[go: up one dir, main page]

WO2024132498A1 - Membranes - Google Patents

Membranes Download PDF

Info

Publication number
WO2024132498A1
WO2024132498A1 PCT/EP2023/084300 EP2023084300W WO2024132498A1 WO 2024132498 A1 WO2024132498 A1 WO 2024132498A1 EP 2023084300 W EP2023084300 W EP 2023084300W WO 2024132498 A1 WO2024132498 A1 WO 2024132498A1
Authority
WO
WIPO (PCT)
Prior art keywords
optionally substituted
group
formula
anion exchange
exchange membrane
Prior art date
Application number
PCT/EP2023/084300
Other languages
English (en)
Inventor
Jacko Hessing
Elisa Huerta Martinez
Original Assignee
Fujifilm Manufacturing Europe Bv
Fujifilm Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Manufacturing Europe Bv, Fujifilm Corporation filed Critical Fujifilm Manufacturing Europe Bv
Publication of WO2024132498A1 publication Critical patent/WO2024132498A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C08F12/28—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

  • Ion exchange membranes are used in electrodialysis, electrolysis, production of acids and bases and a number of other processes. Typically the transport of ions through the membranes occurs under the influence of a driving force such as an electrical potential gradient.
  • Some ion exchange membranes comprise a porous support, which provides mechanical strength. Such membranes are often called “composite membranes” due to the presence of both an ionically charged polymer which discriminates between oppositely charged ions and the porous support which provides mechanical strength.
  • BPMs For generation of acids and bases generally BPMs are used, e.g. in a process called bipolar electrodialysis (BPED).
  • BPED bipolar electrodialysis
  • a BPM has both a cationic layer or anion exchange layer (AEL) and an anionic layer or cation exchange layer (CEL) and thus has both a negatively charged layer and a positively charged layer.
  • AEL cationic layer or anion exchange layer
  • CEL anionic layer or cation exchange layer
  • the monopolar membranes For generation of acids and bases in high concentrations it is important that the monopolar membranes have a very high pH stability and high durability (high pH stability and durability increase the lifetime of the membranes). Also desired is a high efficiency of the process for generating acids and bases. This requires the membranes to have a very high permselectivity to prevent H + and OH’ ions to reach the wrong channel causing recombination of H + and OH’ ions forming water and hence product loss. Especially for anion exchange membranes it is difficult to obtain a high proton blocking performance at high concentrations due to the small size of protons.
  • anion exchange membranes which are mechanically strong and having a high permselectivity at very low pH values which can be achieved by controlling their swelling behavior.
  • an anion exchange membrane obtainable by curing a curable composition comprising: (a) a component (a) of Formula (I); and
  • L is a non-aromatic linking group; each X’ independently is an anion; and
  • AR 1 , AR 2 , AR 3 and AR 4 each independently comprise aromatic groups
  • R a , R b , R c , R d , R e and R f are each independently an optionally substituted C-i-3-alky I group, an optionally substituted C 2 -3-alkenyl group or a vinylbenzyl group; or
  • R a and R b together with the positively charged nitrogen atom to which they are attached, form an optionally substituted 5- or 6-membered ring;
  • one of R a and R b is an optionally substituted C-i-3-alkyl group, an optionally substituted C 2 -3-alkenyl group or a vinylbenzyl group and the other of R a and R b , together with the group of formula AR 1 - (CH 2 ) n - N + , forms an optionally substituted 5- or 6-membered ring; or
  • R a together with the group of formula AR 1 - (CH 2 ) n - N + , forms an optionally substituted 5- or 6-membered ring
  • R b together with the group of formula N + - (CH 2 ) n - AR 2 , forms an optionally substituted 5- or 6-membered ring
  • R c and R d together with the positively charged nitrogen atom to which they are attached, form an optionally substituted 5- or 6-membered ring and R e and R f are each independently an optionally substituted Ci-3-alkyl group, an optionally substituted C 2 -3-alkenyl group or a vinylbenzyl group; or
  • R c and R d together with the positively charged nitrogen atom to which they are attached, form an optionally substituted 5- or 6-membered ring and R e and R f , together with the positively charged nitrogen atom to which they are attached, form an optionally substituted 5- or 6-membered ring; or
  • R c and R d is an optionally substituted Ci-3-alkyl group, an optionally substituted C 2 -3-alkenyl group or a vinylbenzyl group and the other of R c and R d , together with the group of formula AR 3 - (CH 2 ) n - N + , forms an optionally substituted 5- or 6-membered ring, and R e and R f are each independently an optionally substituted Ci-3-alky I group, an optionally substituted C 2 -3-alkenyl group or a vinylbenzyl group; or
  • one of R c and R d is an optionally substituted Ci-3-alkyl group, an optionally substituted C 2 -3-alkenyl group or a vinylbenzyl group and the other of R c and R d , together with the group of formula AR 3 - (CH 2 ) n - N + , forms an optionally substituted 5- or 6-membered ring, and R e and R f , together with the positively charged nitrogen atom to which they are attached, form an optionally substituted 5- or 6-membered ring; or (ix) one of R c and R d and one of R e and R f is an optionally substituted Ci-3-alkyl group, an optionally substituted C2-3-alkenyl group or a vinylbenzyl group and the other of R c and R d , together with the group of formula AR 3 - (CH2)n - N + , forms an optionally substituted 5- or 6-membered ring, and the other of R e and
