# US 2019/0169416 A1 · Fabricating ionic/polyimide membranes > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0169416 A1 - Document ID: US20190169416A1 - Status: Published application - Kind: A1 - Application number: 16/322,051 - Filed: 2017-07-31 - Published: 2019-06-06 - Earliest claimed: 2016-08-05 - Assignees: The Board of Regents of the Nevada System of Higher Education on Behalf of the University of Ne - Applicants: The Board of Regents of the Nevada System of Higher Education On Behalf of the University of Ne - Inventors: Kwang Jin KIM; Dong-Chan LEE; Jungsoo NAM; Tae Seon HWANG - Web page: https://patentgrep.com/patent/US20190169416A1 ## CPC - C08L 27/22: modified by chemical after-treatment - B01D 53/22: by diffusion (manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00) - B01D 67/0088: {Physical treatment with compounds, e.g. swelling, coating or impregnation} - B01D 67/009: {with wave-energy, particle-radiation or plasma} - B01D 67/0093: {Chemical modification} - B01D 69/02: characterised by their properties - B01D 71/36: Polytetrafluoroethylene - B01D 71/64: Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors - C08J 5/225: {containing fluorine} - C08J 5/2268: {based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds, and by reactions not involving this type of bond} - C08J 5/2281: {fluorine containing heterogeneous membranes} - C08J 5/2293: {After-treatment of fluorine-containing membranes} - C08L 79/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors - B01D 53/228: {characterised by specific membranes} - B01D 67/0086: {Mechanical after-treatment} - B01D 71/32: containing fluorine atoms - B01D 2325/14: Membrane materials having negatively charged functional groups - B01D 2325/42: Ion-exchange membranes - C08J 2327/18: Homopolymers or copolymers of tetrafluoroethylene - C08J 2327/22: modified by chemical after-treatment - C08J 2379/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors - C08J 2427/18: Homopolymers or copolymers of tetrafluoroethylene - C08J 2479/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors - C08L 2203/20: use in electrical or conductive gadgets - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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) - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract Disclosed are polyimide blends and methods of making and using same. The disclosed polyimide blends are prepared by first blending an ionic polymer and a poly(amic acid) to form a poly(amic acid) precursor, followed by cyclization. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention. ## Claims ### Claim 1 A method of making a polyimide blend, the method comprising: a) mixing an ionic polymer selected from a perfluorinated ionomer membrane, a poly(acrylic acid) salt, sulfonated polystyrene, sulfonated poly(arylene ether sulfone), sulfonated poly(arylene thioether sulfone), cross-linked poly(styrene-ran-ethylene), sulfonated poly(styrene-b-ethylene-co-butylene-b-styrene), poly(fluoroalkyl methyacrylate-co-acrylic acid), poly(fluoroalkyl methacrylate-co-2-acylamido-2-methyl-1-propanesulfonic acid), poly(fluoroalkyl methacrylate-co-sulfonic acid), poly(fluoroalkyl methacrylate-co-sulfonic acid-co-2-hydroxyethyl methacrylate), poly(vinylidene-g-sulfonated N-ethylenecarbazole), poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethylene-co-tetrafluoroethylene), and Nafion, and a poly(amic acid) comprising at least one residue having a structure represented by a formula selected from: wherein comprises a structure represented by a formula selected from: wherein n is an integer greater than 1; wherein m is 0 or 1; wherein A is selected from —Ar1— and a structure represented by a formula: wherein Z, when present, is selected from O, NR3, CR4aR4b, CO, and SO2; wherein each of R3, R4a, and R4b, when present, is independently selected from hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl; wherein Ar1, when present, is selected from aryl, 5-membered heteroaryl, and 6-membered heteroaryl and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —OH, —CN, —NH2, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy; wherein each of Ar2 and Ar3, when present, is independently selected from aryl, 5-membered heteroaryl, and 6-membered heteroaryl and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —OH, —CN, —NH2, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy; wherein Q, when present, is selected from O, NR1, SO, SO2, C(O), and CR2aR2b; and wherein each of R1, R2a, and R2b, when present, is independently selected from hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl, thereby making a poly(amic acid) blend; and b) cyclizing the poly(amic acid) blend. ### Claim 2 (depends on 1) The method of claim 1, wherein the ionic polymer is Nafion. ### Claim 3 (depends on 1) The method of claim 1, wherein n is greater than 10,000. ### Claim 4 (depends on 1) The method of claim 1, wherein the poly(amic acid) comprises at least one residue having a structure represented by a formula: ### Claim 5 (depends on 1) The method of claim 1, wherein the poly(amic acid) comprises at least one residue having a structure represented by a formula: ### Claim 6 (depends on 1) The method of claim 1, wherein the poly(amic acid) comprises at least one residue having a structure: ### Claim 7 (depends on 1) The method of claim 1, wherein the poly(amic acid) comprises at least one residue having a structure: ### Claim 8 (depends on 1) The method of claim 1, wherein the poly(amic acid) is present in solution. ### Claim 9 (depends on 7) The method of claim 7, wherein the poly(amic acid) solution is present in an amount of from about 20 wt % to about 50 wt %. ### Claim 10 (depends on 7) The method of claim 7, wherein the poly(amic acid) solution comprises an aprotic polar solvent. ### Claim 11 (depends on 10) The method of claim 10, wherein the aprotic polar solvent is selected from N,N-dimethylformamide and N-methyl-2-pyrrolidone. ### Claim 12 (depends on 10) The method of claim 10, wherein the aprotic polar solvent is present in an amount of from about 95 wt % to about 99 wt % of the poly(amic acid) solution. ### Claim 13 (depends on 10) The method of claim 10, wherein the aprotic polar solvent is present in an amount of about 95 wt % of the poly(amic acid) solution. ### Claim 14 (depends on 1) The method of claim 1, wherein the ionic polymer is present in solution and the poly(amic acid) is present in solution, and wherein the ionic polymer and the poly(amic acid) together have a concentration of from about 0.01 g/mL to about 6 g/mL. ### Claim 15 (depends on 1) The method of claim 1, wherein the ionic polymer is present in solution and the poly(amic acid) is present in solution, and wherein the ionic polymer and the poly(amic acid) together have a concentration of from about 0.03 g/mL to about 6 g/mL. ### Claim 16 (depends on 1) The method of claim 1, wherein mixing is blending. ### Claim 17 (depends on 1) The method of claim 1, wherein mixing is solution-casting. ### Claim 18 (depends on 17) The method of claim 17, wherein solution-casting is performed at a temperature of from about 50° C. to about 100° C. ### Claim 19 (depends on 17) The method of claim 17, wherein solution-casting is performed at a temperature of from about 40° C. to about 90° C. ### Claim 20 (depends on 1) The method of claim 1, wherein cyclizing is via heat. ### Claim 21 (depends on 20) The method of claim 20, wherein the heat is applied at a temperature of from about 180° C. to about 250° C. ### Claim 22 (depends on 20) The method of claim 20, wherein the heat is applied for from about 12 h to about 36 h. ### Claim 23 (depends on 20) The method of claim 20, wherein the heat is applied under vacuum, nitrogen, or helium. ### Claim 24 (depends on 1) The method of claim 1, wherein the polyimide blend comprises a polyimide comprising at least one residue having a structure represented by a formula: ### Claim 25 (depends on 24) The method of claim 24, wherein the polyimide comprises at least one residue having a structure represented by a formula: ### Claim 26 (depends on 24) The method of claim 24, wherein the polyimide comprises at least one residue having a structure represented by a formula: ### Claim 27 (depends on 24) The method of claim 24, wherein the polyimide comprises at least one residue having a structure: ### Claim 28 (depends on 24) The method of claim 24, wherein the polyimide is present in an amount of from about 6 wt % to about 30 wt %. ### Claim 29 (depends on 24) The method of claim 24, wherein the polyimide is present in an amount of from about 18 wt % to about 20 wt %. ### Claim 30 (depends on 1) The method of claim 1, further comprising plating a metal electrode onto the polyimide blend. ### Claim 31 (depends on 30) The method of claim 30, wherein the metal is Pt. ### Claim 32 (depends on 30) The method of claim 30, further comprising modifying at least one surface of a polymeric membrane with the polyimide blend. ### Claim 33 (depends on 32) The method of claim 32, wherein modifying is via a bond. ### Claim 34 (depends on 32) The method of claim 32, wherein modifying comprises coating the