviolet radiation, infrared radiation, electron beam radiation, gamma radiation, or x-ray radiation.

27. The method of claim 25 wherein physical crosslinking comprises exposing the multi-polymer hydrogel article to freezing and thawing.

28. The method of claim 25 wherein chemical crosslinking comprises exposing the multi-polymer hydrogel article to a monoaldehyde or a diisocyanate.