Mixed matrix membranes with embedded polymeric particles and networks and related compositions, methods, and systems

• US 10,369,529 B2
• Filed: 07/30/2014
• Issued: 08/06/2019
• Est. Priority Date: 01/30/2012
• Status: Active Grant

• Current Assignee: California Institute of Technology, Korea Advanced Institute of Science and Technology
• Original Assignee: California Institute of Technology
• Inventors: Diallo, Mamadou S., Kotte, Madhusudhana Rao
• Primary Examiner(s): Stelling, Lucas A
• Application Number:
  US14/447,574
• Publication Number:
  US 20150053610A1
• Time in Patent Office: 1,833 Days
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 2323/39 Electrospinning
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 69/1071 Woven, non-woven or net mesh
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 71/34 Polyvinylidene fluoride
• CPC Class Codes: B01D 71/4011 Polymethylmethacrylate
• CPC Class Codes: B01D 71/601 Polyethylenimine
• CPC Class Codes: C02F 1/44 by dialysis, osmosis or reverse osmosis general membrane separation processes B01D61/00, membrane modules B01D63/00, electrodialysis C02F1/4693, combination of membrane modules and bioreactors C02F3/1268
• CPC Class Codes: C02F 1/441 by reverse osmosis
• CPC Class Codes: C02F 1/444 by ultrafiltration or microfiltration
• CPC Class Codes: C02F 2103/08 Seawater, e.g. for desalination
• CPC Class Codes: D01F 1/10 Other agents for modifying properties

Abstract

Described herein are mixed matrix filtration membranes and related, compositions, methods and systems and in particular mixed matrix filtration membranes with an embedded polymer network and/or embedded polymeric micro/nanoparticles functionalized with a functionalization polymer covalently and/or non covalently linked to the micro/nanoparticles and related compositions, methods, and systems.

Claims

1. A filtration membrane comprising:

hyperbranched polymeric molecules covalently cross-linked to form polymeric microparticles and/or nanoparticles embedded in a polymer matrix

wherein the polymer matrix comprises a porous polymeric aggregate formed by a base polymer and a polymeric network formed by a functionalizing polymer; and

wherein the polymeric microparticles and/or nanoparticles are attached to the functionalizing polymer forming the polymeric network of the polymer matrix.

2. The filtration membrane according to claim 1, wherein the porous polymeric aggregate is formed by a polymer according to Formula (I):

3. The filtration membrane according to claim 2, wherein Q, Y, and Z are independently selected from the group consisting of Formulas II-XI:

4. The filtration membrane according to claim 1, wherein the polymeric microparticles and/or nanoparticle comprises a cross-linked dendritic polymer.

5. The filtration membrane according to claim 4, wherein the crosslinked dendritic polymer is a dendritic macromolecule according to general formula (XI)

6. The filtration membrane according to claim 4, wherein the crosslinked dendritic polymer is a dendritic macromolecule according to general formulas XII and XIII:

7. The filtration membrane according to claim 4, wherein the crosslinked dendritic polymer is a dendritic macromolecule according to general formula:

8. The filtration membrane according to claim 4, wherein the crosslinked dendritic polymer is a polyimine.

9. The filtration membrane according to claim 8, wherein the polyimine is poly(ethyleneimine).

10. The filtration membrane according to claim 4, wherein the cross-linked dendritic polymer is present in a concentration of greater than about 20 weight %.

11. The filtration membrane according to claim 4, wherein the cross-linked dendritic polymer is present in a concentration of greater than about 40 weight %.

12. The filtration membrane according to claim 1, wherein the functionalizing polymer is a polymer of formula

13. The filtration membrane according to claim 12, wherein the functionalizing polymer is selected from is a diacrylate, dimethacrylate, diepoxide, dihalide, diisocyanate, diacyl halide, triacyl halides, and dianhydride.

14. The filtration membrane according to claim 12, wherein the functionalizing polymer is an epoxy resin.

15. A method of making a filtration membrane with embedded dendritic nanoparticles according to claim 1, the method comprising:

providing a base polymer substantially soluble in a base polymer solvent;

providing a particle precursor having a portion substantially soluble in the base polymer solvent and a portion substantially insoluble in the base polymer solvent the polymeric particle precursor able to provide a dispersion of segregated domains in the base polymer solvent;

mixing a base polymer with a polymer particle precursor, and the base polymer solvent to provide a blend;

mixing the blend with a functionalizing polymer and a crosslinker and/or an initiator capable of reacting with the polymer particle precursor, for a time and under a condition to permit the in situ formation of covalently crosslinked dendritic polymer microparticles and/or nanoparticles and attaching the functionalizing polymer thus providing a dope solution; and

casting the dope solution to provide a filtration membrane with embedded dendritic molecules covalently cross-linked to form polymeric microparticles and/or nanoparticles.

16. The method of claim 15, wherein contacting the blend is performed by

mixing the blend with the crosslinker and/or an initiator capable of reacting with the polymer particle precursor, and

mixing the blend comprising the crosslinker and/or an initiator capable of reacting with the polymer particle precursor, with the functionalizing polymer to provide the dope solution.

17. A polymeric membrane obtained by the method of claim 15.

18. A bicomposite membrane comprising the filtration membrane of claim 1, wherein a plurality of nanofibers and/or microfibers are attached to the polymer matrix.

19. A filtration membrane comprising

a plurality of nanofibers and/or micro fibers each nanofiber comprising polymeric nanoparticles embedded therein, each microfiber comprising polymeric nanoparticles and/or microparticles embedded therein, the polymer nanoparticles and/or microparticles formed by hyperbranched polymeric molecules covalently cross-linked;

wherein each nanofiber and microfiber of the plurality of nanofibers and/or micro fibers comprises a base polymer and a functionalizing polymer, the functionalizing polymer attaching the polymeric nanoparticles and/or microparticles to form a polymeric network in the nanofibers and/or micro fibers; and

wherein the polymeric nanoparticles and/or microparticles and/or polymeric network present a reactive site on the nanofibers and/or micro fibers to allow selective filtration of a chemical capable of interaction with the reactive site.

20. The filtration membrane of claim 19, wherein the plurality of nanofibers and/or microfibers is arranged in a mesh structure forming a layer comprised in the membrane, alone or in combination with additional layers.

21. The filtration membrane of claim 19, wherein the plurality of nanofibers and/or microfibers are arranged in a substantially parallel configuration.

22. The filtration membrane of claim 19, wherein one or more nanofibers and/or microfibers of the plurality of the nanofibers or microfibers are hollow.

23. A process for providing a nanofiber or microfiber comprising

providing a base polymer substantially soluble in a base polymer solvent;

providing a particle precursor having a portion substantially soluble in the base polymer solvent and a portion substantially insoluble in the base polymer solvent the polymeric particle precursor able to provide a dispersion of segregated domains in the base polymer solvent

mixing a base polymer with a polymer particle precursor, and the base polymer solvent to provide a blend,

mixing the blend with a functionalizing polymer and a crosslinker and/or an initiator capable of reacting with the polymer particle precursor, for a time and under a condition to permit the in situ formation of covalently crosslinked dendritic polymer microparticles and/or nanoparticles and attaching the functionalizing polymer thus providing a dope solution; and

electrospraying and/or electrospinning the liquid mixture to provide a nanofiber or microfiber having embedded therein polymer nanoparticles and/or microparticles formed by dendritic polymeric molecules covalently crosslinked.

24. A polymeric membrane obtained by the method of claim 23.