surface with the polyimide blend. ### Claim 35 (depends on 32) The method of claim 32, wherein modifying comprises exposing the surface to a light source. ### Claim 36 (depends on 1) The method of claim 1, further comprising modifying at least one surface of a polymeric membrane with the polyimide blend. ### Claim 37 (depends on 36) The method of claim 36, wherein modifying is via covalent bonding. ### Claim 38 (depends on 36) The method of claim 36, wherein modifying comprises coating the surface with the polyimide blend. ### Claim 39 (depends on 36) The method of claim 36, wherein modifying comprises exposing the surface to a light source. ### Claim 40 A poly(amic acid) blend comprising: a) an ionic polymer selected from a perfluorinated ionomer membrane, a poly(acrylic acid) salt, sulfonated polystyrene, sulfonated poly(arylene ether sulfone), sulfonated poly(arylene thioether sulfone), cross-linked poly(styrene-ran-ethylene), sulfonated poly(styrene-b-ethylene-co-butylene-b-styrene), poly(fluoroalkyl methyacrylate-co-acrylic acid), poly(fluoroalkyl methacrylate-co-2-acylamido-2-methyl-1-propanesulfonic acid), poly(fluoroalkyl methacrylate-co-sulfonic acid), poly(fluoroalkyl methacrylate-co-sulfonic acid-co-2-hydroxyethyl methacrylate), poly(vinylidene-g-sulfonated N-ethylenecarbazole), poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethylene-co-tetrafluoroethylene), and Nafion; and b) a poly(amic acid) comprising at least one residue having a structure represented by a formula selected from: wherein comprises a structure represented by a formula selected from: wherein n is an integer greater than 1; wherein m is 0 or 1; wherein A is selected from —Ar1— and a structure represented by a formula: wherein Z, when present, is selected from O, NR3, CR4aR4b, CO, and SO2; wherein each of R3, R4a, and R4b, when present, is independently selected from hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl; wherein Ar1, when present, is selected from aryl, 5-membered heteroaryl, and 6-membered heteroaryl and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —OH, —CN, —NH2, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy; wherein each of Ar2 and Ar3, when present, is independently selected from aryl, 5-membered heteroaryl, and 6-membered heteroaryl and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —OH, —CN, —NH2, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy; wherein Q, when present, is selected from O, NR1, SO, SO2, C(O), and CR2aR2b; and wherein each of R1, R2a, and R2b, when present, is independently selected from hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl. ### Claim 41 A polyimide blend comprising: a) an ionic polymer selected from a perfluorinated ionomer membrane, a poly(acrylic acid) salt, sulfonated polystyrene, sulfonated poly(arylene ether sulfone), sulfonated poly(arylene thioether sulfone), cross-linked poly(styrene-ran-ethylene), sulfonated poly(styrene-b-ethylene-co-butylene-b-styrene), poly(fluoroalkyl methyacrylate-co-acrylic acid), poly(fluoroalkyl methacrylate-co-2-acylamido-2-methyl-1-propanesulfonic acid), poly(fluoroalkyl methacrylate-co-sulfonic acid), poly(fluoroalkyl methacrylate-co-sulfonic acid-co-2-hydroxyethyl methacrylate), poly(vinylidene-g-sulfonated N-ethylenecarbazole), poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethylene-co-tetrafluoroethylene), and Nafion; and b) a polyimide comprising at least one residue having a structure represented by a formula: wherein comprises a structure represented by a formula selected from: wherein n is an integer greater than 1; wherein m is 0 or 1; wherein A is selected from —Ar1— and a structure represented by a formula: wherein Z, when present, is selected from O, NR3, CR4aR4b, CO, and SO2; wherein each of R3, R4a, and R4b, when present, is independently selected from hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl; wherein Ar1, when present, is selected from aryl, 5-membered heteroaryl, and 6-membered heteroaryl and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —OH, —CN, —NH2, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy; wherein each of Ar2 and Ar3, when present, is independently selected from aryl, 5-membered heteroaryl, and 6-membered heteroaryl and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —OH, —CN, —NH2, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy; wherein Q, when present, is selected from O, NR1, SO, SO2, C(O), and CR2aR2b; and wherein each of R1, R2a, and R2b, when present, is independently selected from hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl.