DEGRADABLE SUPERABSORBENT POLYMERS

• US 20130065765A1
• Filed: 07/05/2011
• Published: 03/14/2013
• Est. Priority Date: 07/05/2010
• Status: Abandoned Application

• Current Assignee: RELUCEO, Inc., Relucio, Inc.
• Original Assignee: RELUCEO, Inc.
• Inventors: Selifonov, Sergey, Scholten, Marc, Zhou, Ning
• Application Number:
  US13/576,547
• Publication Number:
  US 20130065765A1
• Time in Patent Office: Days
• US Class Current: 504/361
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A01N 25/26 in coated particulate form
• CPC Class Codes: A01N 25/34 Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
• CPC Class Codes: B01J 20/262 obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G
• CPC Class Codes: C08F 216/06 Polyvinyl alcohol ; Vinyl alcohol
• CPC Class Codes: C08F 216/38 by an acetal or ketal radical
• CPC Class Codes: C08F 8/14 Esterification
• CPC Class Codes: C08F 8/28 Condensation with aldehydes or ketones
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: C08G 4/00 Condensation polymers of aldehydes or ketones with polyalcohols; Addition polymers of heterocyclic oxygen compounds containing in the ring at least once the grouping —O—C—O— of cyclic oligomers of aldehydes C08G2/00
• CPC Class Codes: C09D 161/00 Coating compositions based on condensation polymers of aldehydes or ketones with polyalcohols C09D159/00; with polynitriles C09D177/00; Coating compositions based on derivatives of such polymers
• CPC Class Codes: Y10T 428/2933 Coated or with bond, impregnation or core
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 442/20 Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Abstract

The present disclosure relates to degradable superabsorbent materials based on acetals of glyoxylic acid and derivatives thereof with polyvinyl alcohol, and methods of making the polymers. The polymers are used to make superabsorbent particles, coatings, sheets, and fibers. Formulations and articles including the superabsorbent polymers, particles, coatings, sheets, and fibers are also disclosed.

Claims

1. A particle comprising a polymer composition, the polymer composition comprising a neutralized poly(vinyl glyoxylic acid), the particle comprising convoluted surface morphology features.

2. The particle of claim 1 wherein the neutralized poly(vinyl glyoxylic acid) comprises sodium, potassium, lithium, or ammonium carboxylate groups.

3. The particle of claim 1 wherein the convoluted surface features have heights of about 10 nm to 25 μ

m, and periodicity of about 10 nm to 50 μ

m.

4. The particle of claim 1 wherein the convoluted surface morphology features are present on about 10% to 100% of the particle surface.

5. The particle of claim 1 wherein the polymer composition is capable of forming a hydrogel with an aqueous liquid.

6. The particle of claim 1 wherein the particle is capable of absorbing 0.9 wt % NaCl solution at an initial rate of about 1 g to 25 g of solution per gram of polymer composition per minute at 20°

C. to 27°

C.

7. The particle of claim 1 wherein the particle comprises a particle size of between about 1 micrometer and 3 millimeters.

8. The particle of claim 1 wherein the particle comprises a particle size of between about 100 micrometers and 1 millimeter.

9. The particle of claim 1 wherein the particle comprises an absorption capacity of about 16 g to about 50 g of 0.9 wt % NaCl solution per gram of the polymer composition at about 20°

C. to 27°

C.

10. A formulation comprising the particle of claim 1 and one or more formulation components, the formulation components comprising solvents, aqueous liquids, aqueous solvent mixtures, celluloses, starches, lignins, polysaccharides, surfactants, clays, micas, drilling fluids, insecticides, herbicides, fertilizers, fragrances, drugs, fire-retardant agents, personal care formulation components, coating additives, cyclodextrins, fillers, adjuvants, thermal stabilizers, UV stabilizers, colorants, acidulants, metals, microorganisms, spores, encapsulated organic acids, mixtures thereof, and combinations of two or more thereof.

11. The formulation of claim 10 wherein the particle is admixed with the one or more formulation components.

12. The formulation of claim 10 wherein the one or more formulation components is entrained within the particle.

13. An article comprising the particle of claim 1, wherein the article is a diaper for an infant, an adult protective undergarment or incontinence undergarment, a feminine sanitary napkin, an underground power or communications cable, a horticultural water retention agent, control agent for aqueous fluid spill or effluent, a carrier for controlled release of insecticides, herbicides, fragrances, or drugs, a drilling fluid additive, a fire-retardant composition, a mortuary pad, a surgical pad, a wound dressing, a medical or other aqueous waste solidification article, an absorbent pad for food, a food packaging material, a cosmetic or personal care article, a sealing composite, a filter, a fuel monitor system for aviation and motor vehicles, a drown-free water source for caged insects, masking tape designed for use with latex paint, a hot/cold therapy pack, a motionless waterbed, a grow-in-water toy, or artificial snow for motion picture and stage production, or a combination of two or more thereof.

56. An article comprising the formulation of claim 10, wherein the article is a diaper for an infant, an adult protective undergarment or incontinence undergarment, a feminine sanitary napkin, an underground power or communications cable, a horticultural water retention agent, control agent for aqueous fluid spill or effluent, a carrier for controlled release of insecticides, herbicides, fragrances, or drugs, a drilling fluid additive, a fire-retardant composition, a mortuary pad, a surgical pad, a wound dressing, a medical or other aqueous waste solidification article, an absorbent pad for food, a food packaging material, a cosmetic or personal care article, a sealing composite, a filter, a fuel monitor system for aviation and motor vehicles, a drown-free water source for caged insects, masking tape designed for use with latex paint, a hot/cold therapy pack, a motionless waterbed, a grow-in-water toy, or artificial snow for motion picture and stage production, or a combination of two or more thereof.

14. A coating comprising a polymer composition, the polymer composition comprising a neutralized poly(vinyl glyoxylic acid), the coating comprising convoluted surface morphology features.

15. The coating of claim 14 wherein the convoluted surface features have heights of between about 10 nm and 25 μ

m, and periodicity of between about 10 nm and 50 μ

m.

16. The coating of claim 14 wherein the polymer composition is capable of forming a hydrogel with an aqueous liquid.

17. The coating of claim 14 wherein the coating is capable of absorbing 0.9 wt % NaCl solution at an initial rate of about 1 to 25 g of solution per gram of polymer composition per minute at 20°

C. to 27°

C.

18. The coating of claim 14 wherein the coating comprises an absorption capacity of about 16 to 50 g of 0.9 wt % NaCl solution per gram of the polymer composition at 20°

C. to 27°

C.

19. The coating of claim 14 wherein the convoluted surface morphology features are present on about 10% to 100% of the coating surface.

20. The coating of claim 14 wherein the coating is continuous or discontinuous.

21. The coating of claim 14 wherein the coating is disposed on a substrate, the substrate comprising a particle, a fiber, a film, a sheet, a plate, a nonwoven fabric or sheet, a woven fabric, or a coated particle, fiber, film, sheet, plate, or fabric.

22. The coating of claim 14 further comprising one or more solvents, aqueous liquids, aqueous solvent mixtures, celluloses, starches, lignins, polysaccharides, surfactants, clays, micas, drilling fluids, insecticides, herbicides, fertilizers, fragrances, drugs, fire-retardant agents, personal care formulation components, coating additives, cyclodextrins, fillers, adjuvants, thermal stabilizers, UV stabilizers, colorants, acidulants, metals, microorganisms, spores, encapsulated organic acids, a mixture of two or more thereof, or a combination of two or more thereof.

23. An article comprising the coating of claim 14, the article comprising a diaper for an infant, an adult protective undergarment or incontinence undergarment, a feminine sanitary napkin, an underground power or communications cable, a horticultural water retention agent, control agent for aqueous fluid spill or effluent, a carrier for controlled release of insecticides, herbicides, fragrances, or drugs, a drilling fluid additive, a fire-retardant composition, a mortuary pad, a surgical pad, a wound dressing, a medical or other aqueous waste solidification article, an absorbent pad for food, a food packaging material, a cosmetic or personal care article, a sealing composite, a filter, a fuel monitor system for aviation and motor vehicles, a drown-free water source for caged insects, masking tape designed for use with latex paint, a hot/cold therapy pack, a motionless waterbed, a grow-in-water toy, or artificial snow for motion picture and stage production, or a combination of two or more thereof.

24. A method of making a polymer composition, the polymer composition comprising a neutralized poly(vinyl glyoxylic acid), the method comprising

a. combining about 5 wt % to 25 wt % polyvinyl alcohol in water with one or more glyoxylate derivatives to form a reaction mixture;

b. evaporating at least a portion of the water from the reaction mixture;

c. contacting the reaction mixture with a base to form the polymer composition;

d. washing the polymer composition with a water miscible solvent or a solvent mixture, the solvent mixture comprising a water miscible solvent; and

e. removing at least a portion of the water miscible solvent or the mixture.

25. The method of claim 24 wherein the water miscible solvent is methanol, ethanol, isopropanol or acetone.

26. The method of claim 24 wherein the solvent mixture further comprises water.

27. The method of claim 24 wherein the method further comprises coating the reaction mixture on a substrate.

28. The method of claim 24 wherein the method further comprises dividing the reaction mixture or the polymer composition.

29. The method of claim 24 wherein the method is a continuous method.

30. A method of degelling a hydrogel, the hydrogel comprising a neutralized poly(vinyl glyoxylic acid) and an aqueous liquid, the method comprising contacting the hydrogel with a weak organic acid in an amount sufficient to cause degelling of at least a portion of the contacted hydrogel.

31. The method of claim 30 wherein the weak organic acid is citric acid, succinic acid, malic acid, fumaric acid, lactic acid, or O-lactoyllactic acid.

32. The method of claim 30 wherein contacting the weak organic acid with the aqueous liquid causes the weak organic acid to contact the poly(vinyl glyoxylic acid).

33. The method of claim 30 wherein the weak organic acid is encapsulated prior to contacting with the aqueous liquid.

34. The method of claim 30 wherein the weak organic acid is a latent acidulant.

35. The method of claim 30 wherein 10 days after the contacting, at least about 30 wt %, of the contacted hydrogel capable of passing through a paper filter having particle retention capacity of 1-5 μ

m and a Hertzberg flow rate of 1400 seconds.

36. A particle comprising a polymer composition, the polymer composition comprising a neutralized poly(vinyl glyoxylic acid), the particle comprising convoluted surface morphology features, the particle made by the method comprising:

a. forming a hydrogel comprising the polymer composition and water;

b. washing the hydrogel with a water miscible solvent or a solvent mixture, the solvent mixture comprising a water miscible solvent; and

c. evaporating at least a portion of the water miscible solvent or the mixture.

37. The particle of claim 36, wherein the solvent mixture further comprises water.

38. A coating comprising a polymer composition, the polymer composition comprising a neutralized poly(vinyl glyoxylic acid), the coating comprising convoluted surface morphology features, the coating made by the method comprising:

a. coating a reaction mixture onto a substrate, the reaction mixture comprising a mixture of about 5 wt % to 25 wt % polyvinyl alcohol in water and one or more glyoxylate derivatives;

b. evaporating at least a portion of the water;

c. contacting the coated reaction mixture with a base to form a polymer composition;

d. washing the polymer composition with a water miscible solvent or a solvent mixture, the solvent mixture comprising a water miscible solvent; and

e. evaporating at least a portion of the water miscible solvent or the mixture.

39. The particle of claim 38, wherein the solvent mixture further comprises water.

40. A polymer composition comprising the reaction product of a glyoxylate derivative and a polyvinyl alcohol, wherein the polymer composition is capable of forming a hydrogel with an aqueous liquid, the dry polymer composition having an absorption capacity of about 16 to 50 g of 0.9 wt % NaCl solution per gram of the dry polymer composition and is capable of an initial rate of absorption of about 1 to 25 g of 0.9 wt % NaCl solution per gram of dry polymer composition per minute.

41. The polymer composition of claim 40 wherein the polyvinyl alcohol comprises an alcoholyzed polyvinyl acetate having a molecular weight of between about 10,000 g/mol and 3,000,000 g/mol, wherein about 80% to 100% of the acetate groups are alcoholyzed to hydroxyl groups.

