membrane

Abstract

1. A membrane comprising: a) a first layer comprising a first polymer or a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; b) a second layer comprising a second polymer having ionic groups of the same polarity as the polarity of the ionic groups of the third polymer; and c) a third layer comprising a co-continuous polymer network of (ii) a third polymer having ionic groups and a network of voids, and (ii) a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer, wherein layer c) is sandwiched between layers a) and b), and wherein the third polymer is obtainable by a process comprising phase separation of the third polymer from a curable composition used to prepare the third polymer.

Description

[Technical Field]

[0001] The present invention relates to membranes, their preparation methods, and their uses. Ion exchange membranes are used in electrodialysis, electrodialysis reversal, electrolysis, diffusion dialysis, and several other processes. Typically, ion transport through a membrane occurs under the influence of a driving force such as an ion concentration gradient or, alternatively, an electric potential gradient. [Background technology]

[0002] Ion exchange membranes are generally classified as cation exchange membranes or anion exchange membranes depending on their predominant charge. Cation exchange membranes contain negatively charged groups that allow cations to pass but reject anions, while anion exchange membranes contain positively charged groups that allow anions to pass but reject cations. Bipolar membranes have both cation and anion layers.

[0003] Some ion exchange and bipolar membranes include a porous support that provides mechanical strength. Such membranes are often referred to as "composite membranes" due to the presence of both an ionically charged polymer, which discriminates between oppositely charged ions, and a porous support that provides mechanical strength.

[0004] Composite membranes are known, for example, from US 4,253,900, which describes a bipolar membrane containing a monobead layer of ion-exchange resin. WO 2017 / 205458 and an article by McClure in ECS Transactions, 2015, 69(18), pp. 35-44, describe bipolar membranes containing a bonded layer of interpenetrating polymer nanofibers or microfibers of anion-exchange polymers and cation-exchange polymers. Other examples of composite membranes are described, for example, in EP 3,604,404, in which one of the layers contains ion-exchange resin powder, and in US 4,673,454, which discloses the use of ion-exchange resin in the interfacial layer. It would be desirable to provide membranes with improved properties, such as high permselectivity, low electrical resistivity, good mechanical strength, low swelling under aqueous conditions, and stability at extreme pH. Ideally, such membranes could be produced quickly, efficiently, and inexpensively. Summary of the Invention [Means for solving the problem]

[0005] According to a first aspect of the present invention, a) a first layer comprising a first polymer or a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; b) a second layer comprising a second polymer having ionic groups of the same polarity as the polarity of the ionic groups of the third polymer; c) a third layer comprising a bicontinuous polymer network of (i) a third polymer having a network of ionic groups and voids, and (ii) a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; A membrane comprising: layer c) is sandwiched between layers a) and b), and the third polymer is obtainable by a process comprising phase separation of the third polymer from a curable composition used to prepare the third polymer; A membrane is provided.

[0006] In this document (including the claims), the verb "comprise" and its conjugations are used in their open-ended sense to mean that the items following the word are included, but not that items not specifically mentioned are excluded. In addition, reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one of the element is present, unless the context clearly requires that one and only one of the element is present. Thus, the indefinite article "a" or "an" typically means "at least one." Also, in this specification, a first polymer having ionic groups of opposite polarity to the ionic groups of a third polymer may be abbreviated as a "first polymer," a second polymer having ionic groups of the same polarity as the ionic groups of a third polymer may be abbreviated as a "second polymer," a third polymer having ionic groups of opposite polarity to the ionic groups of the first polymer may be abbreviated as a "third polymer," and a fourth polymer having ionic groups of opposite polarity to the ionic groups of the third polymer may be abbreviated as a "fourth polymer."

[0007] To achieve the two opposite polarities required for the third and fourth polymers, one of the third and fourth polymers is a cationic polymer (i.e., has positively charged groups) and the other is an anionic polymer (i.e., has negatively charged groups).

[0008] To achieve the two opposite polarities required for the third polymer and the first polymer, one of the third polymer and the first polymer is a cationic polymer (i.e., has positively charged groups) and the other is an anionic polymer (i.e., has negatively charged groups).

[0009] In a preferred embodiment, the third polymer can be obtained by phase separation of the third polymer from the composition used to prepare it. In this way, the third polymer can be obtained in a form containing a network of voids, and the voids can be used to receive a fourth polymer (or a curable composition used to prepare the fourth polymer) to create the third layer c), providing a bicontinuous polymer network of (i) the third polymer having ionic groups and (ii) the fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer and present within the network of voids of the third polymer.

[0010] In one embodiment, the curable composition used to prepare the fourth polymer is the same as the curable composition used to prepare the first polymer. In this way, a membrane can be obtained in which the first polymer is the same as the fourth polymer. Preferably, the bicontinuous polymer network comprises a third polymer and a fourth polymer, where the third polymer provides a network of pores and the fourth polymer resides within the network of pores.

[0011] Preferably, the third polymer comprises a porous first polymer domain comprising ionic groups and a network of pores. Preferably, the fourth polymer comprises a second polymer domain comprising ionic groups having an opposite charge to that of the ionic groups of the first polymer domain. In this embodiment, the second polymer domain is located in the pores of the first polymer domain (i.e., in the network of pores of the third polymer).

[0012] The bicontinuous polymer network preferably comprises two separate, continuous polymer domains, one of which carries an anionic charge and the other a cationic charge.Preferably, one of the polymer domains is phase-separated, for example, one of the third polymer and the fourth polymer, particularly the third polymer, is obtained by phase separation from the composition used to prepare the polymer in a porous form, and the pores of the polymer are filled with the other polymer, i.e., the fourth polymer.Preferably, the third polymer and the fourth polymer in the third layer (c) are not mixed or encapsulated, and preferably they are not fibrillar.Optionally, the third layer contains one or more additional polymer domains, each of which carries an anionic or cationic charge.

[0013] In a preferred embodiment, the fourth polymer is present in the network of pores of the third polymer and in the first layer a), hi another preferred embodiment, the third polymer has the same charge and / or is chemically identical to the second polymer in the second layer b).

[0014] In a preferred embodiment, the chemical composition of the first polymer is the same as or substantially the same as the chemical composition of the fourth polymer. In another preferred embodiment, the chemical composition of the second polymer is the same or substantially the same as the chemical composition of the third polymer.

[0015] The third layer c) preferably comprises at least two continuous and intermingled polymer domains (one domain originating from a third polymer and the other domain originating from a fourth polymer) that have a large contact area with each other. This may be achieved by a third polymer comprising a network of pores and a fourth polymer that is different from the third polymer (e.g., one is cationic and the other anionic) and resides within the network of pores of the third polymer. As a result of this large contact area between the two (or more) polymers present in the third layer, when the membrane is used as a bipolar membrane, H + and OH - The amount of water molecules dissociated into the bipolar membrane per unit of time increases, thereby increasing the productivity of the bipolar membrane.

[0016] The large contact area between the third and fourth polymers present in the third layer is preferably provided by a bicontinuous network, in which the two (or more) polymer domains derived from the third and fourth polymers are oppositely charged (i.e., one domain has an anionic charge and the other has a cationic charge). The advantage of a bicontinuous network is that newly generated anions (e.g., OH) created at the interface between the third and fourth polymers (i.e., the interface of the two polymer domains) can be easily transported. - ) and cations (e.g., H + ) are separated into distinct polymer domains immediately after their formation, preventing ionic recombination. In addition, the adhesion between the third and fourth polymers in the third layer (i.e., the adhesion between the first and second polymer domains) is extremely strong as a result of the entanglement of the third and fourth polymers and the large contact area between the third and fourth polymers. The strong adhesion between the third and fourth polymers can lead to the formation of large water-filled blisters at the interface between the positively and negatively charged polymers of the bipolar membrane, where OH - and H + This prevents / reduces the so-called balloon effect, whereby carbon dioxide can (undesirably) recombine to form water.

