Reinforced, laminated, impregnated, and composite-like materials as crosslinked polyvinyl alcohol hydrogel structures

• US 6,855,743 B1
• Filed: 10/29/2001
• Issued: 02/15/2005
• Est. Priority Date: 10/29/2001
• Status: Active Grant

• Current Assignee: Hydromedica, LLC
• Original Assignee: Nanosystems Research, Inc.
• Inventors: Gvozdic, Nedeljko Vladimira
• Primary Examiner(s): Morris, Terrel
• Assistant Examiner(s): Chang, Victor S.
• Application Number:
  US10/020,785
• Time in Patent Office: 1,205 Days
• Field of Search: 428/304.4, 428/317.9, 521/141, 521/61, 521/64, 264/41, 264/42
• US Class Current: 521/141
• 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 2329/14 Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
• CPC Class Codes: C08J 3/075 Macromolecular gels
• CPC Class Codes: C08J 3/24 Crosslinking, e.g. vulcanising, of macromolecules mechanical aspects B29C35/00; crosslinking agents C08K
• CPC Class Codes: C08J 5/04 Reinforcing macromolecular compounds with loose or coherent fibrous material
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• 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 29/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/249992 Linear or thermoplastic

Abstract

Reinforced, laminated, impregnated, and materials with composite properties as cross linked polyvinyl alcohol hydrogel structures in bulk or cellular matrix forms that can take essentially any physical shape, or can have essentially any size, degree of porosity and surface texture. They have a wide range of physical properties, unusual and unique combinations of physical properties and unique responses to stress fields, which allows for their use in many end use applications.

Claims

1. A reinforced polyvinyl alcohol structure, said structure comprising

(A) a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel and

(B) a reinforcing material for reinforcing said matrix.

2. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution formed in (II) with a pore-forming material capable of partially dissolving in solution (II) and its solution capable of causing formation of physical cross linking in the polyvinyl alcohol polymer;

(IV) providing conditions at which the polyvinyl alcohol polymer of (III) will undergo physical crosslinking caused by the presence of the partially dissolved pore forming material;

(V) bringing the mixture from (IV) to about room temperature;

(VI) removing the pore forming material by a means which does not significantly affect the crosslinking or pore forming material.

3. A polyvinyl alcohol structure as claimed in claim 2 that is reinforced.

4. A polyvinyl alcohol structure as claimed in claim 2 that is a laminate.

5. A polyvinyl alcohol structure as claimed in claim 2 that is a material with composite properties.

6. A polyvinyl alcohol structure as claimed in claim 2 that is an impregnated solid structure.

7. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution formed in (II) with a pore forming material;

(IV) submersing the mixture from (III) in a bath consisting of a material selected from the group consisting essentially of;

(a) a solvent for the polyvinyl alcohol polymer wherein the solvent is a non-solvent at low temperature for the polyvinyl alcohol polymer;

(b) a non-solvent for the polyvinyl alcohol polymer,

(c) a poor solvent for the polyvinyl alcohol polymer, and

(d) an aqueous solution of a material selected from the group consisting of;

(i) a salt;

(ii) an acid at a low temperature, and

(iii) a base,

to induce crystallization, gellation, coagulation, or a mixture of crystallization, gellation, or coagulation, of the polyvinyl alcohol polymer;

(V) providing conditions at which the polyvinyl alcohol polymer of submersed mixture of (III) will undergo further physical crosslinking in a bath of (IV);

(VI) bringing the mixture from (V) to about room temperature and removing essentially all of the pore forming materials by means which do not significantly affect the crosslinking.

8. A polyvinyl alcohol structure as claimed in claim 7 that is reinforced.

9. A polyvinyl alcohol structure as claimed in claim 7 that is a laminate.

10. A polyvinyl alcohol structure as claimed in claim 7 that is a material with composite properties.

11. A polyvinyl alcohol structure as claimed in claim 7 that is an impregnated solid structure.

12. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution from (II) with a material selected from the group consisting of;

(a) a surface active agent and,

(b) a mixture of surface active agents and frothing said mixture;

(IV) cooling the frothed mixture from (III) to a temperature at which the polyvinyl alcohol polymer will undergo physical crosslinking;

(V) essentially removing any solvent present in the frothed mixture by a means which does not significantly affect the crosslinking;

(VI) bringing the mixture to an elevated temperature for a period of 10 seconds to 8 hours and cooling the mixture to about room temperature.

13. A polyvinyl alcohol structure as claimed in claim 12 that is reinforced.

14. A polyvinyl alcohol structure as claimed in claim 12 that is a laminate.

15. A polyvinyl alcohol structure as claimed in claim 12 that is a composite.

16. A polyvinyl alcohol structure as claimed in claim 12 that is an impregnated solid structure.

17. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution from (II) with a material selected from the groups consisting of;

(a) a surface active agent and,

(b) a mixture of surface active agents and frothing said mixture;

(IV) cooling the frothed mixture from (III) to a temperature at which the polymer will undergo physical crosslinking;

(V) bringing the mixture to about room temperature.

