IP Library Granted Patent US 10,532,330
Granted Patent B2
US 10,532,330 · App. 15/497,174 · Granted Jan 14, 2020

Filtration membranes, and related nano and/or micro fibers, composites, methods and systems

Inventors: Mamadou S. Diallo (Pasadena, CA); William A. Goddard, III (Pasadena, CA); Seong-Jik Park (Seoul, KR); Manki Cho (Changwon, KR)
Assignees: CALIFORNIA INSTITUTE OF TECHNOLOGY; KOREA ADVANCED INSTITUTE OF SCIENCE AND TECHNOLOGY
B01D71/82B01D63/021B01D69/08B01D69/087B01D69/12B01D69/125B01D71/76D01D5/0007D01F11/04B01D2323/39B01D2325/14B01D2325/16B01D2325/40Y10T428/249921Y10T442/10
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Quick Facts
Patent No.
US 10,532,330
App. No.
15/497,174
Granted
Jan 14, 2020
Kind
B2
Abstract

Filtration membrane comprising polymeric nanofibers and/or microfibers attaching dendrimer component presenting reactive sites selective for chemicals to be filtered, and related nanofibers and microfibers, composite materials, compositions, methods and system.

Claims (75)

1. A filtration membrane comprising:

a plurality of fibers comprising nanofibers, microfibers, or a combination thereof, each plurality of fibers having a polymer component and a dendrimer component,

wherein the polymer component provides a fiber scaffold and the dendrimer component is attached to the polymer component and presents reactive sites on the fiber scaffold, and

wherein the dendrimer component comprises dendrimers covalently cross-linked to one another to form water-insoluble dendritic particles.

2. The filtration membrane of claim 1 , wherein the plurality of fibers are arranged in a composite material layer having a mesh structure, the composite material layer comprised in the filtration membrane alone or in combination with one or more additional layers.

3. The filtration membrane of claim 2 , wherein the one or more additional layers comprise a supporting layer comprising a supporting layer polymer component, the supporting layer attached to the composite material layer.

4. The filtration membrane of claim 3 , wherein the supporting layer is functionalized with highly branched dendritic macromolecule or dendritic nanomaterial.

5. The filtration membrane of claim 2 , wherein the one or more additional layers comprise a coating layer attached to the composite material layer, the coating layer comprising a coating layer dendrimer component comprising cross linked highly branched dendritic macromolecule or dendritic nanomaterial.

6. The filtration membrane of claim 3 , wherein the composite material layer polymer component and the supporting layer polymer component are formed by a same polymer.

7. The filtration membrane of claim 5 , wherein the one or more additional layers further comprise a supporting layer polymer component attached to the coating layer and comprising dendritic nanomaterial.

8. The filtration membrane of claim 2 , further comprising a scaffold layer comprising nanofibers, microfibers, or a combination thereof including a polymer component and no dendrimer.

9. The filtration membrane of claim 2 , wherein the one or more additional layers comprise one or more composite material layers having a mesh structure, wherein the dendrimer component of the one or more composite material layers is either the same or different.

10. The filtration membrane of claim 1 , wherein the plurality of fibers are hollow fibers, arranged in a bundle configuration in which the fibers are substantially parallel one with another.

11. The filtration membrane of claim 1 , wherein the polymer component is selected from the group consisting of a substituted or unsubstituted aliphatic polymer, a substituted or unsubstituted unsaturated polymer and a substituted or unsubstituted aromatic polymer, and the dendrimer component is selected from a highly branched dendritic macromolecule or an aggregate nanostructure and/or microstructure thereof, wherein the polymer component and the dendrimer component are attached through binding of corresponding functional group forming a hydrogen bond or a covalent bond.

12. The filtration membrane of claim 1 , wherein the polymer component is selected from the group consisting of polysulfone (PS), polyether sulfone (PES), poly(vinylidene) fluoride (PVDF), poly(tetrafluoroethyelene) (PTFE), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(methacrylic acid) (PMAA), poly(acrylic acid) (PAA), poly(vinyl methyl ketone), and poly(ethylene terephthalate) (PET).