[0017] The membrane of the present invention preferably comprises an interface between the first layer a) and the third layer c) (first interface), and an interface between the third layer c) and the second layer b) (second interface), and preferably both the first interface and the second interface are uninterrupted, with no gaps and / or spaces between the first layer a) and the third layer c), and no gaps and / or spaces between the third layer c) and the second layer b).

[0018] In one embodiment, the third layer c) comprises a blend morphology of two continuous polymer domains, derived from a third and a fourth polymer, respectively, one of which (derived from the fourth polymer) is located within the other (derived from the third polymer), forming the aforementioned bicontinuous polymer network (of the fourth polymer within the network of voids of the third polymer).

[0019] Preferably, each of the first and second polymer domains is contiguous and substantially comprises a single covalently bonded carbon backbone interconnecting it to itself. Preferably, the polymer domains are non-encapsulated, non-segregated, non-interrupted, and non-fibrillar (eg, not produced by electrospinning).

[0020] In the present invention, the third layer c) preferably comprises a porous support and, within the porous structure of the support, a third polymer comprising a network of pores, and a fourth polymer present within those pores, thereby providing a bicontinuous polymer network, e.g., two polymer domains, one carrying an anionic charge and the other carrying a cationic charge. The two (or more) polymer domains (one from the third polymer and the other from the fourth polymer present within the network of pores of the third polymer) occupy the pores of the porous support and preferably comprise seamless (third) interfaces (first and second interfaces at the junctions of the third layer c) with the first and second layers a) and b), respectively. Thus, the membrane preferably includes an interface at the junction of the third layer c) with the first layer a), an interface at the junction of the third layer c) with the second layer b), and a third interface within the third layer c) at the junction of the third polymer with the fourth polymer. Preferably, this third interface is uninterrupted and does not have any gaps and / or spaces between the third polymer and the fourth polymer. Preferably, this third interface is not an interface between a polymer and a fused / compressed fiber, bead, or particle.

[0021] The volume fraction of the third or fourth polymer is defined as the fraction of the volume of the third or fourth polymer as a portion of the total volume of the third layer c) itself. The volume fraction of the third polymer in the third layer c) is preferably 0.1 to 0.9, more preferably 0.2 to 0.8, in particular 0.3 to 0.7, for example about 0.4, about 0.5, or about 0.6.

[0022] In one embodiment, the third polymer is obtained by a method including polymerization-induced phase separation, more preferably, for example, photopolymerization-induced phase separation of the third polymer from the composition used to prepare the polymer. This preference arises because such a method is particularly good at providing a third polymer that includes a network of pores that can accommodate a fourth (oppositely charged) polymer or a curable composition for preparing the fourth (oppositely charged) polymer. In this process, the third polymer is preferably formed by (photo)polymerization.

[0023] Preferably, the third polymer comprises a network of pores with an average pore size of less than 5 μm, more preferably less than 2 μm, and particularly less than 1 μm. The pores in the third polymer may then be filled with a (fourth) curable composition, which may then be cured to provide the fourth polymer within the network of pores of the third polymer. In a preferred embodiment, the network of pores in the third polymer is substantially or completely filled with the fourth polymer. As a result, a third layer is produced in which the third polymer comprises a network of pores filled with the fourth polymer (oppositely charged). Thus, the third and fourth polymers may provide a bicontinuous polymer network comprising two polymer domains, one derived from the third polymer and the other from the fourth polymer. In a preferred embodiment, this bicontinuous polymer network does not contain any other polymers (except any polymers present in the porous support). In one embodiment, there is a covalent bond connecting the third and fourth polymers together. In practice, the voids present in the third polymer may contain more than one polymer, for example, a fourth polymer (from the fourth curable composition) and optionally a second polymer (from the second curable composition), such that the fourth polymer partially fills the voids of the third polymer and the second polymer fills the remaining voids. Furthermore, if desired, the voids in the third polymer may contain one or more additional polymers. [Brief explanation of the drawings]

[0024] [Figure 1A] 1 shows a known membrane; FIG. [Figure 1B] FIG. 1 shows a membrane according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] FIG. 1A illustrates a cross section through a typical membrane described in the prior art. FIG. 1B illustrates a cross section through a membrane according to the present invention. In FIG. 1A, layer 1 is a polymer layer, layer 3 is a central layer containing fibrous elements, and layer 2 is another polymer layer.

[0026] In Figure IB, layer a) is a first layer a) comprising a first polymer or a fourth polymer and, optionally, a porous support (not shown). Layer c) is a third layer c) comprising a third (2') and fourth (1') polymer, black and white, respectively. The third polymer (black) is located within the pores of the porous support (not shown), and the fourth polymer (white) is within the porous network of the third polymer (black). Layer b) is a second layer b) comprising a second polymer and, optionally, a porous support (not shown).

[0027] When a membrane comprises more than one porous support, the porous supports may be physically and chemically identical to each other, or they may be different from one or more of the other porous supports (if any) present in the membrane, depending on the properties desired for the membrane and the intended use of the membrane.

[0028] Preferably, at least one of layers a), b), and c) comprises a porous support. Thus, the membrane of the present invention is preferably a composite membrane. The porous support is useful for imparting mechanical strength, and typically, one or more of layers a), b), and c) comprise a porous support. Each porous support may be located entirely within the layer, or, if desired, at the interface between layer c) and layer a) and / or the interface between layer c) and layer b).

[0029] In one embodiment, a single porous support is present in both the first layer a) and the third layer c), and is common to them. In this embodiment, layer b) optionally comprises a second porous support. In each case, the polymer of the associated layer is preferably present within the pores of the associated porous support.

[0030] In another embodiment, a single porous support is present in both the second layer b) and the third layer c) and is common to them. In this embodiment, layer a) optionally comprises a second porous support. In each case, the polymer of the associated layer is preferably present within the pores of the associated porous support.

[0031] Optionally, only two of layers a), b), and c) comprise a porous support. For example, layers a) and c) comprise a porous support and layer b) does not, or layers b) and c) comprise a porous support and layer a) does not, or layers a) and b) comprise a porous support and layer c) does not. When only two of layers a), b), and c) comprise a porous support, the two layers optionally each comprise a separate support, or the two layers comprise the same single support.

[0032] In a preferred embodiment, at least layer c) comprises a porous support. In another embodiment, layer c) is partially supported by the first porous support and partially unsupported. Preferably, in this embodiment, the membrane comprises a porous support that fully supports layer a) or layer b) and partially supports layer c). The remaining layer (layer b) or layer a)), as the case may be), preferably does not comprise a porous support or comprises a second porous support.

[0033] Examples of porous supports that may be included in layers a), b), and / or c) include synthetic woven and nonwoven fabrics and extruded films, such as wet-laid and dry-laid nonwoven materials, spunbond fabrics, meltblown fabrics, and nanofiber webs made from polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyphenylene sulfide, polyesters, polyamides, polyaryletherketones such as polyetheretherketone, and copolymers thereof. The porous support may also be a porous membrane, such as a polysulfone membrane, a polyethersulfone membrane, a polyphenylene sulfone membrane, a polyphenylene sulfide membrane, a polyimide membrane, a polyetherimide membrane, a polyamide membrane, a polyamideimide membrane, a polyacrylonitrile membrane, a polycarbonate membrane, a polyacrylate membrane, a cellulose acetate membrane, a polypropylene membrane, a poly(4-methyl-1-pentene) membrane, a polyvinylidene fluoride membrane, a polytetrafluoroethylene membrane, a polyhexafluoropropylene membrane, and a polychlorotrifluoroethylene membrane, and derivatives thereof.