18. A polyvinyl alcohol structure as claimed in claim 17 that is reinforced.

19. A polyvinyl alcohol structure as claimed in claim 17 that is a laminate.

20. A polyvinyl alcohol structure as claimed in claim 17 that is a material with composite properties.

21. A polyvinyl alcohol structure as claimed in claim 17 that is an impregnated solid structure.

22. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel and wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution from (II) with a material selected from the group consisting of;

(a) a surface active agent, and

(b) a mixture of surface active agents and frothing said mixture;

(IV) cooling the frothed mixture from (III) to a temperature at which the polyvinyl alcohol polymer will undergo physical crosslinking;

(V) submersing the mixture from (IV) into a bath consisting essentially of a material selected from the group consisting of;

(i) a solvent that is a non-solvent at low temperature for the polyvinyl alcohol polymer,

(ii) a non-solvent for the polyvinyl alcohol polymer,

(iii) a poor solvent for the polyvinyl alcohol polymer,

(iv) an aqueous solution of a salt,

(v) an aqueous solution of an acid at low temperature, and,

(vi) an aqueous solution of a base,

to induce crystallization, gellation, coagulation, or a mixture of crystallization, gellation, or coagulation of said polyvinyl alcohol polymer;

(VI) providing conditions at which the polyvinyl alcohol polymer of frothed mixture of (III) will undergo further physical crosslinking in a bath of (V);

(VII) bringing the mixture to about room temperature.

23. A polyvinyl alcohol structure as claimed in claim 22 that is reinforced.

24. A polyvinyl alcohol structure as claimed in claim 22 that is a laminate.

25. A polyvinyl alcohol structure as claimed in claim 22 that is a material with composite properties.

26. A polyvinyl alcohol structure as claimed in claim 22 that is an impregnated solid structure.

27. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel and wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution from (II) with a material selected from the group consisting of;

(a) a surface active agent and,

(b) a mixture of surface active agents and frothing said mixture;

(IV) combining the froth formed in (III) with polyvinyl alcohol polymer solution containing a pore forming material;

(V) cooling the a material with composite properties mixture from (IV) to a temperature at which the polymer will undergo physical crosslinking;

(VI) bringing the mixture to about room temperature;

(VII) removing the pore forming material by a means which does not significantly affect the crosslinking.

28. A polyvinyl alcohol structure as claimed in claim 27 that is reinforced.

29. A polyvinyl alcohol structure as claimed in claim 27 that is a laminate.

30. A polyvinyl alcohol structure as claimed in claim 27 that is a material with composite properties.

31. A polyvinyl alcohol structure as claimed in claim 27 that is an impregnated solid structure.

32. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel and wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution from (II) with material selected from the group consisting of;

(a) a surface active agent and,

(b) a mixture of surface active agents and frothing said mixture;

(IV) combining the froth formed in (III) with a polyvinyl alcohol polymer solution containing a pore forming material;

(V) cooling the a material with composite properties mixture from (IV) to a temperature at which the polyvinyl alcohol polymer will undergo physical crosslinking;

(VI) submersing the resulting a material with composite properties

material from (V) in a bath consisting of a material selected from the group consisting of;

(a) a solvent that is a non-solvent at low temperature for the polyvinyl alcohol polymer,

(b) a non-solvent for the polyvinyl alcohol polymer,

(c) a poor solvent for the polyvinyl alcohol polymer,

(d) an aqueous solution of a salt,

(e) an aqueous solution of an acid at low temperature, and,

(f) an aqueous solution of a base,

(VII) providing conditions at which the polyvinyl alcohol polymer from (IV) will undergo physical crosslinking;

(VIII) bringing the mixture from (VII) to about room temperature;

(IX) removing the pore forming material by a means which does not significantly affect the crosslinking.

33. A polyvinyl alcohol structure as claimed in claim 32 that is reinforced.

34. A polyvinyl alcohol structure as claimed in claim 32 that is a laminate.

35. A polyvinyl alcohol structure as claimed in claim 32 that is a material with composite properties.

36. A polyvinyl alcohol structure as claimed in claim 32 that is an impregnated solid structure.

37. A polyvinyl alcohol structure, said structure comprising a physically crosslinked polyvinyl alcohol based matrix derived from a cellular physically crosslinkable polyvinyl alcohol hydrogel and wherein the cellular physically crosslinkable polyvinyl alcohol based matrix has been prepared by the method comprising the steps of:

(I) providing a polyvinyl alcohol polymer capable of being physically crosslinked;

(II) dissolving said polyvinyl alcohol polymer in a material selected from the group consisting of;

(i) a single solvent for the polyvinyl alcohol polymer and,

(ii) a mixture of solvents for the polyvinyl alcohol polymer, to form a solution;

(III) mixing the solution from (II) with a material selected from the group consisting of;

(a) a surface active agent and,

(b) a mixture of surface active agents and frothing said mixture;

(IV) combining the froth formed in (III) with a solution of polyvinyl alcohol polymer with a pore forming material into a material with composite properties material;

(V) cooling the material with composite properties mixture from (IV) to a temperature at which the polyvinyl alcohol polymer will undergo physical crosslinking;

(VI) submersing the resulting a material with composite properties material from (V) in a bath consisting of;

(a) a solvent that is a non-solvent at low temperature for the polyvinyl alcohol polymers,

(b) a non-solvent for the polyvinyl alcohol polymer,

(c) a poor solvent for the polyvinyl alcohol polymer,

(d) an aqueous solution of a salt,

(e) an aqueous solution of an acid at low temperature, and,

(f) an aqueous solution of a base,

(VI) providing conditions at which the polyvinyl alcohol polymer from (IV) will undergo physical crosslinking;

(VIII) bringing the mixture from (VII) to about room temperature;

(IX) removing essentially all of the solvents by a means which does not significantly affect the crosslinking or pore forming material,

(X) heating the material at an elevated temperature for a period of time from ten seconds to eight hours, and,

(XI) cooling the mixture from (X) to about room temperature and removing the pore forming material by a means which does not significantly affect the crosslinking.

38. A polyvinyl alcohol structure as claimed in claim 37 that is reinforced.

39. A polyvinyl alcohol structure as claimed in claim 37 that is a laminate.

40. A polyvinyl alcohol structure as claimed in claim 37 that is a material with composite properties.

41. A polyvinyl alcohol structure as claimed in claim 37 that is an impregnated solid structure.