Superabsorbent foams, and method for producing the same

• US 5,573,994 A
• Filed: 05/13/1994
• Issued: 11/12/1996
• Est. Priority Date: 05/13/1994
• Status: Expired due to Term

• Current Assignee: University of Cincinnati
• Original Assignee: University of Cincinnati
• Inventors: Gehrke, Stevin H., Kabra, Bhagwati G.
• Primary Examiner(s): Pal, Asok
• Application Number:
  US08/242,548
• Time in Patent Office: 914 Days
• Field of Search: 502/402, 502/439, 502/514, 521/62, 521/63, 521/64, 264/DIG. 18, 264/DIG. 16, 264/DIG. 9, 604/369
• US Class Current: 502/402
• CPC Class Codes: A61L 15/26 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof A61L15/225 takes precedence
• CPC Class Codes: A61L 15/28 Polysaccharides or their derivatives A61L15/225 takes precedence
• CPC Class Codes: A61L 15/32 Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin A61L15/225 takes precedence
• CPC Class Codes: A61L 15/425 Porous materials, e.g. foams or sponges
• CPC Class Codes: C08J 9/28 by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• CPC Class Codes: C08L 1/28 Alkyl ethers
• CPC Class Codes: Y10S 264/16 Molding foamed polypropylen articles
• CPC Class Codes: Y10S 264/18 Cross-linking a thermoplastic linear foam during molding
• CPC Class Codes: Y10S 502/514 Process applicable either to preparing or to regenerating or to rehabilitating catalyst or sorbent
• CPC Class Codes: Y10S 521/905 Hydrophilic or hydrophobic cellular product
• CPC Class Codes: Y10T 428/249954 With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
• CPC Class Codes: Y10T 428/249979 Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
• CPC Class Codes: Y10T 428/249995 Constituent is in liquid form

Abstract

An absorbent, microporous foam comprising a crosslinked polymer having interconnected fluid cells distributed throughout its mass, wherein the fluid cells have a diameter of between about 0.1 and about 100 μm, and wherein the foam can rapidly absorb at least about twice its dry weight in fluid, is disclosed.

A method for producing a microporous, absorbent foam is also disclosed. This method comprises the steps of:

(a) mixing a cross-linkable polymer and a first solvent to form a stable solution, wherein the stable solution can be induced to phase separate;

(b) inducing the stable solution to phase separate into a polymer-concentrated phase and a polymer-dilute phase after a predetermined period of time;

(c) inducing crosslinking of said polymer, so that the polymer will crosslink in said concentrated phase for a predetermined period of time during phase separation to thereby form a microporous material; and

(d) drying the microporous material to produce the absorbent foam.

Claims

1. A method for producing a microporous, absorbent foam, comprising the steps of:

(a) mixing a cross-linkable polymer and a first solvent to form a stable solution, wherein said stable solution can be induced to phase separate;

(b) inducing said stable solution to phase separate into a polymer-concentrated phase and a polymer-dilute phase;

(c) inducing chemical crosslinking of said polymer, so that said polymer will crosslink in said concentrated phase during said phase separation to thereby form a microporous material; and

(d) drying said microporous material to produce said absorbent foam.

2. The method of claim 1, wherein said stable solution is a substantially homogeneous, single-phase solution.

3. The method of claim 2, wherein said phase separation is induced by changing the temperature of said stable solution.

4. The method of claim 2, wherein said phase separation is induced by adding a phase separation enhancer to said stable solution.

5. The method of claim 4, wherein said phase separation enhancer is either another solute or an additional solvent, and wherein said additional solvent is a non-solvent for said polymer and is miscible with said first solvent.

6. The method of claim 3, wherein said crosslinking is induced prior to said phase separtion, such that crosslinking will occur prior to said phase separation.

7. The method of claim 3, wherein said single-phase solution exhibits a lower consolute solution temperature, and wherein said phase separation is induced by increasing the temperature of said single-phase solution to a point above said lower consolute solution temperature.

8. The method of claim 3, wherein said single-phase solution exhibits an upper consolute solution temperature, and wherein said phase separation is induced by decreasing the temperature of said single-phase solution to a point below said upper consolute solution temperature.

9. The method of claim 3 further comprising the step of adding a phase-separation enhancer to said single-phase solution prior to inducing said phase separation.

10. The method of claim 3, further comprising the step of removing the uncrosslinked sol fraction present in said microporous material prior to said drying step.

11. The method of claim 3, wherein said drying step is accomplished by air-drying.

12. The method of claim 3, wherein said drying step is accomplished by freeze-drying.

13. The method of claim 3, wherein said drying step is accomplished by placing said microporous material in a second solvent, thereby swelling said material with said second solvent and replacing any of said first solvent which is present in said material, followed by air-drying said material so that said second solvent will evaporate.

14. The method of claim 13, wherein said drying step further comprises the step of placing said microporous material swollen with said second solvent in a third solvent, thereby replacing said second solvent with said third solvent, and thereafter air-drying said material so that said third solvent will evaporate.

15. The method of claim 3, wherein said polymer is chosen from the group consisting of:

hydrophobically modified carbohydrate polymers, poly(vinyl alcohol-co-vinyl acetate), poly(methacrylic acid), cyanoethylated or partially formalized poly(vinyl alcohol), poly-N-vinyl-2-oxazolidone, polypeptides, acrylate (or analogous methacrylate) copolymers, and N-alkylacrylamide (or analogous N-alkylmethacrylamide) derivatives.

16. The method of claim 15, wherein said hydrophobically modified carbohydrate polymers include:

hydroxypropyl dextran, hydroxypropyl guar, hydroxypropyl starch, hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), methyl cellulose, hydroxypropylmethyl cellulose, and ethylhydroxyethyl cellulose;

wherein said polypeptides include;

poly(L-proline), and poly(valine-proline-glycine-X-glycine), wherein X=any amino acid;

wherein said acrylate (or analogous methacrylate) copolymers include;

hydroxypropyl acrylate-co-acrylamide, diacetone acrylamide-co-hydroxyethyl acrylate, and hydroxypropyl acrylate-co-hydroxyethyl acrylate; and

wherein said N-alkylacrylamide (or analogous N-alkylmethacrylamide) derivatives include;

ethylacrylamide, cyclopropylacrylamide, n-propylacrylamide, and isopropylacrylamide.

17. The method of claim 16, wherein said polymer is either HPC or HEC.

18. The method of claim 3, wherein said crosslinking is further accomplished by physical means.

19. The method of claim 2, wherein crosslinking is induced by adding a suitable crosslinking agent to said solution.

20. The method of claim 2, wherein said solution is photo-crosslinked.

21. The method of claim 19, wherein said physical crosslinking is accomplished by employing a polymer having hydrophobic polymer side chains capable of interacting with one another.

22. The method of claim 19, wherein said physical crosslinking is accomplished through hydrogen-bonding, van der Waals interactions, ionic bonding, hydrogen bonding, coordination interactions, or salt bridges.

23. The method of claim 2, wherein said crosslinking agent is chosen from the group consisting of:

acetaldehyde, formaldehyde, glutaraldehyde, diglycidyl ether, divinyl sulfone, diisocyanates, dimethyl urea, epichlorohydrin, oxalic acid, phosphoryl chloride, trimetaphosphate, trimethylomelamine, polyacrolein, and ceric ion redox systems.

24. The method of claim 23, wherein said crosslinking agent is divinyl sulfone.

25. A method for producing a microporous, open-celled foam, comprising the steps of:

(a) mixing hydroxypropyl cellulose (HPC) and water to form a substantially homogeneous, single-phase solution;

(b) inducing crosslinking of said HPC by adding a suitable crosslinking agent to said single-phase solution;

(c) inducing phase separation of said single-phase solution into a polymer-concentrated phase and a polymer-dilute phase, wherein said phase separation is induced by increasing the temperature of said single-phase solution to above the lower consolute solution temperature of said single-phase solution;

(d) permitting said crosslinking to continue, so that said HPC will crosslink in said concentrated phase during said phase separation to thereby form a microporous material; and

(e) drying said microporous material to produce said foam.

26. The method of claim 25, wherein said crosslinking agent is divinyl sulfone (DVS).

27. The method of claim 26, wherein the concentration of HPC is between about 1.9 and about 25 weight percent of said single-phase solution, and wherein the pH of said single-phase solution is above about 11.

28. The method of claim 27, wherein the concentration of DVS is between about 0.2 and about 5.5 weight percent of said single-phase solution.

29. The method of claim 28, wherein said phase separation is induced by increasing the temperature of said solution to above about 40°

C.

30. The method of claim 29, wherein said phase separation is induced after said crosslinking has proceeded for between about 1 and about 45 minutes, and said crosslinking is permitted to continue after inducing said phase separation for between about 0.3 and about 100 hours.

31. A method for producing a microporous, open-celled foam, comprising the steps of:

(a) mixing hydroxyethyl cellulose (HEC), water and a phase-separation enhancer to form a substantially homogeneous, single-phase solution, wherein said phase-separation enhancer is chosen from the group consisting of;

a salt, a water-soluble organic solvent, and a combination of a salt and a water-soluble organic solvent;

(b) inducing crosslinking of said HEC by adding a suitable crosslinking agent to said single-phase solution;

(c) inducing phase separation of said single-phase solution into a polymer-concentrated phase and a polymer-dilute phase, wherein said phase separation is induced by increasing the temperature of said single-phase solution to above the lower consolute solution temperature of said single-phase solution; and

(d) permitting said crosslinking to continue, so that said HEC will crosslink in said concentrated phase during said phase separation to thereby form a microporous material; and

(e) drying said microporous material to produce said foam.

32. The method of claim 31, wherein said crosslinking agent is divinyl sulfone (DVS).

33. The method of claim 32, wherein said phase separation enhancer is sodium chloride.

34. The method of claim 32, wherein said phase separation is induced by increasing the temperature of said solution to above about 94°

C.

35. The method of claim 34, wherein the pH of said single-phase solution is above about 11, and wherein the concentration of HEC is between about 1.3 and about 18 weight percent of said single-phase solution.

36. The method of claim 35, wherein the concentration of DVS is between about 0.4 and about 2 weight percent.

37. The method of claim 36, wherein said phase separation is induced after said crosslinking has proceeded for between about 1 and about 3 minutes, and said crosslinking is permitted to continue after said inducing for between about 20 and about 60 minutes.