[0034] Preferably, the porous supports, if present, each independently have an average thickness of between 10 and 400 μm, more preferably between 20 and 150 μm, especially between 30 and 100 μm.

[0035] Preferably, the porous support, if present, has a porosity between 30 and 95%. The porosity of the support may be determined by a porometer, for example a Porolux™ 1000 manufactured by IB-FT GmbH, Germany.

[0036] One or more of the porous supports may be treated to modify its surface energy, for example to a value greater than 45 mN / m, preferably greater than 55 mN / m. Suitable treatments include, for example, corona discharge treatment, plasma glow discharge treatment, flame treatment, ultraviolet radiation treatment, or chemical treatment to improve wettability of and adhesion to the porous support.

[0037] Commercially available porous supports are available from several sources, for example, Freudenberg Filtration Technologies (Novatexx materials), Lydall Performance Materials, Celgard LLC, APorous Inc., SWM (Conwed Plastics, DelStar Technologies), Teijin Limited, Hirose, Mitsubishi Paper Mills, Ltd., and Sefar AG.

[0038] Preferably, each porous support is independently a polymeric support. Preferred supports include synthetic woven or nonwoven fabrics or extruded films that do not have covalently attached ionic groups.

[0039] Preferably, the first layer a), the second layer b), and the third layer c) of the membrane each independently have an average thickness between 10 μm and 200 μm, more preferably between 20 μm and 150 μm, especially between 30 and 100 μm.

[0040] Preferably, the membranes of the invention have an average thickness between 30 μm and 600 μm, more preferably between 60 μm and 450 μm, especially between 90 and 300 μm. Preferably, the membrane of the present invention is a bipolar membrane.

[0041] The first, second, third, and fourth polymers are preferably each independently obtained by a method comprising curing a curable composition comprising a curable compound having an ionic group, e.g., an anionic group or a cationic group. Thus, the first polymer may be obtained from the first curable composition, the second polymer may be obtained from the second curable composition, the third polymer may be obtained from the third curable composition, and the fourth polymer may be obtained from the fourth curable composition.

[0042] The ionic group may be partially or entirely in the form of a salt, depending on the pH of the composition. The curable compound having an ionic group may be cured by the presence of one or more ethylenically unsaturated groups. Therefore, the curable compound having an ionic group preferably comprises an ethylenically unsaturated group and a cationic group or an anionic group. The anionic group has the opposite polarity to the cationic group.

[0043] Preferred ethylenically unsaturated groups include vinyl groups and (meth)acrylic acid groups (e.g., CH2=CR 4 C(O)- groups), in particular allyl groups, aromatic vinyl groups (e.g., styrene groups), (meth)acrylate groups (e.g., CH2=CR 4 C(O)O- group), and (meth)acrylamide groups (e.g., CH2=CR 4 C(O)NR 4 - group) (in the formula, each R 4 are independently H or CH3).

[0044] Preferred anionic groups are acidic groups such as sulfo, carboxy, and / or phosphato groups, especially sulfo groups. Preferred salts are lithium, ammonium, sodium, and potassium salts, and mixtures containing two or more thereof.

[0045] Preferred cationic groups are quaternary ammonium groups. Examples of curable compounds having anionic or quaternary ammonium groups are given below.

[0046] The curable compositions that may be used to prepare the first, second, third, and fourth polymers preferably further comprise a crosslinker, e.g., a curable compound comprising at least two ethylenically unsaturated groups and optionally an ionic group, in an amount of 1 to 88 wt % (or 1 to 70 wt %). Examples of curable compounds comprising at least two ethylenically unsaturated groups and optionally an ionic group are provided below.

[0047] The curable compositions that may be used to prepare the first, second, third, and fourth polymers preferably further comprise a radical initiator, for example, 0 to 10 wt % of a radical initiator. Examples of suitable radical initiators are provided below.

[0048] The curable compositions that may be used to prepare the first, second, third, and fourth polymers preferably further comprise a solvent, for example, 0 to 55 wt %, or 20 to 98 wt % of a solvent. Examples of suitable solvents are given below. Preferably, the first polymer is (a1) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group; (b1) 1 to 88 wt % of a curable compound containing at least two ethylenically unsaturated groups and optionally an ionic group; (c1) 0 to 10 wt% of a radical initiator; (d1) 0 to 55 wt% solvent The curable composition may be obtained by a method comprising the step of curing a first curable composition comprising:

[0049] Preferably, the second polymer is (a2) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group of opposite charge to the curable compound present in the first curable composition; (b2) 1 to 88 wt. % of a curable compound comprising at least two ethylenically unsaturated groups and optionally an ionic group (of opposite charge to the curable compound present in the first curable composition); (c2) 0 to 10 wt% of a radical initiator; (d2) 0 to 55 wt% solvent The curable composition may be obtained by a method comprising the step of curing a second curable composition comprising:

[0050] As mentioned above, the third polymer is preferably obtained by a method involving polymerization-induced phase separation of the third polymer from the third curable composition used to prepare it. This method is particularly useful for providing the third polymer in a form containing a network of pores that can accommodate a fourth curable composition (which may be the same as or different from the first curable composition) to prepare a fourth polymer within the network of pores (and optionally, if desired, on the surface of the third polymer to provide the first layer a) very efficiently). In this way, a network of pores is prepared in the third polymer, and then the fourth curable composition suitable for forming the fourth polymer can be impregnated and cured within the network of pores of the third polymer and, optionally, on the surface of the third polymer to simultaneously produce the third layer c) and layer a).

[0051] Preferably, the third polymer comprising the network of ionic groups and pores comprises: (a3) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group; (b3) 1 to 70 wt % of a curable compound containing at least two ethylenically unsaturated groups and optionally an ionic group; and (c3) 0 to 10 wt% of a radical initiator; (d3) 20 to 98 wt% solvent The composition may be obtained by a method comprising the step of curing a third curable composition comprising:

[0052] Preferably, the polarity of the ionic groups of components (a3 / b3) is the same as the polarity of the ionic groups of components (a2 / b2) and opposite to the polarity of the ionic groups of components (a1 / b1). Preferably, the fourth polymer is obtainable by a method comprising curing a fourth curable composition that fits within the definition given for the first curable composition. The fourth curable composition may be the same as or different from the first curable composition. Preferably, the fourth curable composition comprises a curable compound having one ethylenically unsaturated group and an ionic group of opposite charge to the curable compound present in the third curable composition. Thus, the fourth polymer is (a4) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group of opposite charge to the curable compound present in the third curable composition; (b4) 1 to 88 wt. % of a curable compound comprising at least two ethylenically unsaturated groups and optionally an ionic group (of opposite charge to the curable compounds present in the third curable composition); (c4) 0 to 10 wt% of a radical initiator; (d4) 0 to 55 wt% solvent The fourth curable composition may be obtained by a method comprising the step of curing a fourth curable composition comprising:

[0053] The amount of each of the components (a1), (a2), and (a4) is independently preferably 0 to 40 wt %. The amount of component (a3) ​​is preferably 0 to 30 wt %, particularly preferably 0 to 20 wt %.

