Articles Comprising a Fibrous Support

• US 20080149561A1
• Filed: 12/05/2007
• Published: 06/26/2008
• Est. Priority Date: 12/05/2006
• Status: Active Grant

• Current Assignee: The Research Foundation for The State University of New York (State University of New York)
• Original Assignee: The Research Foundation for The State University of New York (State University of New York)
• Inventors: Yoon, Kyunghwan, Chu, Benjamin, Hsiao, Benjamin
• Granted Patent: US 8,231,013 B2
• Time in Patent Office: Days
• US Class Current: 210/500.38
• CPC Class Codes: A61L 15/425 Porous materials, e.g. foams or sponges
• CPC Class Codes: A61L 2400/12 Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
• CPC Class Codes: A61L 27/56 Porous materials, e.g. foams or sponges
• CPC Class Codes: B01D 67/00412 by deposition of fibres, nanofibres or nanofibrils
• CPC Class Codes: B01D 69/107 Organic support material
• CPC Class Codes: B01D 69/1071 Woven, non-woven or net mesh
• CPC Class Codes: B01D 69/1216 Three or more layers
• CPC Class Codes: B01D 69/1251 by interfacial polymerisation
• CPC Class Codes: D01D 5/0084 Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses

Abstract

Articles comprising a fibrous support of nanofibers and an interfacially polymerized polymer layer disposed on a surface of the fibrous support are useful, e.g., as fluid separation membranes.

Claims

1. An article comprising:

a fibrous support comprising nanofibers; and

an interfacially polymerized polymer layer disposed on a surface of the fibrous support.

2. The article of claim 1, wherein the nanofibers have an average diameter ranging from about 2 nm to about 2000 nm.

3. The article of claim 1, wherein:

the fibrous support is in the form of a sheet comprising a top layer and a bottom layer;

the top layer is disposed between the interfacially polymerized polymer layer and the bottom layer;

each of the top and bottom layers is comprised of nanofibers; and

the average diameter of the nanofibers of the top layer is less than the average diameter of the nanofibers of the bottom layer.

4. The article of claim 3, wherein the average diameter of the nanofibers of the top layer ranges from about 2 nm to about 500 nm, and the average diameter of the nanofibers of the bottom layer ranges from about 500 nm to about 50 μ

m.

5. The article of claim 3, wherein the thickness of the interfacially polymerized polymer layer ranges from about 10 nm to about 500 nm, and the thickness of the fibrous support ranges from about 5 μ

m to about 50 μ

m.

6. The article of claim 3, wherein:

the fibrous support further comprises a middle layer comprised of nanofibers disposed between the top layer and bottom layer; and

the average diameter of the nanofibers of the middle layer is;

less than the average diameter of the nanofibers of the bottom layer, and

greater than the average diameter of the nanofibers of the top layer.

7. The article of claim 6, wherein the average diameter of the nanofibers of the top layer ranges from about 2 nm to about 500 nm, the average diameter of the nanofibers of the middle layer range from about 10 nm to about 500 nm, and the average diameter of the nanofibers of the bottom layer are 500 nm or more.

8. The article of claim 6, wherein the thickness of the interfacially polymerized polymer layer ranges from about 2 nm to about 500 nm, and the thickness of the fibrous support ranges from about 5 μ

m to about 50 μ

m.

9. The article of claim 3, further comprising a substrate layer disposed on the bottom layer, whereby the bottom layer is disposed between the substrate layer and the top layer.

10. The article of claim 9, wherein the substrate layer is a nonwoven fabric.

11. The article of claim 10, wherein the fibers of the nonwoven fabric comprise at least one material selected from the group consisting of poly(ethylene terephthalate), polypropylene, cellulose, polyamide, polyurethane, glass, inorganic fibers, and metallic fibers, their derivatives, and combinations thereof.

12. The article of claim 9, wherein the substrate layer has an average thickness of from about 20 μ

m to about 20 mm.

13. The article of claim 6, further comprising a woven or nonwoven substrate layer disposed on the bottom layer, whereby the bottom layer is disposed between the substrate layer and the middle layer.

14. The article of claim 1, wherein the nanofibers at the surface of the fibrous support penetrate the interfacially polymerized polymer layer from about 1% to about 100% of the thickness of the interfacially polymerized polymer layer.

15. The article of claim 1, wherein the interfacially polymerized polymer layer further comprises at least one hydrophilic or hydrophobic nanoparticulate filler.

16. The article of claim 15, wherein the nanoparticulate filler comprises at least one hydrophilic nanoparticulate filler selected from the group consisting of oxidized carbonaceous nanoparticles, surface grafted carbonaceous nanoparticles, water dispersible nanoclays, and combinations thereof.

