# US 10,369,529 B2 · Mixed matrix membranes with embedded polymeric particles and networks and related compositions, methods, and systems > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,369,529 B2 - Document ID: US10369529B2 - Status: Granted - Kind: B2 - Application number: 14/447,574 - Filed: 2014-07-30 - Published: 2015-02-26 - Granted: 2019-08-06 - Earliest claimed: 2012-01-30 - Assignees: California Institute of Technology; Korea Advanced Institute of Science and Technology - Applicants: California Institute of Technology; Korea Advanced Institute of Science and Technology - Inventors: Mamadou S. Diallo; Madhusudhana Rao Kotte - Web page: https://patentgrep.com/patent/US10369529B2 ## CPC - B01D 69/141: {Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes} - B01D 67/00793: {Dispersing a component, e.g. as particles or powder, in another component} - B01D 69/1071: {Woven, non-woven or net mesh} - B01D 69/12: Composite membranes; Ultra-thin membranes - B01D 71/34: Polyvinylidene fluoride - B01D 71/4011: {Polymethylmethacrylate} - B01D 71/601: {Polyethylenimine} - 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)} - D01F 1/10: Other agents for modifying properties - B01D 2323/30: Cross-linking - B01D 2323/39: Electrospinning - C02F 1/441: {by reverse osmosis} - C02F 1/444: {by ultrafiltration or microfiltration} - C02F 2103/08: Seawater, e.g. for desalination - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes) - D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS ## 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 ### Claim 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. ### Claim 2 (depends on 1) 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. ### Claim 3 (depends on 2) 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 R1-R18 are independently selected from: hydrogen; C1-C20 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. ### Claim 4 (depends on 1) The filtration membrane according to claim 1, wherein the polymeric microparticles and/or nanoparticle comprises a cross-linked dendritic polymer. ### Claim 5 (depends on 4) 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; R1-R8 are independently selected from hydrogen or hyperbranched polymer moieties; X1 is N; and X2-X5 are selected from amine, amide, imide, and carbamate. ### Claim 6 (depends on 4) 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 R1-R4 can be independently hydrogen or hyperbranched polymer moieties. ### Claim 7 (depends on 4) 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 Q1 and Q2 comprises hyperbranched polymer moiety, and R is selected from hydrogen, an alkyl group, or a 2-hydroxyalkyl group. ### Claim 8 (depends on 4) The filtration membrane according to claim 4, wherein the crosslinked dendritic polymer is a polyimine. ### Claim 9 (depends on 8) The filtration membrane according to claim 8, wherein the polyimine is poly(ethyleneimine). ### Claim 10 (depends on 4) The filtration membrane according to claim 4, wherein the cross-linked dendritic polymer is present in a concentration of greater than about 20 weight %. ### Claim 11 (depends on 4) The filtration membrane according to claim 4, wherein the cross-linked dendritic polymer is present in a concentration of greater than about 40 weight %. ### Claim 12 (depends on 1) The filtration membrane according to claim 1, wherein the functionalizing polymer is a polymer of formula wherein: R18 and R19 are selected from in which Y2 is F, Cl, Br or I R32 is H or CH3 n1, l1, and k1 independently are integers ranging between 0-50; at least one of n1, l1, and k1 is not equal to zero; ji 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 n2 n3 n4 and n5=are independently 0 or 1; m2 m3 and m4 are independently an integer ranging from 0-15; Xi, X3 and X3 is a functional group comprising an atom selected from O, S, N, or P, and R20-R31 are independently selected from: a polymer component functional group; hydrogen; C1-C20 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). ### Claim 13 (depends on 12) 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. ### Claim 14 (depends on 12) The filtration membrane according to claim 12, wherein the functionalizing polymer is an epoxy resin. ### Claim 15 (depends on 1) 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. ### Claim 16 (depends on 15) 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. ### Claim 17 (depends on 15) A polymeric membrane obtained by the method of claim 15. ### Claim 18 (depends on 1) A bicomposite membrane comprising the filtration membrane of claim 1, wherein a plurality of nanofibers and/or microfibers are attached to the polymer matrix. ### Claim 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. ### Claim 20 (depends on 19) 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. ### Claim 21 (depends on 19) The filtration membrane of claim 19, wherein the plurality of nanofibers and/or microfibers are arranged in a substantially parallel configuration. ### Claim 22 (depends on 19) The filtration membrane of claim 19, wherein one or more nanofibers and/or microfibers of the plurality of the nanofibers or microfibers are hollow. ### Claim 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. ### Claim 24 (depends on 23) A polymeric membrane obtained by the method of claim 23.