[0054] The amount of each of the components (b1), (b2) and (b4) is independently preferably 5 to 80 wt %, especially 10 to 70 wt %. The amount of component (b3) is preferably 9 to 65 wt%, in particular 14 to 59 wt%, more in particular 19 to 49 wt%.

[0055] The curable compositions that may be used to prepare the first, second, third, and fourth polymers preferably contain a radical initiator (components (c1), (c2), (c3), and (c4)) if the composition is intended to be cured by UV, visible light, or thermally. Alternative methods for curing include electron beam and gamma irradiation, which do not require a radical initiator. Therefore, the amount of components (c1), (c2), (c3), and (c4) present in the relevant composition is preferably 0 to 2 wt %, more preferably 0.001 to 2 wt %, and especially 0.005 to 0.9 wt %, for curing by UV, visible light, or thermally.

[0056] The amounts of components (d1), (d2) and (d4) present in the relevant compositions are preferably between 20 and 45 wt%. Preferably, the solvents used as components (d1), (d2), and (d3) are inert, i.e., they do not react with any of the other components of the curable composition. The amount of component (d3) is preferably 30 to 90 wt%, especially 40 to 85 wt%, more especially 49 to 78 wt%.

[0057] Component (d3) is preferably a single solvent. Component (d3) optionally comprises two or more inert solvents, at least one of which is a solvent for the other components of the curable composition, and at least one of which is a non-solvent for the third polymer formed from curing the composition, e.g., by phase separation to form a third polymer comprising a network of pores capable of accepting a fourth curable composition.

[0058] Examples of inert solvents that may be present in the curable composition include water, alcoholic solvents, etheric solvents, amide solvents, ketone solvents, sulfoxide solvents, sulfone solvents, nitrile solvents, and organic phosphorus solvents. Examples of alcoholic solvents that may be used as component (d3) or in component (d3) (especially in combination with water) include methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and mixtures containing two or more thereof. Preferably, component (d3) is water.

[0059] In addition, preferred inert organic solvents that may be used in component (d3) include dimethyl sulfoxide, dimethylimidazolidinone, sulfolane, N-methylpyrrolidone, dimethylformamide, acetonitrile, acetone, 1,4-dioxane, 1,3-dioxolane, tetramethylurea, hexamethylphosphoramide, hexamethylphosphorotriamide, pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, ethylene glycol diacetate, cyclopentyl methyl ether, methyl ethyl ketone, ethyl acetate, y-butyrolactone, and mixtures containing two or more thereof. Dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone, cyclopentyl methyl ether, methyl ethyl ketone, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, and mixtures containing two or more thereof are preferred.

[0060] In one embodiment, component (d3) comprises at least one solvent from list (i) below and at least one solvent from list (ii) below, wherein at least two solvents are different. List (i): iso-propanol, methanol, ethanol, acetone, tetramethylurea, hexamethylphosphoramide, hexamethylphosphorotriamide, butanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, cyclopentyl methyl ether, propionitrile, acetonitrile, 1,4-dioxane, 1,3-dioxolane, ethyl acetate, y-butyrolactone, and List (ii): Water, glycerol, ethylene glycol, dimethyl sulfoxide, sulfolane, dimethylimidazolidinone, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N-methylmorpholine, acetonitrile, acetone, 1,4-dioxane, 1,3-dioxolane, tetramethylurea, hexamethylphosphoramide, hexamethylphosphorotriamide, pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, ethylene glycol diacetate, cyclopentyl methyl ether, methyl ethyl ketone, ethyl acetate, and γ-butyrolactone.

[0061] The choice of solvent will depend on the other components of the composition. In one embodiment, component (d3) comprises water and one or more other solvents from list (i).

[0062] Preferably, one of the first and second curable compositions contains a curable compound having an ethylenically unsaturated group and an anionic group, and the other contains a curable compound having an ethylenically unsaturated group and a cationic group. Furthermore, preferably, one of the third and fourth curable compositions contains a curable compound having an ethylenically unsaturated group and an anionic group, and the other contains a curable compound having an ethylenically unsaturated group and a cationic group. Examples of curable compounds having an ethylenically unsaturated group and an anionic or cationic group include the following compounds of formula (A), (B), (CL), (SM), (MA), (MB-α), (C), (ACL-A), (ACL-B), (ACL-C), and / or (AM-B):

[0063] [ka]

[0064] [In formulas (A) and (B), R A1 ~R A3 each independently represents a hydrogen atom or an alkyl group, and R B1 ~R B7 each independently represents an alkyl group or an aryl group, Z A1 ~Z A3 each independently represents -O- or -NRa- (wherein Ra represents a hydrogen atom or an alkyl group); L A1 ~L A3 each independently represents a divalent linking group which is an alkylene group, an arylene group, or a combination thereof; R X represents a divalent linking group which is an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof; X A1 ~X A3 each independently represents an organic or inorganic anion, preferably a halide ion or an aliphatic or aromatic carboxylate ion.

[0065] Examples of compounds of formula (A) or (B) include:

[0066] [ka]

[0067] [ka]

[0068] Examples include: Synthetic methods can be found, for example, in US2015 / 0353721, US2016 / 0367980, and US2014 / 0378561.

[0069] [ka]

[0070] [In formulas (CL) and (SM), L 1 represents an alkylene group or an alkenylene group, R a , R b , R c , and R d each independently represents a linear or branched alkyl group or an aryl group; R a and R b , and / or R c and R d may be bonded to each other to form a ring, R 1 , R 2 , and R 3 each independently represents a linear or branched alkyl group or an aryl group; R 1 and R 2 , or R 1 , R 2 and R 3 may be bonded to each other to form an aliphatic heterocycle, n1, n2, and n3 each independently represent an integer of 1 to 10; X1 - , X2 - , and X3 - each independently represents an organic or inorganic anion. Examples of formulas (CL) and (SM) include:

[0071] [ka]

[0072] Examples include: Synthetic methods can be found in EP3184558 and US2016 / 0001238.

[0073] [ka]

[0074] [In formulas (MA) and (MB-α), R A1 represents a hydrogen atom or an alkyl group, Z 1 represents -O- or -NRa- (wherein Ra represents a hydrogen atom or an alkyl group); M + represents an organic or inorganic cation, preferably a hydrogen ion or an alkali metal ion, R A2 represents a hydrogen atom or an alkyl group, R A4 represents an organic group that contains a sulfonic acid group and has no ethylenically unsaturated group, Z 2 represents -NRa- (wherein Ra represents a hydrogen atom or an alkyl group, preferably a hydrogen atom). Examples of formulas (MA) and (MB-α) include:

[0075] [ka]

[0076] Examples include: Synthesis methods can be found, for example, in US2015 / 0353696.

[0077] [ka]

[0078] Synthesis methods can be found, for example, in US2016 / 0369017.

[0079] [ka]

[0080] [In formula (C), L 1 represents an alkylene group, n represents an integer of 1 to 3, preferably 1 or 2; m represents an integer of 1 or 2; L 2 represents an n-valent linking group, R 1 represents a hydrogen atom or an alkyl group, R 2 is -SO3 - M + or -SO3R 3 represents multiple R 2 In the case of each R 2 independently, -SO3M + or -SO3R 3 represents M + represents a hydrogen ion, an inorganic ion, or an organic ion; R 3 represents an alkyl group or an aryl group] Examples of formula (C) include:

[0081] [ka]

[0082] Examples include: Synthetic methods can be found in EP3187516.

[0083] [ka]

[0084] [In formula (ACL-A), formula (ACL-B), formula (ACL-C), and formula (AM-B), R and R' each independently represent a hydrogen atom or an alkyl group; LL represents a single bond or a divalent linking group; LL 1 , L.L. 1 ',LL 2 , and L.L. 2 each of A and A' independently represents a sulfo group in the free acid or salt form; m represents 1 or 2] Examples of formulas (ACL-A), (ACL-B), (ACL-C), and (AM-B) are:

[0085] [ka]

[0086] Examples include: Synthesis methods can be found in US2016 / 0362526. Other suitable monomers include:

[0087] [ka]

[0088] Examples include: 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. However, the curable composition is preferably cured by photocuring, for example, by irradiating the curable composition with visible ultraviolet light, thereby curing and polymerizing the curable components present in the composition.

[0089] Examples of suitable thermal initiators that may be included in the curable composition include 2,2'-azobis(2-methylpropionitrile) (AIBN), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1,1 ... Nitrile), 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'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] disulfate dihydrate, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrate Examples of suitable azobis include 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

[0090] Examples of suitable photoinitiators that may be included in the curable 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 alkylamine compounds. Preferred examples of aromatic ketones, acylphosphine oxide compounds, and thio compounds include compounds having a benzophenone skeleton or a thioxanthone skeleton, as described in "RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY," pp. 77-117 (1993).More preferred examples thereof include alpha-thiobenzophenone compounds described in JP1972-6416B (JP-S47-6416B), benzoin ether compounds described in JP1972-3981B (JP-S47-3981B), alpha-substituted benzoin compounds described in JP1972-22326B (JP-S47-22326B), and alpha-substituted benzoin compounds described in JP1972-23664B (JP-S47-23664B). 4B), aroylphosphonic acid esters described in JP1982-30704A (JP-S57-30704A), dialkoxybenzophenones described in JP1985-26483B (JP-S60-26483B), benzoin esters described in JP1985-26403B (JP-S60-26403B) and JP1987-81345A (JPS62-81345A), alpha-aminobenzophenones described in JP 1989-34242B (JPH01-34242B), U.S. Pat. No. 4,318,791A, and EP 0284561A1, p-di(dimethylaminobenzoyl)benzene described in JP 1990-211452A (JP-H02-211452A), thio-substituted benzophenones described in JP 1986-194062A (JPS61-194062A), and benzophenones described in JP 1989-34242B (JPH01-34242B), U.S. Pat. No. 4,318,791A, and EP 0284561A1, p-di(dimethylaminobenzoyl)benzene described in JP 1990-211452A (JP-H02-211452A), and thio-substituted benzophenones described in JP 1986-194062A (JPS61-194062A). Examples of suitable photoinitiators include aromatic ketones, acylphosphine sulfides described in JP1990-9597B (JP-H02-9597B), acylphosphines described in JP1990-9596B (JP-H02-9596B), thioxanthones described in JP1988-61950B (JP-S63-61950B), and coumarins described in JP1984-42864B (JP-S59-42864B). In addition, photoinitiators described in JP2008-105379A and JP2009-114290A are also preferred. In addition, photoinitiators described in Kato Kiyomi's "Ultraviolet Curing System" on pages 65-148 (Research Center Co., Ltd., 1989) may also be used.

[0091] Particularly preferred photoinitiators include Norrish Type II photoinitiators that have an absorption maximum at wavelengths greater than 380 nm when measured in one or more of the following solvents: water, ethanol, and toluene at a temperature of 23° C. Examples include xanthene, flavin, curcumin, porphyrin, anthraquinone, phenoxazine, camphorquinone, phenazine, acridine, phenothiazine, xanthone, thioxanthone, thioxanthene, acridone, flavone, coumarin, fluorenone, quinoline, quinolone, naphthaquinone, quinolinone, arylmethane, azo, benzophenone, carotenoid, cyanine, phthalocyanine, dipyrrin, squarine, stilbene, styryl, triazine, or anthocyanin-derivatized photoinitiators.

[0092] The curable composition may be continuously applied to a moving substrate by a manufacturing section that preferably includes a curable composition application station, one or more curing stations equipped with an irradiation source for curing the composition, a film collection station, and means for moving the substrate from the curable composition application station to the curing station and back to the film collection station.

[0093] The curable composition application station may be located upstream relative to the curing station, which may be located upstream relative to the membrane recovery station. Examples of application techniques include slot die coating, slide coating, air knife coating, roller coating, screen printing, and dipping. Depending on the technique used and the desired final specifications, it may be necessary to remove excess coating from the substrate, for example, by roll-to-roll squeeze, roll-to-blade or blade-to-roll squeeze, blade-to-blade squeeze, or removal using a coating bar. Visible UV curing provides 40-2000 mJ / cm. 2The thermal cure preferably occurs at a temperature range between 20°C and 100°C for 0 to 20 hours.

[0094] In some cases, additional drying may be required, where temperatures between 40°C and 200°C may be employed. In one embodiment, the film includes a catalyst. The catalyst or a precursor thereof may be included in one or more of the first curable composition, the second curable composition, the third curable composition, and the fourth curable composition. For example, but not limited to, dipping, air knife coating, micro-roller coating, spraying, chemical (vapor) deposition, or physical (vapor) deposition can be used to apply the catalyst or a precursor thereof to the third polymer (e.g., as a post-treatment step) (i.e., after the third curable composition has been cured). In this embodiment, the catalyst is present at the (third) interface between the third and fourth polymers. In a preferred embodiment, the third layer includes the catalyst.

[0095] In one embodiment, at least one of layers a), b), and c) and / or the interface comprises a catalyst. Examples of suitable catalysts include metal salts, metal oxides, organometallic compounds, monomers, polymers, or copolymers. Examples include, but are not limited to, FeCl3, FeCl2, AlCl3, MgCl2, RuCl3, CrCl3, Fe(OH)3, Sn(OH)2, Sn(OH)4, SnCl2, SnCl4, SnO, SnO2, Al2O3, NiO, Zr(HPO4)2, MoS2, graphene oxide, Fe-polyvinyl alcohol complex, polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethyleneimine (PEI), polyacrylic acid (PAA), copolymer of acrylic acid and maleic anhydride (PAAMA), and hyperbranched aliphatic polyesters. Any of these catalysts may be present in a range of up to 5 wt% of the membrane weight, such as 0.001 wt% or 1 wt%.

[0096] According to a second aspect of the present invention, there is provided a method for preparing a membrane, comprising the following steps: (i) providing a second, third, and fourth curable composition, and optionally a first curable composition, each comprising a curable compound having an ionic group; a) the ionic group of the curable compound present in the second curable composition has the same polarity as the ionic group of the curable compound present in the third curable composition; b) the ionic group of the curable compound present in the fourth curable composition has a polarity opposite to that of the ionic group of the curable compound present in the third curable composition; c). When a first curable composition is provided, the ionic groups of the curable compounds present in the first curable composition have a polarity opposite to that of the ionic groups of the curable compounds present in the third curable composition; Steps and (ii) impregnating the porous support with a third curable composition; (iii) curing the third curable composition present within the porous support by a process comprising phase separation of a third polymer from the third curable composition, wherein the third polymer comprises ionic groups and a network of pores, thereby providing a base layer comprising the porous support and the third polymer, the base layer having a first side and a second side opposite the first side; (iv) contacting the first side of the substrate with a fourth curable composition such that at least a portion of the fourth curable composition enters at least some of the pores of the third polymer, optionally providing a layer of the fourth curable composition on the first side of the substrate; (v) contacting the second side of the substrate with the second curable composition such that the second curable composition enters all remaining pores of the third polymer to provide a layer of the second curable composition on the second side of the substrate; (vi) if the step of contacting the first side of the substrate with the fourth curable composition does not provide a layer of the fourth curable composition on the first side of the substrate, contacting the first side of the substrate with the first curable composition so as to provide a layer of the first curable composition on the first side of the substrate; (vii) curing, in any order or simultaneously, the layers of the curable composition present on each side of the base layer and the layer of the curable composition present within the pores of the third polymer; a first layer a) comprising a first polymer or a fourth polymer in each case having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; a second layer b) comprising a second polymer having ionic groups of the same polarity as the polarity of the ionic groups of the third polymer; a third layer c) comprising a bicontinuous polymer network of (i) a third polymer having ionic groups and (ii) a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer and present within the network of pores of the third polymer; forming a Layer c) is sandwiched between layers a) and b), and A method is provided, comprising:

[0097] In one embodiment of the method, in step (i), no first curable composition is provided, and in step (vi), contacting the first side of the substrate with a fourth curable composition provides a layer of the fourth curable composition on the first side of the substrate (thus, it is not necessary to contact the first side of the substrate with the first curable composition so that a layer of the first curable composition is provided on the first side of the substrate, because the fourth curable composition provides the first layer a) in addition to the fourth polymer present in layer c).

[0098] In another embodiment, in step (iv), a layer of a fourth curable composition is provided on the first side of the substrate, and this layer is contacted in step (vi) with the first curable composition such that a layer of the first curable composition is provided on the layer of the fourth curable composition present on the first side of the substrate, the other steps being as described above.

[0099] The method of the second aspect of the invention preferably provides a membrane according to the first aspect of the invention. In another preferred embodiment, one of the first layer a) and the second layer b) comprises a porous support, which may be achieved by including the porous support or the second curable composition in the first curable composition during the above-described method.

[0100] In a preferred embodiment, the first and fourth curable compositions each comprise a curable compound having an anionic group, and the second and third curable compositions both comprise a curable compound having a cationic group.

[0101] In yet another preferred embodiment, step (ii) of the method further comprises placing the porous support impregnated with the third curable composition between transparent foils to obtain a sandwich of the impregnated porous support and two foils, and then removing any excess third curable composition, for example by squeezing the sandwich between a roller or blade. After curing step (iii), the transparent foil may be removed before performing step (iv). In a further preferred embodiment, curing the third curable composition in step (iii) is performed under an inert atmosphere, for example, under nitrogen, carbon dioxide, or argon gas.

[0102] The membranes of the present invention may be used for a variety of applications, including electrodialysis and acid / base generation. The membranes of the present invention may also be applied as bipolar membranes, particularly because they have good durability in acidic and basic media, low swelling, and can be manufactured cheaply, quickly, and efficiently.

[0103] The invention will now be described in more detail by the following non-limiting examples in which all parts and percentages are by weight unless otherwise specified. [Example]

[0104] [Table 1]

[0105] [Table 2]

[0106] Membrane preparation Example 1 First, second, and third curable compositions were prepared by mixing the components shown in Table 2. In this example, the first curable composition was also used as the fourth curable composition.

[0107] A 100 μm thick layer of the third curable composition was applied to a transparent PET foil sheet using a Mayer bar. A porous substrate (FO2223-10C) was applied to the layer of the third curable composition, thereby impregnating the third curable composition. A second transparent PET foil sheet was applied to the impregnated porous substrate, sandwiching the impregnated porous substrate between two transparent foils. A roller was used to gently squeeze all air out of the porous substrate.

[0108] To cure the third curable composition present in the porous support, the impregnated porous support sandwiched between two transparent foils was irradiated using a Fusion UV Systems Light Hammer LH10 equipped with a D bulb operating at 60% intensity at a speed of 5 m / min. After curing, the transparent PET foil was removed and the cured product was dried in air at room temperature to yield a base layer having a first side and a second side (i.e., a porous support comprising a third polymer containing ionic groups and a network of pores).

[0109] The substrate was immersed in a catalyst solution containing 1.35 wt% tin(II) chloride in a slightly acidic aqueous solution and allowed to dry at room temperature, followed by immersion in a 0.12 N NaOH solution to precipitate the catalyst and drying at room temperature.

[0110] Using an 80 μm Meyer bar, the first curable composition was applied to a transparent PET foil. A catalyst-containing substrate prepared as described above was then placed on top of the layer of first curable composition, with the first side of the substrate in contact with the first curable composition, so that some of the first composition (in this case doubling as the fourth composition) entered the pores of the third polymer. This resulted in a substrate impregnated with the first curable composition (in this case doubling as the fourth composition), providing a layer of the first curable composition (in this case doubling as the fourth composition) on the first side of the substrate.

[0111] A substrate impregnated with a first curable composition and having on its first side a layer of the first composition (in this case doubling as a fourth composition) was irradiated on its second side (i.e., the side not having the first curable composition) using a Light Hammer LH10 from Fusion UV Systems, fitted with a D bulb operating at 50% intensity at a speed of 5 m / min. The resulting cured film was a laminate of layer a) and layer c) in which the pores of the third polymer were filled with the cured first curable composition.

[0112] A 100 μm layer of a second curable composition was applied to the second side of the laminate of layers a) and c) not containing layer a) using a Mayer bar, and a second porous support (FO2223-10C) was applied to the layer of second curable composition. After 5 seconds, excess second curable composition was removed using a 4 μm Mayer bar.

[0113] To cure the second curable composition, the resulting product was irradiated on both sides using a Light Hammer LH10 from Fusion UV Systems equipped with a D bulb operating at 50% intensity at a speed of 5 m / min. Finally, the PET foil was removed to obtain a bipolar composite membrane according to the first embodiment of the present invention, comprising a first layer a), a second layer b), and a third layer c) sandwiched between the first layer a) and the second layer b).

[0114] Example 2 First, second, third, and fourth curable compositions were prepared by mixing the ingredients shown in Table 2.

[0115] A 60 μm thick layer of the third curable composition was applied to the porous substrate placed on a transparent PET foil sheet using a Mayer bar. A 4 μm Mayer bar was used to remove excess curable composition from the porous substrate, ensuring that the porous substrate was impregnated with the third curable composition. A second transparent PET foil sheet was applied to the impregnated porous substrate, sandwiching the impregnated porous substrate between two transparent foils. A roller was used to gently squeeze all air out of the porous substrate.

[0116] To cure the third curable composition present in the porous support, the impregnated porous support sandwiched between two transparent foils was irradiated using a Light Hammer LH10 from Fusion UV Systems equipped with a D bulb operating at 60% intensity at a speed of 5 m / min. After curing, the PET foil was removed and the cured product was dried in air at room temperature to obtain a base layer having a first side and a second side (i.e., a porous support including a third polymer containing ionic groups and a network of pores).

[0117] The substrate was immersed in a catalyst solution containing 1.35 wt% tin(II) chloride in a slightly acidic aqueous solution and allowed to dry at room temperature, followed by immersion in a 0.12 N NaOH solution to precipitate the catalyst and drying at room temperature.

[0118] The catalyst-containing substrate prepared as described above was placed on its second side on a transparent PET foil. A 24 μm Mayer bar was used to apply the fourth curable composition to the first side (containing the catalyst) of the substrate, thereby impregnating the porous network of the third polymer with the fourth curable composition. A 4 μm Mayer bar was used to remove excess fourth curable composition.

[0119] The first curable composition was applied to another transparent PET foil using a 60 μm Mayer bar. A base layer containing a third polymer and a fourth curable composition in the porous network of the third polymer was placed on the first curable composition layer, with the first side of the base layer in contact with the first curable composition. As a result, a base layer was formed having the fourth curable composition in the porous network of the third polymer and the first curable composition on the first side of the base layer.

[0120] The substrate having the fourth curable composition present in the voids of the third polymer and a layer of the first curable composition on the first side of the substrate was irradiated on the second side (i.e., the side not having the first curable composition) using a Light Hammer LH10 from Fusion UV Systems equipped with a D bulb operating at 50% intensity at a speed of 5 m / min, after which the transparent PET foil on the second side of the substrate was removed. The resulting cured film was a laminate of layer a) and layer c) in which the voids of the third polymer were filled with the fourth polymer obtained by curing the fourth curable composition.

[0121] The second curable composition was applied to a second porous support (FO2223-10C) using a 60 μm Meyer bar to obtain an impregnated second porous support. The impregnated second porous support was then applied to the second side (opposite layer a) of the laminate of layers a) and c). After 5 seconds, excess second curable composition was removed using a 4 μm Meyer bar. To cure the second curable composition, both sides of the resulting product were irradiated using a Light Hammer LH10 (Fusion UV Systems) equipped with a D bulb operating at 50% intensity at a speed of 5 m / min. Finally, the transparent PET foil was removed to obtain a bipolar composite membrane according to the first embodiment of the present invention, comprising a first layer a), a second layer b), and a third layer c) sandwiched between the first layer a) and the second layer b). Membrane characterization: The volume fraction is the volume fraction of the third polymer in the third layer c) (or the volume fraction of the fourth polymer, the latter being the same as the first polymer in Example 1 and different in Example 2). The volume fractions were determined by embedding the samples of Examples 1 and 2 in resin and cutting thin sections using a microtome. The thin sections were analyzed using an atomic force microscope (AFM) equipped with an infrared probe. Line spectra were acquired over 80 μm, and IR spectra were recorded every 3 μm, followed by principal component analysis using the characteristic frequencies in the IR spectra. The resulting image showed the third polymer and the fourth polymer as individual, separate polymers, with the third polymer identified in green and the fourth polymer in blue. The third and fourth polymers were found to be a bicontinuous network in the third layer c).

[0122] The volume fractions of each of the two polymers (i.e., the relative volumes of the third polymer and the fourth polymer in the third layer c) were estimated by their colors, and the fractions are shown in Table 3 below.

[0123] The electrochemical properties of the membranes from Examples 1 and 2, as well as their bipolar characteristics, were compared with those of a commercially available bipolar membrane (BPM) by determining their so-called current-voltage characteristics (IU curves), from which the voltage at a certain current density is derived. This evaluation showed that the voltage of the bipolar composite membrane of the present invention was 800 A / cm 2 It was found that the voltage at this current density was lower than that of a commercially available BPM. The results are shown in Table 3 below.

[0124] [Table 3]

[0125] Synthesis of anionic monomers with crosslinkers and their precursors Cl-SS

[0126] [ka]

[0127] In a double-walled reactor actively cooled to 5°C, thionyl chloride (109 mL, 178.46 g, 1.5 mol, 3 moleq) was added dropwise to a solution of 4-vinylbenzenesulfonic acid lithium salt (95.08 g, 0.500 mol, 1 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in DMF (300 mL). After the addition was complete, the solution was slowly heated to room temperature and stirred for an additional 16 h. The reaction mixture was then poured into 1 L of cold 1 M KCl in a separatory funnel. The bottom layer was removed and dissolved in 500 mL of diethyl ether. This solution was washed with 1 M KCl solution (300 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo to give a yellow oil. The crude product (CL-SS) was used in the next step without further purification. The typical yield is 89.5 g (88%). HPLC-MS purity >98%; 1 H-NMR: <2 wt% DMF, 0% diethyl ether. Cl-DVBS

[0128] [ka]

[0129] In a double-walled reactor actively cooled to 5°C, thionyl chloride (75 mL, 123.1 g, 1.034 mol, 3 moleq) was added dropwise to a solution of divinylbenzenesulfonate sodium salt (80 g, 0.345 mol, 1 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in DMF (300 mL). After the addition was complete, the solution was slowly heated to room temperature and stirred for an additional 16 h. The reaction mixture was then poured into 1 L of cold 1 M KCl in a separatory funnel. The bottom layer was removed and dissolved in 500 mL of diethyl ether. This solution was washed with 1 M KCl solution (300 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo to give a yellow oil. The crude product (Cl-DVBS) was used in the next step without further purification. Typical yield: 62 g (79%). HPLC-MS purity: >98%. 1 H-NMR: <2 wt% DMF, 0% diethyl ether. NH2-SS

[0130] [ka]

[0131] In a double-walled reactor actively cooled to 5°C, thionyl chloride (109 mL, 178.46 g, 1.5 mol, 3 moleq) was added dropwise to a solution of 4-vinylbenzenesulfonic acid lithium salt (95.08 g, 0.500 mol, 1 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in DMF (300 mL). After the addition was complete, the solution was slowly heated to room temperature and stirred for an additional 16 h. The reaction mixture was then poured into 1 L of cold 1 M KCl via a separatory funnel. The bottom layer was removed and added dropwise to a solution of 25% ammonium hydroxide in water (250 mL, 3.67 mol, 15 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in a double-walled reactor actively cooled to 5°C. After the addition was complete, the solution was stirred for 1 h. The solution was then heated to room temperature and stirred for 1 h. The reaction mixture was then cooled back to 5°C and the product was filtered off and washed with 50 mL of cold water. The product (NH2-SS) was dried in vacuo at 30°C overnight and used without further purification. Typical yield is 66.8 g (73%). HPLC-MS purity >95%. Synthesis of XL-D

[0132] [ka]

[0133] Prior to synthesis, methanesulfonamide was dried overnight in a vacuum oven (30°C, vac). To a solution of dried methanesulfonamide (8.32 g, 0.087 mol, 1 mol eq) and 4OH-TEMPO (30 mg, 500 ppm) in THF (100 mL) was added LiH (1.53 g, 0.192 mol, 2.2 mol eq) as a solid in one portion. The reaction mixture was stirred for 30 min at room temperature. Then, a solution of Cl-DVBS (20 g, 0.087 mol, 1 mol eq) in THF (50 mL) was added to the reaction mixture. After the addition, the reaction mixture was heated to 60°C (water bath temperature). After 2 days, the reaction mixture was filtered through Celite to remove excess LiH. The filtrate was concentrated in vacuo to give a pale yellow foam. The resulting foam was dissolved in 500 mL of ethyl acetate. Celite was added, and the resulting slurry was stirred for 5 min. The Celite was then filtered off and washed with 100 mL of ethyl acetate. This Celite step was then repeated. The solvent was then evaporated in vacuo, and the resulting white foam was washed with 500 mL of diethyl ether overnight. The resulting white powder was filtered off and dried in a vacuum oven at 30° C. for 16 hours to obtain a hygroscopic white solid. The typical achieved yield is 15.5 g (60%). HPLC-MS purity >95%; 1 H-NMR: <3 wt% residual solvent; 2 wt% divinylbenzenesulfonate; ICP-OES: 24-30 g Li / kg product.