  • R c and R d is an optionally substituted Ci-3-alkyl group, an optionally substituted C2-3-alkenyl group or a vinylbenzyl group, and the other of R c and R d is connected to L, forming an optionally substituted ring, and R e and R f are each independently an optionally substituted Ci-3-alkyl group, an optionally substituted Coalkenyl group or a vinylbenzyl group; and wherein the component (a) of Formula (I) and the component (b) of Formula (II) each comprises at least two curable ethylenically unsaturated groups.
  • the water uptake of the anion exchange membrane is between 11 and 16.5%.
  • the ion exchange capacity of the anion exchange membrane is between 0.7 and 1.0 meq/g dry membrane.
  • the molar fraction of component (a) in relation to component (b) is at least 0.60 and not more than 0.96, more preferably at least 0.65 and not more than 0.95, especially at least 0.65 and not more than 0.90, more especially at least 0.70 and not more than 0.80.
  • Preferred curable ethylenically unsaturated groups are vinyl groups and allyl groups, most preferably vinyl groups.
  • the curable ethylenically unsaturated groups are capable of reacting with other curable ethylenically unsaturated groups to form covalent bonds therewith, e.g. when heated and/or irradiated with light (e.g. ultraviolet light) or an electron beam.
  • light e.g. ultraviolet light
  • electron beam e.g. ultraviolet light
  • L is a non-aromatic linking group comprising from 2 to 7 carbon atoms and optionally one or more atoms selected from oxygen, nitrogen and sulphur (e.g. an optionally interrupted C2-7-alkylene group or C2-7-alkelene group or an optionally substituted Cs-Ce-cycloalkylene group, wherein the optional interruptions are selected from oxygen, nitrogen and sulphur) or L forms a ring with one of the positively charged nitrogen atoms and one of R c , R d , R e and R f .
  • Examples of L include e.g.
  • ethylene (-CH2CH2-), propylene (-C3H6-), butylene (-C4H8-), 2,2-dimethylpropylene, methoxymethylene, diethylene ether (-CH2CH2-O-CH2CH2-), diethylenethioether (-CH2CH2-S-CH2CH2-), diallylpropylene, cyclopentylene and cyclohexylene.
  • both component (a) and component (b) comprise at least two curable ethylenically unsaturated groups, more preferably two and only two curable ethylenically unsaturated groups.
  • the curable ethylenically unsaturated groups present in component (a) are present in AR 1 and/or AR 2 , and in component (b) in AR 3 and/or AR 4 .
  • AR 1 , AR 2 , AR 3 and AR 4 each comprise one and only one curable ethylenically unsaturated group and component (a) and component (b) each have a total of two curable ethylenically unsaturated groups.
  • Additional curable ethylenically unsaturated groups may be present in one or more of R a , R b , R c , R d , R e and R f .
  • the positively charged nitrogen atom (N + ) shown in Formula (I) is non-aromatic, i.e. is not part of an aromatic heterocyclic ring.
  • the anion X’ does not react with the other components of the curable composition, i.e. X’ is inert.
  • Preferred anions represented by X’ include hydroxide, fluoride, chloride, bromide, iodide, nitrate, thiocyanate, hexafluoroborate, methanesulfonate, trifluoromethanesulfonate, formate and acetate.
  • Most X’ is a chloride anion because this can provide a component of Formula (I) with good solubility without dramatically increasing the molecular weight of component (a) of Formula (I).
  • each n independently has a value of 1 .
  • both n have a value of 1 .
  • C-i-3-alkyl groups e.g. methyl, ethyl, propyl or isopropyl
  • one of R a and R b is an optionally substituted C-i-3-alkyl group, an optionally substituted C2-3-alkenyl group or a vinylbenzyl group and the other of R a and R b , together with the group of formula AR 1 - (CH2)n - N + (wherein AR 1 and n are as hereinbefore defined), forms an optionally substituted 5- or 6-membered ring, for example an optionally substituted pyrrolidinium, pyrrolinium, piperidinium or morpholinium ring, in each case having an aromatic ring (e.g. a benzene ring) fused thereon (preferably with two or more, preferably one curable ethylenically unsaturated groups attached to the benzene ring).
  • an aromatic ring e.g. a benzene ring
  • R a together with the group of formula AR 1 - (CH2)n - N + (wherein AR 1 and n are as hereinbefore defined), forms an optionally substituted 5- or 6-membered ring and R b , together with the group of formula N + - (CH2)n - AR 2 (wherein AR 2 and n are as hereinbefore defined), forms an optionally substituted 5- or 6-membered ring.
  • one of R c and R d and/or one or both of R e and R f is an optionally substituted C-i-3-alky I group, an optionally substituted C2-3-alkenyl group or a vinylbenzyl group and the other of R c and R d , together with the group of formula AR 3 - (CH2)n - N + (wherein AR 3 and n are as hereinbefore defined), forms an optionally substituted 5- or 6-membered ring, for example an optionally substituted pyrrolidinium, pyrrolinium, piperidinium or morpholinium ring, in each case having an aromatic ring (e.g.
  • a benzene ring fused thereon (preferably with two or more preferably one curable ethylenically unsaturated groups attached to the benzene ring) and/or the other of R e and R f , together with the group of formula N + - (CH2)n - AR 4 (wherein AR 4 and n are as hereinbefore defined), forms an optionally substituted 5- or 6-membered ring.
  • the preferred optionally substituted 5- or 6-membered rings are as hereinbefore defined (one example is a 6-azoniaspiro[5.5]undecylene ring for component (a)).
  • Preferred optional substituents are curable ethylenically unsaturated groups (as hereinbefore described and preferred).
  • component (a) is of Formula (III):
  • Component (a) optionally comprises one or more than one component (a) of Formula (I) (more preferably Formula (III)), for example a mixture of isomers wherein curable unsaturated groups present in AR 1 and/or AR 2 are in different positions (e.g. ortho, meta and/or para position).
  • monomers which may be used as component (a) include the compounds AXL-1 to AXL-14 shown below:
  • component (b) is of Formula (IV):
  • Component (b) optionally comprises one or more than one component (b) of Formula (II) (more preferably Formula (IV)), for example a mixture of isomers wherein curable unsaturated groups present in AR 3 and/or AR 4 are in different positions (e.g. ortho, meta and/or para position).
  • monomers which may be used as component (b) include the compounds AXL2-1 to AXL2-18 shown below:
  • the anion exchange membrane according to the first aspect of the present invention comprises at least 1 ppm of component (a), preferably at least 10 ppm, especially at least 100 ppm, and at least 1 ppm of component (b), preferably at least 10 ppm, especially at least 100 ppm (typically as a result of incomplete curing when the membrane is formed).
  • the anion exchange membrane comprises less than 20,000 ppm of component (a), more preferably less than 10,000 ppm, and less than 20,000 ppm of component (b), more preferably less than 10,000 ppm.
  • the amounts present in the anion exchange membrane may be determined by the method described on page 19 of WO2022162083.
  • the curable composition preferably comprises 35 to 70wt%, more preferably 40 to 70wt%, especially 40 to 65wt%, more especially 45 to 65wt%, most preferably 50 to 60wt% of component (a), and preferably 3 to 40wt%, more preferably 4 to 35wt%, especially 5 to 34wt%, more especially 5 to 30wt%, most preferably 15 to 30wt% of component (b).
  • the curable composition further comprises a monomer comprising a cationically charged group and one and only one curable ethylenically unsaturated group as component (c).
  • the curable composition is free from component (c) or the composition comprises a small amount of component (c), e.g. the curable composition preferably comprises 0 to 10wt% of component (c), more preferably 0 to 7wt% of component (c).
  • the cationically charged group is preferably a quaternary ammonium group.
  • the one and only curable ethylenically unsaturated group present in component (c) is preferably a vinyl or allyl group, more preferably a vinyl group.
  • Component (c) may comprise one or more than one monomer comprising a cationically charged group and one and only one curable ethylenically unsaturated group.
  • component (c) is of Formula (SM) wherein R 1 , R 2 and R 3 each independently represents an alkyl group or an aryl group, or 2 or 3 of R 1 , R 2 and R 3 together with the positively charged nitrogen atom to which they are attached form an optionally substituted 5- or 6-membered ring; n3 represents an integer of 1 to 3; and X3 0 represents an anion, preferably chloride, bromide, iodide or hydroxide.
  • R 1 , R 2 and R 3 each independently represents an alkyl group or an aryl group, or 2 or 3 of R 1 , R 2 and R 3 together with the positively charged nitrogen atom to which they are attached form an optionally substituted 5- or 6-membered ring; n3 represents an integer of 1 to 3; and X3 0 represents an anion, preferably chloride, bromide, iodide or hydroxide.
  • component (c) of Formula (SM) include the following: compounds.
  • the curable composition optionally further comprises a radical initiator as component (d).
  • Preferred radical initiators include thermal initiators, photoinitiators and combinations thereof.
  • the curable composition preferably comprises 0 to 10 wt% of radical initiator, more preferably 0 to 3wt%.
  • the curable composition preferably 0.001 to 2wt%, especially 0.005 to 1 ,5wt%, of radical initiator.
  • thermal initiators examples include 2,2’-azobis(2-methylpropionitrile) (AIBN), 4,4’-azobis(4-cyanovaleric acid), 2,2’-azobis(2,4-dimethyl valeronitrile), 2,2’-azobis(2-methylbutyronitrile), 1 ,1’- azobis(cyclohexane-1 -carbonitrile), 2,2’-azobis(4-methoxy-2,4-dimethyl valeronitrile), dimethyl 2,2’-azobis(2-methylpropionate), 2,2’-azobis[N-(2-propenyl)-2- methylpropionamide, 1 -[(1 -cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2- methylpropionamide), 2,2'-Azobis(N-cyclohexyl-2-methylpropionamide), 2,2'- Azobis(2-methylpropionamidine) dihydroch
  • Suitable photoinitiators which may be included in the curable composition as component (d) include aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkyl amine compounds.
  • Preferred examples of the aromatic ketones, the acylphosphine oxide compound, and the thio-compound include compounds having a benzophenone skeleton or a thioxanthone skeleton described in "RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY", pp.77-117 (1993).
  • More preferred examples thereof include an alpha-thiobenzophenone compound described in JP1972-6416B (JP-S47-6416B), a benzoin ether compound described in JP1972-3981 B (JP-S47-3981 B), an alpha-substituted benzoin compound described in JP1972-22326B (JP-S47-22326B), a benzoin derivative described in JP1972-23664B (JP-S47-23664B), an aroylphosphonic acid ester described in JP1982-30704A (JP-S57-30704A), dialkoxybenzophenone described in JP1985- 26483B (JP-S60-26483B), benzoin ethers described in JP1985-26403B (JP-S60- 26403B) and JP1987-81345A (JPS62-81345A), alpha-amino benzophenones described in JP1989-34242B (JP H01
  • JP1990-211452A JP-H02- 211452A
  • a thio substituted aromatic ketone described in JP1986-194062A
  • an acylphosphine sulfide described in JP1990-9597B
  • an acylphosphine described in JP1990-9596B JP-H02-9596B
  • thioxanthones described in JP1988-61950B (JP-S63-61950B
  • coumarins described in JP1984-42864B JP-S59-42864B
  • photoinitiators described in JP2008-105379A and JP2009-114290A are also preferable.
  • photoinitiators described in pp. 65 to 148 of "Ultraviolet Curing System” written by Kato Kiyomi may be used.
  • Especially preferred photoinitiators include Norrish Type II photoinitiators having an absorption maximum at a wavelength longer than 380nm, when measured in one or more of the following solvents at a temperature of 23°C: water, ethanol and toluene.
