Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • 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
  • B01J43/00—Amphoteric ion-exchange, i.e. using ion-exchangers having cationic and anionic groups; Use of material as amphoteric ion-exchangers; Treatment of material for improving their amphoteric ion-exchange properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
  • B01D61/44—Ion-selective electrodialysis
  • B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0002—Organic membrane manufacture
  • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
  • B01D67/0013—Casting processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
• • 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
  • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/16—Organic material
  • B01J39/18—Macromolecular compounds
  • B01J39/20—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
  • 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
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
  • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
  • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
• • 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
  • C08F212/00—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
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/30—Sulfur
• • 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
  • C08F212/00—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
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—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
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • 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
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/18—Membrane materials having mixed charged functional groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/42—Ion-exchange membranes
• • 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
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• This invention relates to membranes (including bipolar membranes) and to processes for their preparation and use.
• Ion exchange membranes are used in electrodialysis, reverse electrodialysis, electrolysis, diffusion dialysis 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 ion concentration gradient or, alternatively, an electrical potential gradient.
• a driving force such as an ion concentration gradient or, alternatively, an electrical potential gradient.
• Ion exchange membranes are generally categorized as cation exchange membranes (CEMs) or anion exchange membranes (AEMs), depending on their predominant charge.
• CEMs cation exchange membranes
• AEMs anion exchange membranes
• Cation exchange membranes comprise negatively charged groups that allow the passage of cations but reject anions
• anion exchange membranes comprise positively charged groups that allow the passage of anions but reject cations.
• Bipolar membranes BPMs have both a cationic layer and an anionic layer.
• bipolar membranes comprise a porous support which provides mechanical strength. Such membranes are often called “composite bipolar membranes” due to the presence of anionic and cationic polymers which discriminates between ions and the porous support which provides mechanical strength.
• bipolar membranes having improved properties, e.g. high permselectivity, low electrical resistance, good mechanical strength and stability at extremes of pH.
• bipolar membranes may be produced quickly, efficiently and cheaply.
• a membrane comprising an anion exchange layer (AEL) and a cation exchange layer (CEL) wherein the CEL is obtainable by a process comprising curing a curable composition comprising a compound of Formula (I):
• X is of the formula -OC n H2n+i or -OC q H2q-i, wherein n has a value of 1 to 6 and q has a value of 5 or 6; and m has a value of 1 or 2.
• the verb "comprise” and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.
• reference to an element by the indefinite article “a” or “an” does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements.
• the indefinite article “a” or “an” thus usually mean "at least one”.
• the composition used to form the AEL is often abbreviated herein to “the AEL composition”.
• the composition used to form the layer which is or becomes the CEL is often abbreviated herein to “the CEL composition”.
• the -SO2X group shown in Formula (I) is convertible to an anionic group and thus is useful for providing the CEL with anionic groups.
• the -SO2X group in Formula (I) (wherein X is as hereinbefore defined) is advantageous over analogous compounds wherein X is Cl or OSO2R (wherein R is C1-6- alkyl or C6-12- aryl) due to their lower reactivity with nucleophiles.
• the compounds of Formula (I) wherein X is as hereinbefore defined have better stability than corresponding compounds wherein X is Cl or OSO2R (wherein R is C1-6- alkyl or C6-12- aryl).
• the compounds of Formula (I) are known and many such compounds are available commercially.
• m has a value of 1 or 2 and n has a value of 2 (i.e. X is ethyloxy) or q has a value of 6 (i.e. X is cyclohexyloxy).
• Component (a) is preferably highly miscible with apolar compounds, for example non-charged aromatic molecules, e.g. with divinylbenzene.
• Examples of compounds of Formula (I) include the following: wherein R is X is -0C n H2n+i or -OC q H2q-i, wherein n has a value of 1 to 6 and q has a value of 5 or 6, for example methoxy, ethoxy, propoxy, tert-butoxy or cyclohexyloxy.
• the curable composition from which the CEL may be obtained preferably comprises the following ingredients: (a) the compound of Formula (I) (as hereinbefore defined); optionally (b) a compound comprising at least two ethylenically unsaturated groups; optionally (c) a non-aqueous solvent; optionally (d) a radical initiator; and optionally (e) an anionic monomer comprising one and only one ethylenically unsaturated group.
• the CEL composition comprises component (b) and/or component (c).
• the CEL composition comprises at least one, more preferably at least two, especially at least three and more especially all four of components (b), (c), (d) and (e) (as defined above).
• the CEL composition comprises:
• component (b) 10 to 60 wt% of component (b);
• component (e) 0 to 15 wt% of component (e).
• the CEL composition comprises 20 to 88wt%, more preferably 30 to 80wt%, most preferably 40 to 75wt% of component (a).
• Component (b) typically functions as a crosslinking agent and can provide CEL layers having a desirably high crosslinking density.
• a high crosslinking density is preferred to limit swelling of the bipolar membrane when in aqueous environments.
• component (b) comprises an aromatic group, e.g. a phenyl or phenylene group (e.g. as is found in styrene).
• aromatic group e.g. a phenyl or phenylene group (e.g. as is found in styrene).
• Preferred ethylenically unsaturated groups include (meth)acrylic groups and/or vinyl groups (e.g. vinyl ether groups, aromatic vinyl compounds, N-vinyl compounds and allyl groups).
• vinyl groups e.g. vinyl ether groups, aromatic vinyl compounds, N-vinyl compounds and allyl groups.
• Acrylic groups are preferred over methacrylic groups because acrylic groups are more reactive.
• ethylenically unsaturated groups are free from ester groups because this can improve the stability and the pH tolerance of the resultant composition.
• Ethylenically unsaturated groups which are free from ester groups include vinyl groups.
• compounds which may be used as component (b) there may be mentioned the following:
• component (b) can be obtained for commercial sources, for example from Sigma-Aldrich.
• component (b) is or comprises divinylbenzene because this compound is widely available at low cost (often as a mixture of isomers).
• the CEL composition comprises 10 to 60wt%, more preferably 20 to 60wt%, most preferably 20 to 55wt% of component (b).
• the molar ratio of component (a) to component (b) is preferably in the range of 3:1 to 1 :2, more preferably 2:1 to 1 :2 and especially 2:1 to 1 :1 , respectively.
• Component (c) is preferably inert, i.e. incapable of reacting with any of the other components of the CEL composition.
• component (c) is miscible with the other compounds of the CEL composition.
• component (c) may be used to dilute the other components of the CEL composition to provide a low viscosity CEL composition suitable for use in coating machines and apparatus.
• non-aqueous solvents which may be used as component (c) of the CEL composition there may be mentioned alcohol-based solvents, ether- based solvents, amide-based solvents, ketone-based solvents, sulfoxide-based solvents, sulfone-based solvents, nitrile-based solvents and organic phosphorus based solvents.
• alcohol-based solvents which may be used as or in component (c) include methanol, ethanol, isopropanol, 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 (c) include dimethyl sulfoxide, dimethyl imidazolidinone, sulfolane, N- methyl pyrrolidone, 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.
• Dimethyl sulfoxide, N- methyl pyrrolidone, , dimethyl formamide, dimethyl imidazolidinone, sulfolane, acetone, cyclopentylmethylether, methylethylketone, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran and mixtures comprising two or more thereof are preferable.
• component (c) of the CEL composition include apolar non- protic solvents, e.g. toluene, xylene, chloroform, dichloromethane, pyrrole, N-methyl pyrole, pyridine, pyrazine, and mixtures comprising two or more of the foregoing.
• apolar non- protic solvents e.g. toluene, xylene, chloroform, dichloromethane, pyrrole, N-methyl pyrole, pyridine, pyrazine, and mixtures comprising two or more of the foregoing.
• the CEL composition comprises a small amount of component (c) to enable the preparation of a dense CEL. If a large amount of component (c) is present in the CEL composition during curing a film (or CEL) having an open structure may be formed in which component (c) fills the open spaces. After drying, such open structures tend to swell in aqueous environments leading to a reduced permselectivity, which is not desirable.
• the CEL composition comprises 0 to 30wt% of component (c), more preferably 4 to 20wt%, especially 2 to 15wt% of component (c).
• Component (d) of the CEL composition preferably is or comprises a thermal initiator, a photo initiator or a combination thereof. Most preferably component (d) is or comprises a thermal 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) dihydrochloride, 2,2'
• the CEL composition is free from component (d) or comprises 0.001 to 2wt%, more preferably 0.2 to 1wt% of component (d).
• component (d) is not necessary.
• the CEL composition further comprises a small amount of component (e).
• Component (e) can be useful for providing the CEL with a small degree of hydrophilicity which aids to speed up hydrolysis processes.
• anionic monomers comprising one and only one ethylenically unsaturated group which may be used as component (e) include sulfonated styrene in free acid or salt form, especially in the form of a lithium salt, a sodium salt or a mixed lithium and sodium salt.
• the CEL composition contains 0 to 15 wt%, more preferably less than 15wt%, of component (e).
• the CEL composition and/or the AEL composition comprises at least 60wt% of curable compounds.
• the membranes of the present invention comprise a porous support.
• a porous support may be included in the CEL, in the AEL, at the junction between the AEL and the CEL or in two or more of the aforementioned locations. Also more than one porous support may be provided in each location.
• porous supports there may be mentioned woven and nonwoven 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 200pm, more preferably between 20 and 150pm.
• the porous support has a porosity of 30 and 95%.
• the porosity of the support 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.
• 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 support is a polymeric support.
• the support is a woven or non-woven synthetic fabric or an extruded film without covalently bound ionic groups.
• the membrane according to the first aspect of the present invention is preferably a bipolar membrane or a membrane which is convertible by hydrolysis to a bipolar membrane.
• the AEL of the membranes of the present invention is preferably obtainable by curing a composition comprising a curable cationic compound (i.e. ‘the AEL composition’).
• the AEL composition preferably comprises a curable cationic compound (referred to in the composition described below as component (a2)).
• a preferred curable cationic compound comprises at least two ethylenically unsaturated groups, e.g. a compound of Formula (II):
• L 1 is an alkylene group or an alkenylene group
• R a , R b , R c , and R d are each independently an alkyl group or an aryl group, or
• R a and R b , and/or R c and R d may, together with the atoms to which they are attached, form a ring; n1 and n2 each independently represent an integer of 1 to 10; and
• X-r and X2’ each independently represent an anion.
• L 1 is preferably ethylene, propylene, hexylene or vinylene.
• R a , R b , R c , and R d is an alkyl group it is preferably a C- -alkyl group, especially methyl.
• R a , R b , R c , and R d is an aryl group it is preferably a Ce- -aryl group, especially phenyl.
• the ring is preferably a 5-or 6-membered ring.
• the anions represented by Xr and 2 are preferably each independently halo, especially Cl’.
• AEL composition preferably comprises the following ingredients:
• (a2) a curable cationic compound comprising at least two ethylenically unsaturated groups; optionally (b2) a compound comprising one and only one ethylenically unsaturated group; optionally (c2) a solvent; and optionally (d2) a radical initiator.
• the AEL composition comprises at least one, more preferably at least two, especially all three of components (b2), (c2) and (d2).
• Examples of compounds of Formula (II) include the following:
• the AEL composition preferably comprises 30 to 80wt% of the compound of component (a2), more preferably between 40 and 70wt% of component (a2).
• the AEL_composition comprises:
• Component (b2) preferably comprises an aromatic group.
• Component (b2) preferably comprises a cationic group.
• Examples of compounds which may be used as component (b2) of the AEL composition include the following:
• the molar ratio of component (a2) to component (b2) in the AEL composition is in the range 9:1 to 1 :4.
• the AEL composition comprises 0 to 60wt%, more preferably 5 to 45wt%, most preferably 10 to 40wt% of component (b2).
• Component (c2) of the AEL composition preferably 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 the compound of Formula (II) and component (c2), when present.
• the solvent is useful for reducing the viscosity and/or surface tension of the composition.
• suitable solvents which may be used as component (c2) of the AEL composition include water, alcohol-based solvents, ether-based solvents, amide-based solvents, ketone-based solvents, sulfoxide-based solvents, sulfone- based solvents, nitrile-based solvents, organic phosphorus based solvents and mixtures comprising two or more thereof.
• suitable solvents which may be used as component (ii) (especially in combination with water) include methanol, ethanol, isopropanol, 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 (ii) include dimethyl sulfoxide, dimethyl imidazolidinone, sulfolane, 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.
• Dimethyl sulfoxide, N- methyl pyrrolidone, dimethyl formamide, dimethyl imidazolidinone, sulfolane, acetone, cyclopentylmethylether, methylethylketone, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran and mixtures comprising two or more thereof are preferable.
• the AEL composition comprises 10 to 40wt%, more preferably 10 to 35wt%, most preferably 15 to 30wt% of component (c2).
• components (c2) to (d2) which may be included in the AEL composition used to form the AEL are as described above in relation to the CEL composition as components (c) and (d) respectively.
• component (c2) of the AEL composition is preferably aqueous.
• Component (d2) preferably is or comprises a thermal initiator, a photoinitiator or a combination thereof. Most preferably component (d) is or comprises a photoinitiator.
• Suitable photoinitiators which may be used as component (d2) of the AEL composition 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 an 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 -342
• JP1990-211452A JP-H02- 211452A
• a thio-substituted aromatic ketone described in JP1986-194062A
• JPS61 -194062A an acylphosphine sulfide described in JP1990-9597B
• JP-H02-9597B an acylphosphine described in JP1990-9596B
• JP-H02-9596B JP-H02-9596B
• thioxanthones described in JP1988-61950B JP-S63-61950B
• coumarins described in JP1984-42864B
• 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 which may be used as component (d2) of the AEL composition 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.
• Examples include a xanthene, flavin, curcumin, porphyrin, anthraquinone, phenoxazine, camphorquinone, phenazine, acridine, phenothiazine, xanthone, thioxanthone, thioxanthene, acridone, flavone, coumarin, fluorenone, quinoline, quinolone, naphtaquinone, quinolinone, arylmethane, azo, benzophenone, carotenoid, cyanine, phtalocyanine, dipyrrin, squarine, stilbene, styryl, triazine or anthocyanin-derived photoinitiator.
• the AEL composition preferably comprises 0.001 to 2wt% of component (d2), more preferably 0.005 to 0.9wt%.
• the AEL composition and the CEL composition optionally each independently further comprise a polymerization Inhibitor.
• a polymerization Inhibitor can be useful for making the composition(s) stable during storage and use.
• polymerization inhibitor well-known polymerization inhibitors can be used. Examples thereof include phenol compounds, hydroquinone compounds, certain amine compounds, mercapto compounds, and nitroxyl radical compounds.
• phenol compounds include hindered phenols (phenols having a t-butyl group in an ortho position, and representatively 2,6-di-t-butyl-4- methylphenol), and bisphenols.
• hydroquinone compounds include monomethyl ether hydroquinone.
• amine compounds include N-nitroso-N-phenyl hydroxylamine and N,N-diethylhydroxylamine.
• nitroxyl radical compounds include 4-hydroxy TEMPO (4-hydroxy- 2,2,6,6-tetramethylpiperidine-1 -oxyl free radical).
• the AEL composition and the CEL composition optionally each independently further comprise two or more polymerisation inhibitors.
• the content is preferably 0.01 to 5wt%, more preferably 0.01 to 1wt%, and further preferably 0.01 to 0.5wt%, relative to the total weight of the composition.
• the AEL composition and the CEL composition optionally each independently further comprise a surfactant, a polymer dispersing agent and/or a crater inhibitor.
• Suitable polymer compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinylic resins, acrylic resins, rubberbased resins, waxes, and natural resins and combinations of two or more of the foregoing.
• the AEL composition and the CEL composition optionally each independently further comprise a surfactant, e.g. a nonionic surfactant, a cationic surfactant, an organic fluoro surfactant, or the like.
• a surfactant e.g. a nonionic surfactant, a cationic surfactant, an organic fluoro surfactant, or the like.
• surfactants include anionic surfactants (e.g.
• alkylbenzene sulfonic acid salt alkylnaphthalene sulfonic acid salts, higher fatty acid salts, sulfonic acid salts of higher fatty acid esters, sulfuric acid ester salts of higher alcohol ethers, sulfonic acid salts of higher alcohol ethers, alkylcarboxylic acid salts of higher alkylsulfone amides and alkylphosphoric acid salts
• non-ionic surfactants e.g.
• poly(oxyethylene) alkyl ethers poly(oxyethylene) alkyl phenyl ethers, poly(oxyethylene) fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of acetylene glycol, ethylene oxide adducts of glycerin, and polyoxyethylene sorbitan fatty acid esters).
• suitable surfactants include amphoteric surfactants (e.g. alkyl betaines and amide betaines), silicone-based surfactants and a fluorine-based surfactant.
• the surfactant can be suitably selected from the surfactant known in the art or a derivative thereof.
• the AEL composition and the CEL composition optionally each independently further comprise a polymer dispersant.
• polymer dispersant examples include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol and polyacryl amide. Among these, it is preferable to use polyvinyl pyrrolidone.
• the AEL composition and the CEL composition optionally each independently further comprise a crater inhibitor (sometimes referred to as a surface conditioner), a levelling agent, or a slipping agent to prevent unevenness on the CEL or AEL surface, examples of which include organomodified polysiloxanes (mixtures of polyether siloxane and polyether), polyether-modified polysiloxane copolymers and Silicon-modified copolymers.
• a crater inhibitor sometimes referred to as a surface conditioner
• a levelling agent or a slipping agent to prevent unevenness on the CEL or AEL surface
• Examples of the commercially available crater inhibitors which may be included in the compositions used to form AEL and/or the CEL include Tego GlideTM 432, Tego GlideTM 110, Tego GlideTM 130, Tego GlideTM 406, Tego GlideTM 410, Tego GlideTM 411 , Tego GlideTM 415, Tego GlideTM 420, Tego GlideTM 435, Tego GlideTM 440, Tego GlideTM 450, Tego GlideTM 482, Tego GlideTM A115, Tego GlideTM B1484 and Tego GlideTM ZG400 (all are product names), manufactured by Evonik industries GmbH.
• the AEL composition and the CEL composition preferably each independently comprise 0 to 10wt%, more preferably 0 to 5wt% and especially 1 to 2wt% of crater inhibitor (relative to the total weight of the relevant composition).
• the membranes according to the present invention comprise a catalyst.
• a catalyst may be included in the AEL composition and/or the CEL composition.
• suitable catalysts include metal salts, metal oxides, organometallic compounds, monomers, polymers or co-polymers.
• suitable catalysts include, but are not limited to, FeCh, FeCl2, AICI3, MgCl2, RuCh, CrCh, Fe(OH)s, AI2O3, NiO, Zr(HPO4)2, M0S2, graphene oxide, Fe-polyvinyl alcohol complexes, polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethyleneimine (PEI), polyacrylic acid (PAA), co-polymer of acrylic acid and maleic anhydride (PAAMA) and hyperbranched aliphatic polyester and combinations comprising two or more of the foregoing.
• PVA polyvinyl alcohol
• PEG polyethylene glycol
• PEI polyethyleneimine
• PAA polyacrylic acid
• PAAMA co-polymer of acrylic acid and maleic anhydride
• hyperbranched aliphatic polyester and combinations comprising two or more of the foregoing.
• the amount of catalyst is preferably up to 5wt%, e.g. 0.001wt% to 1wt%, relative to the weight of the relevant composition.
• the amount of catalyst in the AEL and/or CEL, when the catalyst is present, is preferably up to 5wt%, e.g. 0.001 wt% to 1wt%.
• step (ii) preferably the AEL composition is photocured, e.g. using ultraviolet light. Therefore preferably component (d2) of the AEL composition is or comprises a photoinitiator.
• step (ii) preferably the AEL composition is cured to such an extent that the resultant AEL can be processed in a curable composition application station while still having unreacted ethylenically unsaturated groups that are available for crosslinking to the monomers of the CEL composition.
• step (iv) the CEL composition is preferably cured thermally. Therefore preferably component (d) of the CEL composition is or comprises a thermal initiator.
• a suitable temperature for curing the CEL composition is from 50 to 120°C, more preferably from 50 to 100°C, especially 60 to 85°C.
• Thermal curing of the CEL composition typically takes from one minute or more to several hours.
• the CEL composition is cured after being sandwiched between polymer films to prevent evaporation of component (c), when present.
• the compositions are preferably applied in step (i) and (iii) in a continuous manner, preferably by means of a manufacturing unit comprising composition application stations, one or more curing stations comprising irradiation source(s) when a composition is photocurable, one or more curing stations comprising a one or more heat source(s) when a composition is thermally curable, a membrane collecting station and a means for moving the supports from the composition application stations to the curing station(s) and to the membrane collecting station.
• a manufacturing unit comprising composition application stations, one or more curing stations comprising irradiation source(s) when a composition is photocurable, one or more curing stations comprising a one or more heat source(s) when a composition is thermally curable, a membrane collecting station and a means for moving the supports from the composition application stations to the curing station(s) and to the membrane collecting station.
• composition application stations may be located at an upstream position relative to the curing station(s) and the curing station(s) is/are located at an upstream position relative to the membrane collecting station.
• Examples of application techniques include slot die coating, slide coating, air knife coating, roller coating, screen printing, and dipping.
• it might be necessary to remove excess composition 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.
• Photocuring by ultraviolet or visible light is preferably performed at a wavelength between 100 nm and 800 nm, typically using a dose of light of between 40 and 1500 mJ/cm 2
• Thermal curing is preferably performed at a temperature of between 20°C and 100°C, e.g. for a period of 0.01 hour to 24 hours.
• the process according to the second aspect further comprises of converting the group X into a hydroxyl group, e.g. by hydrolysis.
• the membranes may be converted into bipolar membranes or into bipolar membranes having a larger number of acidic groups.
• Suitable hydrolysis methods include hydrolysis under acidic or alkaline conditions, e.g. using an acid (e.g. hydrochloric acid) or an alkali (e.g. a metal hydroxide, especially sodium hydroxide or potassium hydroxide).
• a membrane comprising an anion exchange layer (AEL) and a layer comprising -SO2X groups wherein X is as defined above.
• AEL anion exchange layer
• a process for preparing a bipolar membrane comprising hydrolysing at least some the -SO2X groups in the membrane according to the first aspect of the present invention to -SO2OH groups or a salt thereof.
• the SO2X groups are hydrolysed to -SO2OH groups (in free acid or salt form) by contact with aqueous acid and/or alkali.
• the hydrolysis may be achieved by, for example, immersing the membrane of the first aspect of the present invention in aqueous acid and/or alkali, preferably at an elevated temperature (e.g. at 50 to 100°C).
• the hydrolysis is preferably performed by contact with the aqueous acid and/or alkali for a total period of 1 hour to 1 month, especially 5 hours to 1 week.
• the aqueous acid and/or alkali comprises a surfactant.
• the aqueous acid and/or alkali comprises a water-miscible organic solvent.
• the aqueous acid and/or alkali is aqueous, especially at a strength of 0.05 to 1.0N.
• Suitable acids include hydrochloric acid and sulphuric acid.
• Suitable alkalis include sodium carbonate, ammonium hydroxide, tetramethyl ammonium hydroxide, potassium hydroxide and sodium hydroxide.
• the acid and/or alkali comprises a polar solvents, e.g. dimethylsulphoxide, isopropylalcohol, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate or two or more of the foregoing.
• a polar solvents e.g. dimethylsulphoxide, isopropylalcohol, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate or two or more of the foregoing.
• the extent of the hydrolysis can be monitored over time by infrared spectroscopy.
• the process of the second aspect or fourth aspect of the present invention further comprises the step (vi) of drying the resultant membrane, preferably at a temperatures of between 40°C and 200°C.
• the membranes of the present invention may be manufactured by a number of alternative processes, including the processes described above.
• the membranes of the present invention may be used for various applications, including electrodialysis and acid/base production.
• the present membranes comprising a CEL and an AEL may also be used as bipolar membranes, particularly as they have good durability in acidic and basic media, low swelling, and may be produced cheaply, quickly and efficiently.
• the performance of the bipolar membranes according to the present invention were characterized by means of an intensity versus voltage plot. For measuring this plot a six compartment cell was used.
• the 1 st electrode compartment contained a platinum plate as cathode and was separated from the 2 nd compartment by a CEM (CMX from Astom).
• the electrode compartment was filled with 0.5 M Na2SO4.
• CMX from Astom
• the electrode compartment was filled with 0.5 M Na2SO4.
• a reference BPM from Fumatech
• Both the 2 nd and the 3 rd compartment contained a 0.5M NaCI solution.
• the BPM to be analyzed was placed.
• the 4 th and 5 th compartments are also filled with a 0.5M NaCI solution.
• the 6 th compartment containing a platinum plate as anode is an electrode compartment and contained 0.5 M Na2SO4.
• auxiliary membranes were CMX and AMX from Tokuyama Soda, Japan;
• the ER (NaCI) of the membranes is lower than 5 ohm/cm 2
• the membrane to be analysed was placed in a two-compartment system. One compartment was filled with a 0.05M solution of NaOH and the other with a 0.5M solution of NaOH.
• the PS (NaOH) of the membranes was preferably above 70%.
• Toluene (600 mL) was added and the complete mixture was filtered over Celite to remove undissolved material. The water layer was extracted twice with toluene (300 mL), and the combined toluene layers were washed once with a saturated KCI- solution (500 mL). The toluene solution was dried over sodium sulfate, filtrated and concentrated in vacuo to give a yellow oil (ca. 120 gram; 84%). The crude product was used without further purification in the second step. The synthesis was confirmed by 1 H NMR.
• step 1 A solution of the product obtained in step 1 (120 g; 0.525 mol) and TEMPOL (4-OH-TEMPO; 60 mg, ca. 500 ppm) in pyridine (150 mL) was added dropwise to an ice-cooled (0 °C) stirred solution of ethanol (46 mL, 36 g; 0.787 mol, 1.5 moleq.) in pyridine (75 mL). After two hours stirring in an ice bath of 0°C, the reaction mixture was poured into an ice-cooled 1 :1 mixture of ice and concentrated 36%-HCI (600 mL total volume). Chloroform (ca. 800 mL) was added and the mixture was transferred to a separation funnel.
• ethanol 46 mL, 36 g; 0.787 mol, 1.5 moleq.
• Coating compositions comprising EtSS, DVB, LiSS, a solvent and 0.5wt% of V-65B were prepared according to the compositions CELC 1 to 4 described in the Table 1.
• the compositions were coated onto a porous substrate and laminated between two PET foils and then were thermally cured in an oven at 70°C for 16 hrs,.
• the resulting CEM precursor films PF1 to PF4 were then subjected to a hydrolysis process at 50°C.
• the hydrolysis conditions and the properties of the resulting cation exchange membranes (CEMs) are shown in Table 2.
• An AEL composition (AELC1 ) was prepared containing 58wt% of 1 ,4- diazoniabicyclo[2.2.2]octane, 1 ,4-bis[(4-ethenylphenyl)methyl]-, chloride, 19wt% of water, 6wt% of IPA, 1wt% of OmniradTM TPO-L and 1wt% of OmniradTM 1173.
• the AEL composition was coated on a non-woven polyethylene fabric and cured by UV to give an AEL.
• CEL compositions were prepared according to Table 3 below. Each CEL composition was coated on the AEL prepared above, then a second non-woven polyethylene fabric was placed onto the layer of CEL composition and excess CEL composition was wiped off. Subsequently, the membrane was placed between PET sheets and cured in an oven at 80°C for 16 hours. The resultant membrane was placed in a 0.1 N NaOH solution with 10% IPA for 72 hours to hydrolyse the -SO2X (ester) groups into the corresponding sulfonic acid sodium salts to give BPMs.
• a Comparative CEL Composition (CExCELCI ) was prepared in which the CEL layer of a BPM was obtained from a composition consisting of 30 wt% Na- AMPS (calculated based on pure material), 30 wt% M-11 , 39 wt% water and 1 wt% V-65B.
• the AEL was prepared exactly the same as described for the Examples of the invention.

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