Hydrogel composites and superporous hydrogel composites having fast swelling, high mechanical strength, and superabsorbent properties

• US 6,271,278 B1
• Filed: 05/13/1997
• Issued: 08/07/2001
• Est. Priority Date: 05/13/1997
• Status: Expired due to Fees

• Current Assignee: Purdue Research Foundation (The Trustees of Purdue University (d/b/a Purdue University))
• Original Assignee: Purdue Research Foundation (The Trustees of Purdue University (d/b/a Purdue University))
• Inventors: Chen, Jun, Park, Haesun, Park, Kinam
• Primary Examiner(s): COONEY, JOHN M
• Application Number:
  US08/855,499
• Time in Patent Office: 1,547 Days
• Field of Search: 521/102, 521/109.1, 521/121, 521/125, 521/128, 521/130, 521/140, 521/142, 521/146, 521/149, 521/150, 521/182, 521/183, 521/186, 521/187
• US Class Current: 521/150
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: A61P 3/04 Anorexiants; Antiobesity agents
• CPC Class Codes: C08F 251/00 Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Abstract

A superporous hydrogel composite is formed by polymerizing one or more ethylenically-unsaturated monomers, and a multiolefinic crosslinking agent, in the presence of particles of a disintegrant and a blowing agent. The disintegrant, which rapidly absorbs water, serves to greatly increase the mechanical strength of the superporous hydrogel and significantly shorten the time required to absorb water and swell. Superporous hydrogel composites prepared by this method have an average pore size in the range of 10 μm to 3,000 μm. Preferred particles of disintegrant include natural and synthetic charged polymers, such as crosslinked sodium carboxymethylcellulose, crosslinked sodium starch glycolate, and crosslinked polyvinylpyrrolidone. The blowing agent is preferably a compound that releases gas bubbles upon acidification, such as NaHCO₃. Improved hydrogel composites formed without a blowing agent are also provided.

Claims

1. A hydrogel composite comprising an interpenetrating network of a crosslinked polymer and particles of a disintegrant, wherein:

said crosslinked polymer is formed from at least one ethylenically-unsaturated monomer and a multi-olefinic crosslinking agent; and

said disintegrant is at least one of (i) a crosslinked natural or synthetic polyelectrolyte, (ii) a crosslinked neutral hydrophilic polymer, (iii) a non-crosslinked natural or synthetic polyelectrolyte having a particulate shape, (iv) a non-crosslinked neutral hydrophilic polymer having a particulate shape, or (v) a porous inorganic material that provides wicking by capillary forces.

2. The hydrogel composite of claim 1, wherein the ratio of disintegrant to polymer is in the range of 1:

100 to 100;

100.

3. The hydrogel composite of claim 1, wherein the ratio of multi-olefinic crosslinking agent to monomer is in the range of 0.01:

100 to 10;

100.

4. The hydrogel composite of claim 1, wherein the at least one ethylenically-unsaturated monomer is selected from the group consisting of (meth)acrylic acid, salts of (meth)acrylic acid, esters of (meth)acrylic acid, salts and acids of esters of (meth)acrylic acid, amides of (meth)acrylic acid, N-alkyl amides of (meth)acrylic acid, salts and acids of N-alkyl amides of (meth)acrylic acid, N-vinyl pyrrolidinone, acrylamide, acrylamide derivatives, methacrylamide, methacrylamide derivatives, and mixtures thereof.

5. The hydrogel composite of claim 1, wherein the at least one ethylenically-unsaturated monomer is selected from the group consisting of acrylamide (AM), N-isopropylacrylamide (NIPAM), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), N-vinyl pyrrolidinone (VP), acrylic acid (AA), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), 3-sulfopropyl acrylate potassium salt (SPAK), 2-(acryloyloxy)ethyltrimethyl-ammonium methyl sulfate (ATMS), inorganic salts thereof, and mixtures thereof.

6. The hydrogel composite of claim 1, wherein the crosslinking agent is selected from the group consisting of N,N′

-methylenebisacrylamide, ethylene glycol di(meth)acrylate, piperazine diacrylamide, glutaraldehyde, epichlorohydrin, crosslinking agents containing 1,2-diol structures, crosslinking agents containing functionalized peptides, and crosslinking agents containing proteins.

7. The hydrogel composite of claim 1, wherein the particles of disintegrant are selected from the group consisting of crosslinked sodium carboxymethylcellulose, crosslinked sodium starch glycolate, crosslinked sodium carboxymethyl starch, crosslinked dextran sulfate, crosslinked chitosan, crosslinked hyaluronic acid, crosslinked sodium alginate, crosslinked pectinic acid, crosslinked deoxyribonucleic acids, crosslinked ribonucleic acid, crosslinked gelatin, crosslinked albumin, polyacrolein potassium, sodium glycine carbonate, crosslinked poly(acrylic acid), crosslinked poly(styrene sulfonate), crosslinked poly(aspartic acid), crosslinked polylysine, crosslinked polyvinylpyrrolidone, crosslinked ultramylopectin, crosslinked poly(ethylene glycol), crosslinked neutral cellulose derivatives, microcrystalline cellulose, powdered cellulose, cellulose fiber, and crosslinked starch.

8. The hydrogel composite of claim 1, which has a swelling ratio in the range of 2 to 1,000.

9. The hydrogel composite of claim 1, which has a compression modulus in the range of 0.01 to 5 kg/cm².

10. The hydrogel composite of claim 1, which has a swelling time in the range of 10 seconds to 10 hours for a sample having a size in the range of 0.01 cm³ and larger.

11. A superporous hydrogel composite having a superporous pore structure comprising an interpenetrating network of a crosslinked polymer and particles of a disintegrant, wherein:

said crosslinked polymer is formed from at least one ethylenically-unsaturated monomer and a multi-olefinic crosslinking agent; and

said disintegrant is at least one of (i) a crosslinked natural or synthetic polyelectrolyte, (ii) a crosslinked neutral hydrophilic polymer, (iii) a non-crosslinked natural or synthetic polyelectrolyte having a particulate shape, (iv) a non-crosslinked neutral hydrophilic polymer having a particulate shape, or (v) a porous inorganic material that provides wicking by capillary forces.

12. The superporous hydrogel composite of claim 11, wherein the ratio of disintegrant to polymer is in the range of 1:

100 to 100;

100.

13. The superporous hydrogel composite of claim 11, wherein the ratio of multi-olefinic crosslinking agent to monomer is in the range of 0.01:

100 to 10;

100.

14. The superporous hydrogel composite of claim 11, wherein the at least one ethylenically-unsaturated monomer is selected from the group consisting of (meth)acrylic acid, salts of (meth)acrylic acid, esters of (meth)acrylic acid, salts and acids of esters of (meth)acrylic acid, amides of (meth)acrylic acid, N-alkyl amides of (meth)acrylic acid, salts and acids of N-alkyl amides of (meth)acrylic acid, N-vinyl pyrrolidinone, acrylamide, acrylamide derivatives, methacrylamide, methacrylamide derivatives, and mixtures thereof.

15. The superporous hydrogel composite of claim 11, wherein the at least one ethylenically-unsaturated monomer is selected from the group consisting of acrylamide (AM), N-isopropylacrylamide (NIPAM), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), N-vinyl pyrrolidinone (VP), acrylic acid (AA), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), 3-sulfopropyl acrylate potassium salt (SPAK), 2-(acryloyloxy)ethyltrimethyl-ammonium methyl sulfate (ATMS), inorganic salts thereof, and mixtures thereof.

16. The superporous hydrogel composite of claim 11, wherein the crosslinking agent is selected from the group consisting of N,N′

-methylene-bisacrylamide, ethylene glycol di(meth)acrylate, piperazine diacrylamide, glutaraldehyde, epichlorohydrin, crosslinking agents containing 1,2-diol structures, crosslinking agents containing functionalized peptides, and crosslinking agents containing proteins.

17. The superporous hydrogel composite of claim 11, wherein the particles of disintegrant are selected from the group consisting of crosslinked sodium carboxymethylcellulose, crosslinked sodium starch glycolate, crosslinked sodium carboxymethyl starch, crosslinked dextran sulfate, crosslinked chitosan, crosslinked hyaluronic acid, crosslinked sodium alginate, crosslinked pectinic acid, crosslinked deoxyribonucleic acids, crosslinked ribonucleic acid, crosslinked gelatin, crosslinked albumin, polyacrolein potassium, sodium glycine carbonate, crosslinked poly(acrylic acid), crosslinked poly(styrene sulfonate), crosslinked poly(aspartic acid), crosslinked polylysine, crosslinked polyvinylpyrrolidone, crosslinked ultramylopectin, crosslinked poly(ethylene glycol), crosslinked neutral cellulose derivatives, microcrystalline cellulose, powdered cellulose, cellulose fiber, and crosslinked starch.