13. The filtration membrane of claim 11 , wherein the dendrimer component comprises one or more highly branched dendritic macromolecule selected from the group consisting of generation-3 poly(amidoamine) (PAMAM) dendrimer, generation-4 poly(amidoamine) (PAMAM) dendrimer, generation-5 poly(amidoamine) (PAMAM) dendrimer, generation-3 poly(propyleneimine) (PPI) dendrimer, generation-4 poly(propyleneimine) (PPI) dendrimer, generation-5 poly(propyleneimine) (PPI) dendrimer, generation-3 poly(bis(methylol)propionic acid) (MPA) dendrimer, generation-4 poly(bis(methylol)propionic acid) (MPA) dendrimer, generation-5 poly(bis(methylol)propionic acid) (MPA) dendrimer, generation-3 poly(ethyleneimine) dendrimer, generation-4 poly(ethyleneimine) dendrimer, generation-5 poly(ethyleneimine) dendrimer, and hyperbranched poly(ethyleneimine), or aggregate nanostructures and/or microstructure thereof.

14. The filtration membrane of claim 1 , wherein the reactive sites are selected to retain a chemical of interest.

15. The filtration membrane of claim 1 , wherein reactive sites are selected to reject a chemical of interest.

16. The filtration membrane of claim 1 , wherein the reactive sites are electrically charged.

17. A nanofiber or microfiber comprising:

a polymeric component providing a fiber scaffold; and

a dendrimer component attached to the polymeric component to present reactive sites on the fiber scaffold,

wherein the dendrimer component comprises dendrimers covalently cross-linked to one another to form water-insoluble dendritic particles.

18. The nanofiber or microfiber of claim 17 , wherein the dendrimer component is formed by one or more highly branched dendritic macromolecules, aggregate nanostructures, microstructure or combinations thereof.

19. The nanofiber or microfiber of claim 17 , wherein the dendrimer component attaches the polymer component through hydrogen bond between corresponding functional groups in the dendrimer component and in the polymer component.

20. The nanofiber or microfiber of claim 17 , wherein the dendrimer component attaches the polymer component through covalent bond between corresponding functional groups in the dendrimer component and in the polymer component.

21. The nanofiber or microfiber of claim 17 , wherein the polymer component has a formula:

wherein:

Q, Y, and Z comprise saturated aliphatic hydrocarbon, aromatic hydrocarbon, or unsaturated aliphatic hydrocarbons;

m, l, and k independently are integers ranging between 0-50;

at least one of m, l, or k is not equal to zero;

j is an integer ranging between 50-500; and

at least one of Q (when Q≠0), Y (when Y≠0), or Z (when Z≠0), comprises the polymer component functional group.

22. The nanofiber or microfiber of claim 21 , wherein Q, Y, and Z are independently selected from the following formulas:

wherein:

n=0 or 1;

m is an integer ranging from 0-15;

X is a functional group comprising an atom selected from O, S, N, P, or F; and

R 1 -R 18 are independently selected from: the polymer component functional group; hydrogen; C1-C20 linear, branched, saturated, unsaturated, or aryl hydrodrocarbon which are either substituted or unsubstituted with O, N, B, S, P; or substituted O, N, B, S, or P

at least one of R 1 -R 18 the polymer component functional group.

23. The nanofiber or microfiber of claim 17 , wherein the polymer component comprises polysulfone (PS), polyether sulfone (PES), poly(vinylidene) fluoride (PVDF), poly(tetrafluoroethyelene) (PTFE), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(methacrylic acid) (PMAA), poly(acrylic acid) (PAA), and/or poly(vinyl methyl ketone).

24. The nanofiber or microfiber of claim 17 , wherein the dendrimer component has a formula:

wherein:

n and m are integers ranging from 2-5;

R 1 -R 8 are independently selected from hydrogen or hyperbranched polymer moieties;

X 1 is N; and

X 2 -X 5 are selected from amine, amide, imide, and carbamate.

25. The nanofiber or microfiber of claim 24 , wherein the dendrimer component further comprises a second dendrimer component of formula (XIII), or a third dendrimer component of formula (XIV), or a combination thereof

wherein n and m are integers ranging from 2-5, and wherein R 1 -R 4 can be independently selected from hydrogen or hyperbranched polymer moieties.

26. The nanofiber or microfiber of claim 17 , wherein the dendrimer component comprises polyethyleneimine (PEI).

27. The nanofiber or microfiber of claim 17 , wherein the reactive sites are positively charged, negatively charged, or a combination of positively charged and negatively charged reactive sites.

28. The nanofiber or microfiber of claim 17 , wherein the reactive sites comprise N donors, 0 donors, S donors or a combination thereof.

29. The nanofiber or microfiber of claim 17 , wherein the reactive sites comprise functional groups selected from the group consisting of amines, quaternary ammonium groups, amides, hydroxyl groups, ethers, carboxylates, esters, sulfonates, sulfiniates, sulfonate esters, sulfinate esters, sulfonamides, phosphates, carbamates, ureas, imidines, guanidines, oximes, imidazoles, pyridines, thiols, thioethers, and thiocarboxylates.

30. A composite material comprising:

a plurality of the nanofibers or microfibers of claim 17 .

31. The composite material of claim 30 , wherein the plurality of nanofibers or microfibers are arranged in a mesh structure or in a bundle configuration in which the plurality of nanofibers or microfibers or a combination thereof are substantially parallel one with the another.

32. A filtration system comprising:

at least one filtration membrane according to claim 1 selective for a first chemical in combination with one or more additional filtration membranes, each selective for the first chemical, an additional chemical, or combinations thereof.

33. The filtration system of claim 32 , wherein the at least one filtration membrane and the one or more additional filtration membranes are arranged in units, wherein a first unit comprises an alternating series of membranes configured to reject cations and membranes configured to reject anions, and a second unit comprises a parallel series of membranes configured to absorb ions of interest.

34. The filtration system of claim 32 , wherein the at least one filtration membrane and/or the one or more additional filtration membranes comprise a plurality of nanofibers, a plurality of microfibers or a plurality of nanofibers or microfibers, arranged in a mesh structure or in a bundle configuration in which the plurality of fibers are substantially parallel with each other.

35. A process for manufacturing a composite material comprising:

aggregating a plurality of nanofibers or microfibers according to claim 17 in a mesh structure or in a bundle configuration in which the nanofibers or microfibers are substantially parallel one with each other.

36. The process of claim 35 , wherein the aggregating the plurality of nanofibers or microfibers in a mesh structure is performed by

mixing a polymeric component dissolved in a suitable solvent with a dendritic component dissolved in a suitable solvent, and

applying an electrical charge to the liquid mixture of polymeric components and dendritic components until a continuous stream of the liquid mixture of polymeric components and dendritic components is pulled to a rotating collector having an electrical charge opposite that of the liquid mixture of polymeric components and dendritic components such that the continuous stream forms a mesh of nanofibers.

37. A filtration method comprising:

filtering a liquid through a filtration membrane of claim 1 .

38. The filtration method of claim 37 , wherein the filtration membrane is formed by a plurality of filtration membranes each selective for one or more chemicals and the filtering is performed by passing the liquid through the plurality of filtration membranes to remove and/or absorb the one or more chemicals in a controlled fashion.

39. The filtration method of claim 38 , wherein at least one of the plurality of filtration membranes comprises electrically charged reactive sites and the filtering is performed by passing the liquid through the plurality of filtration membranes to remove or absorb electrically charged chemicals.

40. The filtration method of claim 38 , wherein the at least one of the plurality of filtration membranes comprises alternating positive and negative charged filtration membranes arranged in a configuration suitable to remove charged chemicals from the liquid.

41. The filtration method of claim 38 wherein the at least one of the plurality of filtration membranes comprises alternating positive and negative charged filtration membranes arranged in a configuration suitable to absorb charged chemicals from the liquid.

42. The filtration method of claim 37 , further comprising filtering the liquid through one or more conventional nanofiltration membranes to remove particles and dissolved organic matter.

43. The filtration method of claim 37 , wherein the liquid is water.

44. The filtration membrane of claim 1 , wherein the dendrimer component is attached to a surface of the polymeric component to present reactive sites on the fiber scaffold.

45. The filtration membrane of claim 1 , wherein the dendritic particles have an average particle size larger than 300 nm.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 10, 2018
From: GODDARD, WILLIAM A., III
To: CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 045774/0706 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 10, 2018
From: DIALLO, MAMADOU S.
To: CALIFORNIA INSTITUTE OF TECHNOLOGY; KOREA ADVANCED INSTITUTE OF SCIENCE AND TECHNOLOGY
Reel/Frame 045774/0771 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 10, 2018
From: PARK, SEONG-JIK; CHO, MANKI
To: KOREA ADVANCED INSTITUTE OF SCIENCE AND TECHNOLOGY
Reel/Frame 045774/0828 →
CONFIRMATORY LICENSE Recorded Apr 27, 2017
From: CALIFORNIA INSTITUTE OF TECHNOLOGY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 042163/0663 →
Continuity (5)
Continuation 13570221 · Aug 8, 2012
Provisional Application 61601410 · Feb 21, 2012
Provisional Application 61592409 · Jan 30, 2012
Provisional Application 61521290 · Aug 8, 2011
Related Publication 20180071693A1 · Mar 15, 2018
Cited By (34)
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