  • the curable composition further comprises a monomer free from cationically charged groups, preferably comprising at least two curable ethylenically unsaturated groups, as component (e).
  • the curable composition comprises 0 to 5wt% of component (e). More preferably the curable composition is free from component (e).
  • the curable composition preferably further comprises solvent as component (f).
  • the solvent is preferably an inert solvent. Inert solvents do not react with any of the other components of the curable composition.
  • component (f) comprises water and optionally an organic solvent, especially where some or all of the organic solvent is water miscible.
  • the water is useful for dissolving components (a) and (b) and possibly also component (c) and the organic solvent is useful for dissolving any organic components present in the curable composition.
  • Component (f) is useful for reducing the viscosity and/or surface tension of the curable composition.
  • the curable composition comprises 10 to 40wt%, especially 20 to 30 wt%, of component (f).
  • inert solvents which may be used as or in component (f) include water, alcohol-based solvents, ether-based solvents, amide-based solvents, ketone- based solvents, sulphoxide-based solvents, sulphone-based solvents, nitrile-based solvents and organic phosphorus-based solvents.
  • examples of alcohol-based solvents which may be used as or in component (f) (especially in combination with water) include methanol, ethanol, isopropanol, n-propanol, n-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and mixtures comprising two or more thereof.
  • organic solvents which may be used in component (f) include dimethyl sulphoxide, dimethyl imidazolidinone, sulpholane, N- methylpyrrolidone, dimethyl formamide, acetonitrile, acetone, 1 ,4-dioxane, 1 ,3- dioxolane, tetramethyl urea, hexamethyl phosphoramide, hexamethyl phosphorotriamide, pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, ethylene glycol diacetate, cyclopentylmethylether, methylethylketone, ethyl acetate, y-butyrolactone and mixtures comprising two or more thereof.
  • the curable composition may further comprise other components such as inhibitors, wetting agents for improving coating properties, biocides, stabilizers, preferably in low amounts such as between 0 and 3wt%.
  • the AEMs preferably have a low water permeance so that (hydrated) ions may pass through the membrane and (free) water molecules do not easily pass through the membrane.
  • the water permeance of the AEMs is lower than 1.10’ 11 m 3 /m 2 .s.kPa, more preferably lower than 5.1 O’ 12 m 3 /m 2 .s.kPa, especially lower than 4.10’ 12 m 3 /m 2 .s.kPa.
  • the distance between the two cationically charged nitrogen atoms in component (b) is preferably at least 0.35 nm as this enhances pH stability of the resultant membrane.
  • the distance between the two cationically charged nitrogen atoms in component (b) is less than 1.5 nm since a short distance enhances crosslinking density of the resultant membrane.
  • component (a) and component (b) each have a molecular weight of less than 600 Dalton, more preferably less than 550 Dalton. A higher molecular weight would lead to a membrane having a high electrical resistance.
  • the molar fraction of the sum of component (a) and component (b) in relation to all curable compounds present in the curable composition is preferably at least 0.95.
  • a high ratio of components (a) and (b) in relation to all curable compounds present in the curable composition is preferred to obtain a membrane having a high crosslink density and hence a high permselectivity.
  • the molar fraction of components (a) and (b) in relation to all curable compounds present in the curable composition is preferably up to 1.0.
  • the molar fraction of the sum of components (a) and (b) in relation to all curable compounds present in the curable composition may be calculated by dividing the sum of the molar amount of components (a) and (b) by the sum of the molar amounts of all curable compounds present in the curable composition.
  • the molar fraction may be determined by measuring the extractables from the anion exchange membrane, e.g. as described on page 19 of WO2022162083.
  • the permselectivity (PS) of the membranes of the present invention for protons is preferably at least 50%, more preferably at least 60%, when determined as described below (in a 0.05M - 4M HCI system).
  • the electrical resistance of the membranes of the present invention is preferably less than 15 ohm/cm 2 , more preferably less than 12 ohm/cm 2 , especially less than 10 ohm/m 2 , when determined as described below (in 2M NaCI).
  • the ion exchange capacity (IEC) of the anion exchange membrane according to the present invention is at least 0.7 meq/g dry membrane, more preferably at least 0.8 meq/g dry membrane when measured by the method described below.
  • IECs can provide anion exchange membranes having low electrical resistance.
  • the IEC of the anion exchange membrane according to the present invention is below 1.00 meq/ g dry membrane, more preferably below 0.95 meq/g dry membrane when measured by the method described below.
  • Such lECs can provide anion exchange membranes which do not swell too much and therefore retain good permselectivity in use.
  • the IEC of the anion exchange membrane according to the present invention is between 0.7 and 1 .0 meq/g dry membrane when measured by the method described below.
  • the PS is as high as possible, and the ER is low as possible.
  • the skilled person knows that there is generally a trade-off between PS and ER: a very high PS can be achieved at the cost of a higher ER and when a low ER is desired one has to sacrifice permselectivity.
  • the membranes of the present invention exhibit a very high PS and an acceptable ER.
  • a suitable parameter to select good membranes in a simple way is to measure the water uptake (Wil) of the membrane.
  • the water uptake is preferably between 11 and 16%, more preferably between 12 and 16%.