17. The article of claim 16, wherein the nanoparticulate filler comprises an oxidized carbonaceous nanoparticle selected from the group consisting of oxidized single-walled carbon nanotubes, oxidized multi-walled carbon nanotubes, oxidized carbon nanofibers, and oxidized graphene sheets.

18. The article of claim 16, wherein the nanoparticulate filler comprises a carbonaceous nanoparticle surface grafted with oligomeric or polymeric water-soluble polymers;

and

the carbonaceous nanoparticles surface grafted with oligomeric or polymeric water-soluble polymers are selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, and graphene sheets.

19. The article of claim 16 wherein the nanoparticulate filler comprises a water dispersible nanoclay selected from the group consisting of lucentite and montmorillonite clays.

20. The article of claim 15, wherein the nanoparticulate filler comprises at least one hydrophobic nanoparticulate filler selected from the group consisting of carbonaceous nanoparticles, hydrophobically surface functionalized carbonaceous nanoparticles, nano-organoclays, and polyhedral oligomeric silsesquioxane caged molecules.

21. The article of claim 20, wherein the nanoparticulate filler comprises a carbonaceous nanoparticle selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, and graphene sheets.

22. The article of claim 20, wherein the nanoparticulate filler comprises a carbonaceous nanoparticle surface reacted with an acyl chloride;

and

the carbonaceous nanoparticles surface reacted with the acyl chloride are selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, and graphene sheets.

23. The article of claim 20, wherein the nanoparticulate filler comprises a nano-organoclay.

24. The article of claim 17, wherein the nanofiber filler has an average diameter of about 2 nm to about 2000 nm.

25. The article of claim 1, wherein the interfacially polymerized polymer layer further comprises a functionalized molecule.

26. The article claim 25, wherein the functionalized molecule is selected from the group consisting of a hydrophobic molecules, hydrophilic molecules, organic molecules, inorganic molecules, organic-inorganic polymer composites, antibodies, antigens, DNA, RNA, proteins, peptides, positively charged molecules, negatively charged molecules, amphiphilic molecules, and combinations thereof.

27. The article of claim 1, wherein the interfacially polymerized polymer layer comprises a polymer selected from the group consisting of a crosslinked or uncrosslinked polyamide, a crosslinked or uncrosslinked polyimide, a crosslinked or uncrosslinked polyester, a crosslinked or uncrosslinked polyurea, a crosslinked or uncrosslinked polyurethane, a crosslinked or uncrosslinked polysulfone, a crosslinked or uncrosslinked polycarbonate, derivatives thereof, and combinations thereof.

28. The article of claim 1, wherein the nanofibers comprise a polymer selected from the group consisting of polyolefins, polysulfones, polyethersulfones, fluoropolymers, polyvinylidene fluorides, polyesters, polyamides, polycarbonates, polystyrenes, polyacrylamides, polyacrylates, polyacrylonitriles, poly(meth)acrylates, polyvinyl acetates, polyvinyl alcohols, polysaccharides, chitosan, proteins, polyalkyleneoxides, polyurethanes, polyureas, polyvinyl chlorides, polyimines, polyvinylpyrrolidones, polyacrylic acids, polymethacrylic acids, polysiloxanes, poly(ester-co-glycol) polymers, poly(ether-co-amide) polymers, cross-linked forms thereof, derivatives thereof, and copolymers thereof.

29. The article of claim 28, wherein the nanofibers comprise polyamide, polyacrylonitrile, polysulfone, polyvinyl alcohol, or derivatives thereof.

30. The article of claim 28, wherein the nanofibers comprise a polymer functionalized with a hydrophilic group.

31. A membrane comprising the article of claim 1.

32. The membrane of claim 31, wherein the membrane is an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, or a forward osmosis membrane.

33. A membrane module comprising:

at least one membrane of claim 31;

means for contacting a fluid mixture with the surface of the interfacially polymerized polymer layer of the at least one membrane;

means for removing a retentate from the surface of the interfacially polymerized polymer layer; and

means for removing a permeate from the surface of the fibrous support opposite the surface of the fibrous support contacting the interfacially polymerized polymer layer.

34. The membrane module of claim 33, wherein the membrane module is a spiral wound membrane module or a flat sheet membrane module.

35. A fluid separation system comprising at least one membrane module of claim 33.

36. A fluid separation system comprising at least one membrane module of claim 34.

37. A method of making the article of claim 1, comprising:

forming a fibrous support comprising nanofibers;

depositing a first solution comprising at least one first polyfunctional monomer dissolved in a first solvent onto the fibrous support, thereby forming a fibrous support wetted with the first solution;

depositing a second solution comprising at least one second polyfunctional monomer dissolved in a second solvent onto the fibrous support wetted with the first solution,

wherein the at least one second polyfunctional monomers reacts with the at least one first polyfunctional monomer and the first solvent and second solvent are substantially immiscible in each other;

allowing the first polyfunctional monomer to react with the second polyfunctional monomer, thereby forming an interfacially polymerized polymer layer at the interface between the first solvent and the second solvent;

removing excess first and second polyfunctional monomers; and

removing the first and second solvents.

