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

Patent metadata

Field	Value
Publication number	US-10369529-B2
Application number	US-201414447574-A
Country	US
Kind code	B2
Filing date	Jul 30, 2014
Priority date	Jan 30, 2012
Publication date	Aug 6, 2019
Grant date	Aug 6, 2019

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.

First claim

The invention claimed is:

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):

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, 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 a polymer component functional group.

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

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: hydrogen; C 1 -C 20 linear, branched, saturated, unsaturated, or aryl hydrocarbon which are either substituted or unsubstituted with O, N, B, S, P; or substituted O, N, B, S, or P.

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)

wherein:
n and m are integers ranging from 2 to 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.

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

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

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

where n is an integer ranging from 2-5, each of Q 1 and Q 2 comprises hyperbranched polymer moiety, and R is selected from hydrogen, an alkyl group, or a 2-hydroxyalkyl group.

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

wherein:
R 18 and R 19 are selected from

in which Y2 is F, Cl, Br or I
R 32 is H or CH3

n 1 , l 1 , and k 1 independently are integers ranging between 0-50;
at least one of n 1 , l 1 , and k 1 is not equal to zero;
j i is an integer ranging between 50-500; and

and wherein
Q1, Y1, and Z1 independently comprise saturated aliphatic hydrocarbon, aromatic hydrocarbon, or unsaturated aliphatic hydrocarbons or are independently selected from the following formulas

in which
n 2 n 3 n 4 and n 5 =are independently 0 or 1;
m 2 m 3 and m 4 are independently an integer ranging from 0-15;
X i , X 3 and X 3 is a functional group comprising an atom selected from O, S, N, or P, and
R 20 -R 31 are independently selected from: a polymer component functional group; hydrogen; C 1 -C 20 linear, branched, saturated, unsaturated, or aryl hydrocarbon which are either substituted or unsubstituted with O, N, B, S, P; or substituted O, N, B, S, or P, Y2 or a group of Formulas (XXI) to (XXIV).

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 nanof

Assignees

• California Inst Of Techn
• Korea Advanced Inst Sci & Tech

Inventors

• Diallo Mamadou S
• Kotte Madhusudhana Rao

Classifications

• C02F1/444

  by ultrafiltration or microfiltration · CPC title

• C02F1/441

  by reverse osmosis · CPC title

• B01D71/34

  Polyvinylidene fluoride · CPC title

• B01D71/022

  Metals · CPC title

• B01D71/40

  Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters · CPC title