18. The superporous hydrogel composite of claim 11, which has a swelling ratio in the range of 5 to 5000.

19. The superporous hydrogel composite of claim 11, which has a swelling time in the range of 1 second to 1 hour for a sample having a size in the range of 0.01 cm³ and larger.

20. A superporous hydrogel composite comprising an interpenetrating network of a crosslinked polymer and particles of a disintegrant, said composite prepared by a process comprising:

combining at least one ethylenically-unsaturated monomer, a multi-olefinic crosslinking agent, particles of a disintegrant, and a blowing agent to form an admixture thereof; and

subjecting said admixture to polymerization and foaming conditions to form said superporous hydrogel composite,

wherein said disintegrant is at least one of (i) a crosslinked natural or synthetic polyelectrolyte, (ii) a crosslinked neutral hydrophilic polymer, (iii) a non-crosslinked natural or synthetic polyelectrolyte having a particulate shape, (iv) a non-crosslinked neutral hydrophilic polymer having a particulate shape, or (v) a porous inorganic material that provides wicking by capillary forces.

21. The superporous hydrogel composite of claim 20, which has an average pore size in the range of 10 μ

m to 3,000 μ

m.

22. The superporous hydrogel composite of claim 20, which has an average pore size in the range of 50 μ

m to 1,000 μ

m.

23. The superporous hydrogel composite of claim 20, which has an average pore size in the range of 100 μ

m to 600 μ

m.

24. The superporous hydrogel composite of claim 20, wherein the ratio of disintegrant to polymer is in the range of 1:

100 to 100;

100.

25. The superporous hydrogel composite of claim 20, wherein the ratio of crosslinking agent to monomer is in the range of 0.01:

100 to 10;

100.

26. The superporous hydrogel composite of claim 20, wherein the blowing agent is NaHCO₃, Na₂CO₃, CaCO₃, or gas bubbles introduced from an external source.

27. The superporous hydrogel composite of claim 20, wherein the swelling ratio is in the range of 5 to 5,000.

28. The superporous hydrogel composite of claim 20, wherein the swelling time is in the range of 1 second to 1 hour.

29. The superporous hydrogel composite produced by drying the composite formed in claim 20 by air-drying or by replacing water in the composite with an organic solvent followed by air drying.

30. The superporous hydrogel composite of claim 29, which upon drying exhibits elastic properties of compression, extension, and folding without breaking.

31. The superporous hydrogel composite produced by drying the superporous hydrogel composite formed in claim 20 by freeze-drying after partial swelling or equilibrium swelling in aqueous solution.

32. The superporous hydrogel composite of claim 31, which upon drying exhibits elastic properties of compression, extension, and folding without breaking.

33. A method of forming a hydrogel composite comprising:

combining at least one ethylenically-unsaturated monomer, a multi-olefinic crosslinking agent, and particles of a disintegrant, to form an admixture thereof; and

subjecting the admixture to polymerization conditions to form said hydrogel composite.

34. The method of claim 33, further combining water with said admixture prior to subjecting the admixture to said polymerization conditions.

35. The method of claim 33, further combining a polymerization initiator with said admixture prior to subjecting the admixture to said polymerization conditions.

36. A method of forming a superporous hydrogel composite comprising:

combining at least one ethylenically-unsaturated monomer, a multi-olefinic crosslinking agent, particles of a disintegrant, and a blowing agent, to form an admixture thereof; and

subjecting the admixture to polymerization and foaming conditions to form said superporous hydrogel composite.

37. The method of claim 36, wherein said at least one ethylenically-unsaturated monomer, multi-olefinic crosslinking agent, and particles of a disintegrant are combined prior to combining the blowing agent therewith.

38. The method of claim 36, further combining water with said admixture prior to subjecting the admixture to said polymerization and foaming conditions.

39. The method of claim 36, further combining a foam stabilizing agent with said admixture prior to subjecting the admixture to said polymerization and foaming conditions.

40. The method of claim 36, further combining a polymerization initiator with said admixture prior to subjecting the admixture to said polymerization and foaming conditions.