38. The method of claim 37, wherein said forming a fibrous support comprises electro-spinning, electro-blowing, blowing-assisted electro-spinning, solution blowing, and solution casting [nanofibers/polymer mixture suspensions].

39. The method of claim 38, wherein the fibrous support is formed on a substrate layer.

40. The method of claim 37, wherein:

said forming a fibrous support comprises forming at least two layers of nanofibers by sequentially forming each succeeding layer of nanofibers on a surface of a preceeding layer of nanofibers.

41. The method of claim 40, wherein the fibrous support comprises a top layer of nanofibers and a bottom layer of nanofibers;

the top layer of the fibrous support contacts the interfacially polymerized polymer layer and is disposed between the interfacially polymerized polymer layer and the bottom layer; and

the average diameter of the nanofibers in the top layer is less than the average diameter of the nanofibers on the bottom layer.

42. The method of claim 41, further comprising a middle layer of nanofibers disposed between the top layer of nanofibers and the bottom layer of nanofibers;

wherein the average diameter of the nanofibers in the middle layer is greater than the average diameter of the nanofibers in the top layer and less than the average diameter of the nanofibers in the bottom layer.

43. The method of claim 37, wherein said depositing a first solution comprises dipping the fibrous support into the first solution.

44. The method of claim 37, wherein said depositing a second solution comprises dipping the fibrous support wetted with the first solution into the second solution.

45. The method of claim 37, wherein the first solvent comprises water.

46. The method of claim 45, wherein the first polyfunctional monomer comprises at least one polyamine.

47. The method of claim 45, wherein the first solution further comprises a base.

48. The method of claim 45, wherein the first solution further comprises at least one hydrophilic additive.

49. The method of claim 48, wherein the hydrophilic additive is at least one compound selected from the group consisting of alcohols, polyols, polar aprotic solvents, ionic liquids.

50. The method of claim 49, wherein:

the alcohols are selected from the group consisting of methanol, ethanol, isopropanol, and mixtures thereof;

the polyols are selected from the group consisting of ethylene glycol, glycerol, saccharides, and mixtures thereof;

the polar aprotic solvents are selected from the group consisting of DMF, DMAc, DMSO, NMP, and mixtures thereof; and

the ionic liquids are N-alkylimidazolonium cations having the general formula 1-C_nH_2n+1-3-methylimidazolonium X⁻

, wherein n is an integer of from 1-12 and X⁻

is selected from the group consisting of PF₆⁻

, BF₄⁻

, Cl⁻

, and Br⁻

.

51. The method of claim 45, wherein the first solution further comprises at least one hydrophilic nanoparticulate filler.

52. The method of claim 51, wherein the hydrophilic nanoparticulate filler is selected from the group consisting of oxidized carbonaceous nanoparticles, surface grafted carbonaceous nanoparticles, water dispersible nanoclays, and combinations thereof.

53. The method of claim 46, wherein the polyamine is selected from the group consisting of aromatic polyamines, heteroaromatic polyamines, cyclic polyamines, aliphatic polyamines, and polyamino polyethers.

54. The method of claim 46, wherein the polyamine is selected from the group consisting of piperazine, 4,4′

-bipiperidine, phenylene diamine, diaminobenzoic acid, diaminobenzene sulfonic acid, bis-amino PEG, bis-amino PPG, bis-amino PEG/PPG copolymers, tris-amino PEG, tris-amino PPG, tris-amino PEG/PPG copolymers, salts thereof, and combinations thereof.

55. The method of claim 45, wherein the second solvent is substantially immiscible in water.

56. The method of claim 55, wherein the second solvent comprises a liquid hydrocarbon.

57. The method of claim 55, wherein the at least one second polyfunctional monomer comprises a poly(acid chloride), polyanhydride, or a polyisocyanate.

58. The method of claim 57, wherein the second solution comprises trimesoyl chloride dissolved in a liquid hydrocarbon.

59. The method of claim 55, wherein the second solution further comprises at least one hydrophilic nanoparticulate filler.

60. The method of claim 59, wherein the at least one hydrophilic nanoparticulate filler is selected from the group consisting of carbonaceous nanoparticles, hydrophobically surface functionalized carbonaceous nanoparticles, nano-organoclays, and polyhedral oligomeric silsesquioxane caged molecules.