  • the ion exchange capacity (IEC) has a large influence on the swelling properties and thus on the permselectivity as well as on the electrical resistance of the membrane.
  • a more precise method to select a good membrane is therefore based on both the water uptake and the ion exchange capacity, e.g. the product of the water uptake value and the ion exchange capacity value.
  • Wil * IEC is between 8.5 and 15.5, more preferably between 9.0 and 15.0, especially between 9.2 and 14.7, wherein the water uptake is expressed in percentage (%) and the ion exchange capacity in meq/g dry membrane.
  • the water uptake and ion exchange capacity may be determined as described below in the experimental section.
  • the anion exchange membrane of the present invention preferably further comprises a porous support.
  • porous supports which may be used there may be mentioned woven and non-woven synthetic fabrics and extruded films.
  • examples include wetlaid and drylaid non-woven material, spunbond and meltblown fabrics and nanofiber webs made from, e.g. polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyphenylenesulfide, polyester, polyamide, polyaryletherketones such as polyether ether ketone and copolymers thereof.
  • Porous supports may also be porous membranes, e.g.
  • the porous support preferably has an average thickness of between 10 and 800pm, more preferably between 15 and 300pm, especially between 20 and 150pm, more especially between 30 and 130pm, e.g. around 60pm or around 100pm.
  • the porous support has a porosity of between 30 and 95%, more preferably of 55 to 75%, wherein (in the final membrane) the pores are filled with an anion exchange polymer derived from curing the composition, i.e. the membrane preferably comprises 25 to 45vol% of porous (non-charged) support material and 75 to 55vol% of anion exchange polymer material (i.e. cured composition according to a first aspect of the present invention).
  • the free volume of the porous support may be calculated from thickness (m) and weight (g/m 2 ) and fiber density (g/m 3 ) data.
  • the porosity of the support, prior to making the membrane may be determined by a porometer, e.g. a PoroluxTM 1000 from IB-FT GmbH, Germany.
  • the porous support when present, may be treated to modify its surface energy, e.g. to values above 45 mN/m, preferably above 55mN/m.
  • Suitable treatments include corona discharge treatment, plasma glow discharge treatment, flame treatment, ultraviolet light irradiation treatment, chemical treatment or the like, e.g. for the purpose of improving the wettability of and the adhesiveness to the porous support to the anion exchange membrane.
  • porous supports are available from a number of sources, e.g. from Freudenberg Filtration Technologies (Novatexx materials), Lydall Performance Materials, Celgard LLC, APorous Inc., SWM (Conwed Plastics, DelStar Technologies), Teijin, Hirose, Mitsubishi Paper Mills Ltd and Sefar AG.
  • the porous support is a porous polymeric support.
  • the porous support is a woven or non-woven synthetic fabric or an extruded film without covalently bound ionic groups.
  • the anion exchange membrane of the present invention has an average thickness of between 15pm and 600pm, more preferably of between 15 and 300 pm, especially of between 20pm and 200pm and more especially between 50 and 140pm.
  • a process for preparing an anion exchange membrane comprising curing a curable composition as defined (and preferred) in relation to the first aspect of the present invention.
  • the process according to the second aspect of the present invention preferably comprises the steps of: i. providing a porous support; ii. impregnating the porous support with the curable composition; and iii. curing the curable composition; wherein the curable composition is as defined above.
  • the curable composition may be cured by any suitable process, including thermal curing, photocuring, electron beam (EB) irradiation, gamma irradiation, and combinations of the foregoing.
  • thermal curing photocuring
  • electron beam (EB) irradiation electron beam irradiation
  • gamma irradiation gamma irradiation
  • the process according to the second aspect of the present invention comprises a first curing step and a second curing step (dual curing). Dual curing is preferred since it increases the crosslink density of the resultant anion exchange membrane which in turn improves permselectivity.
  • the curable composition is cured first by photocuring, e.g. by irradiating the curable composition with ultraviolet (UV) or visible light, or by gamma or electron beam radiation, and thereby causing curable components present in the curable composition to polymerise, and then applying a second curing step.
  • the second curing step preferably comprises thermal curing, gamma irradiation or EB irradiation of the product of the first curing step whereby the second curing step preferably applies a different curing technique to the first curing step.
  • the process according to the second aspect of the present invention comprises curing the curable composition in a first curing step to form the anion exchange membrane, winding the anion exchange membrane onto a core (optionally together with an inert polymer foil) and then performing the second curing step on the wound product of the first curing step.
  • first and second curing steps are respectively selected from (i) UV curing (first curing step) then thermal curing (second curing step); (ii) UV curing then electron beam curing; and (iii) electron beam curing then thermal curing.
  • Component (d) may comprise just one radical initiator or more than one radical initiator, e.g. a mixture of several photoinitiators (e.g. for single curing) or a mixture of photoinitiators and thermal initiators (e.g. for dual curing).
  • the second curing step is performed using gamma or electron beam (EB) irradiation.
  • EB electron beam
  • a dose of 60 to 200 kGy is applied to the product of the first curing step, more preferably a dose of 80 to 150 kGy is applied.
  • thermal curing is preferred.
  • the thermal curing is preferably performed at a temperature between 50 and 100°C, more preferably between 60 and 90°C.
  • the thermal curing is preferably performed for a period between 2 and 72 hours, e.g. around 3 hours for a sheet, between 8 and 16 hours, e.g. about 10 hours for a small roll and between 24 and 72 hours for a large roll.
  • a polymer foil is applied to the product of the first curing step before winding it onto a spool (this reduces oxygen inhibition, drying out and/or sticking of the product of the first curing step to itself).
  • the curable composition application station may be located at an upstream position relative to the irradiation source(s) and the irradiation source(s) is/are located at an upstream position relative to the membrane collecting station.
  • suitable coating techniques for applying the curable composition to a support include slot die coating, slide coating, air knife coating, roller coating, screen-printing, and dipping. Depending on the used technique and the desired end specifications, it might be desirable to remove excess coating from the substrate by, for example, roll-to-roll squeeze, roll-to-blade or blade-to-roll squeeze, blade-to-blade squeeze or removal using coating bars.
  • Curing by light is preferably done for the first curing step, preferably at a wavelength between 300 nm and 800 nm using a dose between 40 and 20000 mJ/cm 2 . In some cases additional drying might be needed for which temperatures between 40°C and 200°C could be employed.
  • gamma or EB curing irradiation may take place under low oxygen conditions, e.g. below 200 ppm oxygen.
  • a third aspect of the present invention there is provided use of (a method of using) the anion exchange membrane according to the first aspect of the present invention for use in electromembrane processes, for example for the treatment of polar liquids (e.g. desalination), for the production the acids and bases or for the generation or storage of electricity.
  • polar liquids e.g. desalination
  • the water uptake (Wil) was determined as follows:
  • Membrane samples (having a size of at least 44cm 2 ) were equilibrated in deionized water for 24 hours at room temperature and gently dried with a tissue to remove hanging water droplets. Each sample was placed in a dry open container, and the container with sample was dried for 24 hours at 80°C. After 24 hours the container was closed with a lid and the container was allowed to cool to room temperature. The container with sample was weighed again and the water uptake was calculated by Formula (A) wherein the weight of the membrane was determined by subtracting the weight of the empty container from the weight of the container containing the membrane sample.
  • Formula (A) Formula (A) wherein the weight of the membrane was determined by subtracting the weight of the empty container from the weight of the container containing the membrane sample.
  • PS permselectivity
  • the anion exchange membrane to be tested was placed in a two-compartment system. One compartment was filled with a 0.05M solution of HCI and the other with a 4M solution of HCI with the membrane under test separating the two compartments. Settings: • the capillaries as well as the Ag/AgCI reference electrodes (Metrohm type 6.0750.100) contained 3M KCI;
  • the anion exchange membrane samples were equilibrated for at least 1 hr in a 0.25M HCI solution prior to measurement.
  • the voltage was read from a regular VOM (multitester) after 20 minutes.
  • the PS was calculated from the voltage reading using the Nernst equation.
  • the PS for HCI was at least 50%, more preferably at least 60%.
  • the membranes Prior to measurement, the membranes are brought in the chloride form by immersing the samples in 2 M NaCI solution for 1 hour. The 2 M NaCI solution was refreshed once, and the samples were equilibrated for another 24 hours. Subsequently, the membrane samples were rinsed with Milli-Q® water, immersed for 1 hour in fresh Milli-Q® water and rinsed once more with Milli-Q® water.
  • Y is the amount of 0.1 M KBr (in ml) used in the titration of the blank AgNOs solution
  • X is the amount of 0.1 M KBr (in ml) used in the titration of the AgNOs solution in which the membrane sample had been soaked combined with the Milli-Q® water used for rinsing the membrane sample after soaking in the AgNOs solution;
  • W is the dry weight of the membrane (in gram).
  • the porosity of the porous support was calculated from thickness (m) and weight (g/m 2 ) and fiber density (g/m 3 ) data as provided by the supplier.
  • the UV cured samples were covered by a 60pm polyethylene terephthalate (PET) foil (from Toray) without any surface treatment and were placed into a metallized bag. The bag was vacuumized and sealed. The bag containing the membrane was placed in a regular oven and the membrane was thermally cured for 3 hours at 90°C.
  • PET polyethylene terephthalate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une membrane échangeuse d'anions pouvant être obtenue par durcissement d'une composition durcissable comprenant : (a) un composant (a) de formule (I) ; et AR1 – (CH2)n – N+(RaRb) – (CH2)n – AR2, X- formule (I) (b) un composant (b) de formule (II) ; AR3 – (CH2)n – N+(RcRd) – L – N+(ReRf)– (CH2)n – AR4, 2X- formule (II) dans laquelle : n, L, X-, Ra, Rb, Rc, Rd, Re et Rf sont tels que définis dans la revendication 1 ; AR1, AR2, AR3 et AR4 comprennent chacun indépendamment des groupes aromatiques ; et le composant (a) de formule (I) et le composant (b) de formule (II) comprenant chacun au moins deux groupes éthyléniquement insaturés durcissables.
PCT/EP2023/084300 2022-12-22 2023-12-05 Membranes WO2024132498A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2033794 2022-12-22
NL2033794 2022-12-22

Publications (1)

Publication Number Publication Date
WO2024132498A1 true WO2024132498A1 (fr) 2024-06-27

Family

ID=85726272

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/084300 WO2024132498A1 (fr) 2022-12-22 2023-12-05 Membranes

Country Status (1)

Country Link
WO (1) WO2024132498A1 (fr)

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS473981B1 (fr) 1968-06-11 1972-02-03
JPS476416B1 (fr) 1968-04-16 1972-02-23
JPS4722326B1 (fr) 1968-07-26 1972-06-22
JPS4723664B1 (fr) 1968-07-26 1972-07-01
JPS5730704A (en) 1980-06-24 1982-02-19 Bayer Ag Photopolymerizable mixture containing aroylphosphoric acid ester as photoinitiator
US4318791A (en) 1977-12-22 1982-03-09 Ciba-Geigy Corporation Use of aromatic-aliphatic ketones as photo sensitizers
JPS5942864B2 (ja) 1979-04-13 1984-10-18 京セラミタ株式会社 投影用原稿の作成方法及びそれに用いる静電写真用転写フイルム
JPS6026483B2 (ja) 1972-07-28 1985-06-24 チバ・ガイギ−・アクチエンゲゼルシヤフト 不飽和化合物を含む重合系の光重合反応用増感剤
JPS6026403B2 (ja) 1977-05-17 1985-06-24 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング 不飽和化合物の光重合用光増感剤
JPS61194062A (ja) 1985-02-21 1986-08-28 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング チオ置換ケトン化合物を用いる光重合開始剤
JPS6281345A (ja) 1985-09-28 1987-04-14 チバ―ガイギー　アクチェンゲゼルシャフト 共重合性光開始剤
EP0284561A2 (fr) 1987-03-26 1988-09-28 Ciba-Geigy Ag Alpha-aminoacétophénones comme photo-initiateurs
JPS6361950B2 (fr) 1981-03-16 1988-11-30
JPH029596B2 (fr) 1980-05-27 1990-03-02 Basf Ag
JPH029597B2 (fr) 1980-09-15 1990-03-02 Basf Ag
JPH02211452A (ja) 1988-12-01 1990-08-22 Polychrome Corp 光開始剤
JP2008105379A (ja) 2006-09-29 2008-05-08 Fujifilm Corp インクジェット記録方法及びインクジェット記録装置
JP2009114290A (ja) 2007-11-05 2009-05-28 Fujifilm Corp 光硬化性組成物、インクジェット記録用インク組成物、および、インクジェット記録方法
WO2014170645A1 (fr) * 2013-04-15 2014-10-23 Itm Power (Research) Limited Réticulants ionomères et membranes formées avec ces réticulants
US20160177006A1 (en) 2013-08-30 2016-06-23 Fujifilm Corporation Ion exchange film, composition for forming ion exchange film, and production method for ion exchange film
WO2020058665A1 (fr) * 2018-09-21 2020-03-26 Fujifilm Manufacturing Europe Bv Membranes formées à partir de monomères cationiques appropriés pour détecter, filtrer et/ou purifier des biomolécules
WO2022162083A1 (fr) 2021-01-28 2022-08-04 Fujifilm Manufacturing Europe Bv Films polymères
WO2022207470A1 (fr) * 2021-03-29 2022-10-06 Fujifilm Manufacturing Europe Bv Membranes chargées cationiquement

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS476416B1 (fr) 1968-04-16 1972-02-23
JPS473981B1 (fr) 1968-06-11 1972-02-03
JPS4722326B1 (fr) 1968-07-26 1972-06-22
JPS4723664B1 (fr) 1968-07-26 1972-07-01
JPS6026483B2 (ja) 1972-07-28 1985-06-24 チバ・ガイギ−・アクチエンゲゼルシヤフト 不飽和化合物を含む重合系の光重合反応用増感剤
JPS6026403B2 (ja) 1977-05-17 1985-06-24 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング 不飽和化合物の光重合用光増感剤
US4318791A (en) 1977-12-22 1982-03-09 Ciba-Geigy Corporation Use of aromatic-aliphatic ketones as photo sensitizers
JPH0134242B2 (fr) 1977-12-22 1989-07-18 Ciba Geigy
JPS5942864B2 (ja) 1979-04-13 1984-10-18 京セラミタ株式会社 投影用原稿の作成方法及びそれに用いる静電写真用転写フイルム
JPH029596B2 (fr) 1980-05-27 1990-03-02 Basf Ag
JPS5730704A (en) 1980-06-24 1982-02-19 Bayer Ag Photopolymerizable mixture containing aroylphosphoric acid ester as photoinitiator
JPH029597B2 (fr) 1980-09-15 1990-03-02 Basf Ag
JPS6361950B2 (fr) 1981-03-16 1988-11-30
JPS61194062A (ja) 1985-02-21 1986-08-28 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング チオ置換ケトン化合物を用いる光重合開始剤
JPS6281345A (ja) 1985-09-28 1987-04-14 チバ―ガイギー　アクチェンゲゼルシャフト 共重合性光開始剤
EP0284561A2 (fr) 1987-03-26 1988-09-28 Ciba-Geigy Ag Alpha-aminoacétophénones comme photo-initiateurs
JPH02211452A (ja) 1988-12-01 1990-08-22 Polychrome Corp 光開始剤
JP2008105379A (ja) 2006-09-29 2008-05-08 Fujifilm Corp インクジェット記録方法及びインクジェット記録装置
JP2009114290A (ja) 2007-11-05 2009-05-28 Fujifilm Corp 光硬化性組成物、インクジェット記録用インク組成物、および、インクジェット記録方法
WO2014170645A1 (fr) * 2013-04-15 2014-10-23 Itm Power (Research) Limited Réticulants ionomères et membranes formées avec ces réticulants
US20160177006A1 (en) 2013-08-30 2016-06-23 Fujifilm Corporation Ion exchange film, composition for forming ion exchange film, and production method for ion exchange film
WO2020058665A1 (fr) * 2018-09-21 2020-03-26 Fujifilm Manufacturing Europe Bv Membranes formées à partir de monomères cationiques appropriés pour détecter, filtrer et/ou purifier des biomolécules
WO2022162083A1 (fr) 2021-01-28 2022-08-04 Fujifilm Manufacturing Europe Bv Films polymères
WO2022207470A1 (fr) * 2021-03-29 2022-10-06 Fujifilm Manufacturing Europe Bv Membranes chargées cationiquement

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DLUGOLECKI ET AL., J. OF MEMBRANE SCIENCE, vol. 319, 2008, pages 217 - 218
KATO KIYOMI: "Ultraviolet Curing System", 1989, RESEARCH CENTER CO., LTD., pages: 65 - 148
MARCUS D HANWELLDONALD E CURTISDAVID C LONIETIM VANDERMEERSCHEVA ZUREKGEOFFREY R HUTCHISON: "Avogadro: An advanced semantic chemical editor, visualization, and analysis platform", JOURNAL OF CHEMINFORMATICS, vol. 4, 2012, pages 17, XP021138024, DOI: 10.1186/1758-2946-4-17
RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY, 1993, pages 77 - 117
SATA T ET AL: "PREPARATION AND TRANSPORT PROPERTIES OF ANION-EXCHANGE MEMBRANES CONTAINING VIOLOGEN MOIETIES AS ANION-EXCHANGE GROUPS IN THE PRESENCE OR ABSENCE OF PHOTOIRRADIATION", JOURNAL OF THE CHEMICAL SOCIETY. FARADAY TRANSACTIONS, ROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE, GB, vol. 93, no. 15, 7 August 1997 (1997-08-07), pages 2553 - 2560, XP000659932, ISSN: 0956-5000, DOI: 10.1039/A701285C *

Similar Documents

Publication Publication Date Title
EP3112401B1 (fr) Membrane échangeuse d'ions et son procédé de production
AU2012285540B2 (en) Curable compositions and membranes
EP4314092A1 (fr) Membranes chargées cationiquement
CN104918986B (zh) 高分子功能性膜及其制造方法
KR101951509B1 (ko) 이온 교환 조성물, 제조 방법 및 이로부터 제조된 물질
CA2946976C (fr) Compositions et membranes durcissables
WO2022162083A1 (fr) Films polymères
CN104220469A (zh) 可固化组合物和膜
EP4222227A1 (fr) Composés, compositions et films polymères
CN105473648A (zh) 离子交换膜的制造方法及通过该制造方法而得到的离子交换膜
CN115244089A (zh) 膜及其应用
WO2024132498A1 (fr) Membranes
WO2022049193A1 (fr) Membrane composite
WO2023186622A1 (fr) Membranes bipolaires
WO2024068595A1 (fr) Membranes
WO2024068598A1 (fr) Membranes
EP4499276A1 (fr) Membranes bipolaires
WO2024132502A1 (fr) Membranes
WO2024068601A1 (fr) Membranes
WO2022207469A1 (fr) Films polymères
WO2023151941A1 (fr) Membranes
JP2016137434A (ja) 高分子機能性膜及びその製造方法、積層体、並びに、装置
WO2023052506A1 (fr) Membranes
WO2022069386A1 (fr) Membranes
EP4499737A1 (fr) Membranes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23818399

Country of ref document: EP

Kind code of ref document: A1