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

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 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 .