42. The polymer composition of claim 41 wherein the polyvinyl alcohol has a molecular weight of between about 10,000 g/mol and 250,000 g/mol.

43. The polymer composition of claim 41 wherein about 95% to 99% of the acetate groups are alcoholyzed to hydroxyl groups.

44. The polymer composition of claim 40 wherein between about 30% and 90% of the hydroxyl groups of the polyvinyl alcohol are reacted with the glyoxylate derivative.

45. The polymer composition of claim 40 wherein between about 50% and 75% of the hydroxyl groups of the polyvinyl alcohol are reacted with the glyoxylate derivative.

46. The polymer composition of claim 40 wherein the glyoxylate derivative comprises sodium glyoxylate, potassium glyoxylate, glyoxylic acid, or a combination of two or more thereof.

47. The polymer composition of claim 40 wherein the reaction product further comprises crosslinks attributable to a dialdehyde.

48. The polymer composition of claim 47 wherein the dialdehyde is glyoxal or glutaraldehyde.

49. The polymer composition of claim 40 wherein the polymer composition comprises a coating, a sheet, or a fiber.

50. The polymer composition of claim 40 wherein the polymer composition comprises a particle comprising a particle size of between about 50 nanometers and 3 millimeters and a water content of less than about 5 wt %.

51. The polymer composition of claim 50 wherein the particle comprises a particle size of between about 100 micrometers and 1 millimeter.

52. The polymer composition of claim 40 wherein the polymer composition comprises convoluted surface morphology features.

53. A formulation comprising the polymer composition of claim 40 and one or more formulation components, the formulation components comprising solvents, aqueous liquids, surfactants, aqueous solvent mixtures, celluloses, starches, lignins, polysaccharides, clays, micas, drilling fluids, insecticides, herbicides, fertilizers, fragrances, drugs, fire-retardant agents, personal care formulation components, coating additives, cyclodextrins, fillers, adjuvants, thermal stabilizers, UV stabilizers, colorants, acidulants, metals, microorganisms, spores, encapsulated organic acids, mixtures thereof, and combinations of two or more thereof.

54. An article comprising the polymer composition of claim 40, wherein the article is a diaper for an infant, an adult protective undergarment or incontinence undergarment, a feminine sanitary napkin, an underground power or communications cable, a horticultural water retention agent, control agent for aqueous fluid spill or effluent, a carrier for controlled release of insecticides, herbicides, fragrances, or drugs, a drilling fluid additive, a fire-retardant gel, a mortuary pad, a surgical pad, a wound dressing, a medical waste solidification article, an absorbent pad for food, a food packaging material, a cosmetic or personal care article, a sealing composite, a filter, a fuel monitor system for aviation and motor vehicles, a drown-free water source for caged insects, masking tape designed for use with latex paint, a hot/cold therapy pack, a motionless waterbed;

a grow-in-water toy, or artificial snow for motion picture and stage production, or a combination of two or more thereof.

55. A polymer composition comprising a neutralized poly(vinyl glyoxylic acid), the polymer composition made by the method comprising

a. combining about 5 wt % to 25 wt % polyvinyl alcohol in water with a mixture of glyoxylic acid and a glyoxylate salt to form a reaction mixture;

b. evaporating at least a portion of the water from the reaction mixture; and

c. contacting the reaction mixture with a base.

57. An article comprising the formulation of 53, wherein the article is a diaper for an infant, an adult protective undergarment or incontinence undergarment, a feminine sanitary napkin, an underground power or communications cable, a horticultural water retention agent, control agent for aqueous fluid spill or effluent, a carrier for controlled release of insecticides, herbicides, fragrances, or drugs, a drilling fluid additive, a fire-retardant gel, a mortuary pad, a surgical pad, a wound dressing, a medical waste solidification article, an absorbent pad for food, a food packaging material, a cosmetic or personal care article, a sealing composite, a filter, a fuel monitor system for aviation and motor vehicles, a drown-free water source for caged insects, masking tape designed for use with latex paint, a hot/cold therapy pack, a motionless waterbed;

a grow-in-water toy, or artificial snow for motion picture and stage production, or a combination of two or more thereof.