[0134] Synthesis of XL-2 [ka]

[0135] Prior to synthesis, styrenesulfonamide (NH2-SS) was dried overnight in a vacuum oven (30 °C, vac). To a solution of dried styrenesulfonamide (16.90 g, 0.092 mol, 2.05 mol eq) and 4OH-TEMPO (30 mg, 500 ppm) in THF (100 mL) was added LiH (1.50 g, 0.189 mol, 4.2 mol eq) as a solid in one portion. The reaction mixture was stirred for 30 min at room temperature. Then, a solution of 1,3-benzenedisulfonyl chloride (12.38 g, 0.045 mol, 1 mol eq) in THF (50 mL) was added to the reaction mixture. After the addition, the reaction mixture was heated to 60 °C (water bath temperature). After 2 days, the reaction mixture was filtered through Celite to remove excess LiH. The filtrate was concentrated in vacuo to give a pale yellow foam. The resulting foam was dissolved in 500 mL of ethyl acetate. Celite was added and the resulting slurry was stirred for 5 minutes. The Celite was then filtered off and washed with 100 mL of ethyl acetate. This Celite procedure was then repeated. The solvent was then evaporated in vacuo and the resulting white foam was washed with 500 mL of diethyl ether overnight. The resulting white powder was filtered off and dried in a vacuum oven at 30°C for 16 hours to give a hygroscopic white solid. The typical achieved yield is 14.5 g (54%). HPLC-MS purity >96%; 1 H-NMR: <2 wt% residual solvent; <2 wt% styrenesulfonamide; ICP-OES: 35-40 g Li / kg product.

[0136] Synthesis of MM-M [ka]

[0137] Prior to synthesis, methanesulfonamide was dried overnight in a vacuum oven at 30°C. To a solution of dried methanesulfonamide (0.100 mol, 1 mol eq) and 4OH-TEMPO (30 mg, 500 ppm) in THF (100 mL), LiH (0.300 mol, 3 mol eq) was added as a solid in one portion. The reaction mixture was stirred for 30 min at room temperature. Then, a solution of vinylbenzylsulfonyl chloride (Cl-SS) (0.100 mol, 1 mol eq) in THF (50 mL) was added, and the reaction mixture was heated to 60°C (water bath temperature) for 16 h. The resulting solution was filtered through Celite, and the resulting foam was dissolved in 500 mL of ethyl acetate. Celite was added, and the resulting slurry was stirred for 5 min. The Celite was then filtered off and washed with 100 mL of ethyl acetate. The solvent was then evaporated in vacuo, and the resulting white foam was triturated with 500 mL of diethyl ether overnight. The resulting product was collected by filtration and isolated as a white, hygroscopic powder (80% yield, >94% purity). The present invention includes the following aspects. [1] a) a first layer comprising a first polymer or a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; b) a second layer comprising a second polymer having ionic groups of the same polarity as the polarity of the ionic groups of the third polymer; c) a third layer comprising a bicontinuous polymer network of (i) a third polymer having a network of ionic groups and voids, and (ii) a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; A membrane comprising: layer c) is sandwiched between layers a) and b), and the third polymer is obtainable by a process comprising phase separation of the third polymer from a curable composition used to prepare the third polymer; film. [2] 11. The membrane of 1, wherein the method comprises polymerization-induced phase separation of the third polymer from the composition used to prepare the third polymer. [3] 3. The membrane of 2, wherein the polymerization-induced phase separation comprises photopolymerization-induced phase separation of a third polymer from a composition used to prepare the third polymer. [4] 4. The membrane of any one of 1 to 3, wherein the co-continuous polymer network comprises a third polymer and a fourth polymer, the third polymer providing a network of pores and the fourth polymer present within the network of pores. [5] 5. The membrane of any one of 1 to 4, wherein at least the third layer c) comprises a porous support. [6] 6. The membrane of any one of 1 to 5, wherein the third layer c) does not comprise ionically charged fibers and beads. [7] 7. The membrane of any one of 1 to 6, comprising a seamless interface at the junction of the third polymer and the fourth polymer. [8] 8. The membrane according to any one of claims 1 to 7, wherein the third polymer provides a network of pores and the third layer c) is obtained by a process comprising the steps of impregnating the network of pores with a composition used to make a fourth polymer and curing the fourth curable composition within the network of pores of the third polymer. [9] 9. The membrane of any one of 1 to 8, wherein the chemical composition of the first polymer is substantially the same as the chemical composition of the fourth polymer.

[10] 10. The membrane of any one of 1 to 9, wherein the chemical composition of the second polymer is substantially the same as the chemical composition of the third polymer.

[11] 11. The membrane of any one of 1 to 10, wherein the bicontinuous polymer network comprises two separate, continuous polymer domains, one carrying an anionic charge and the other carrying a cationic charge.

[12] 12. The membrane of any one of 1 to 11, wherein at least one of the first layer a) and the second layer b) comprises a porous support.

[13] 13. The membrane of any one of claims 1 to 12, comprising a porous support at the interface between layer c) and layer a) and / or at the interface between layer c) and layer b).

[14] 14. The membrane according to any one of claims 1 to 13, wherein a single porous support is present in both the first layer a) and the third layer c) and common to them.

[15] 15. The membrane of any one of claims 1 to 14, wherein each of the first layer a), second layer b), and third layer c) independently has an average thickness between 10 μm and 200 μm.

[16] 16. The membrane of any one of 1 to 15, having an average thickness between 30 μm and 600 μm.

[17] 17. The membrane of any one of claims 1 to 16, comprising an interface (first interface) at the junction of the first layer a) and the third layer c), and an interface (second interface) at the junction of the third layer c) and the second layer b), wherein both the first interface and the second interface are uninterrupted, and there are no gaps and / or spaces between the first layer a) and the third layer c), and there are no gaps and / or spaces between the third layer c) and the second layer b).

[18] 18. The membrane of any one of 1 to 17, comprising an uninterrupted interface at the junction of the third polymer and the fourth polymer (third interface), without any gaps and / or spaces between the third polymer and the fourth polymer.

[19] 19. The membrane of any one of 1 to 18, wherein the first, second, third, and fourth polymers are each independently obtained by a process comprising curing a curable composition comprising a curable compound having an ionic group.

[20] each of the first and fourth polymers independently comprises: (a1) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group; (b1) 1 to 88 wt % of a curable compound containing at least two ethylenically unsaturated groups and optionally an ionic group; (c1) 0 to 10 wt% of a radical initiator; (d1) 0 to 55 wt% solvent 20. A film according to any one of 1 to 19, obtainable by a process comprising the step of curing a composition comprising

[21] The second polymer is (a2) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group; (b2) 1 to 88 wt % of a curable compound containing at least two ethylenically unsaturated groups and optionally an ionic group; and (c2) 0 to 10 wt% of a radical initiator; (d2) 0 to 55 wt% solvent 21. A film according to any one of 1 to 20, obtainable by a process comprising the step of curing a composition comprising

[22] a third polymer (a3) 0 to 60 wt % of a curable compound having one kind of ethylenically unsaturated group and an ionic group; (b3) 1 to 70 wt % of a curable compound containing at least two ethylenically unsaturated groups and optionally an ionic group; (c3) 0 to 10 wt% of a radical initiator; (d3) 20 to 98 wt% solvent 22. A film according to any of 1 to 21, obtainable by a process comprising the step of curing a composition comprising

[23] 23. The membrane of any one of 1 to 22, which is a bipolar membrane.

[24] 24. The membrane of any one of claims 1 to 23, wherein the volume fraction of the third polymer in the third layer is 0.1 to 0.9.

[25] 25. The membrane of any one of 1 to 24, wherein at least one of the layers and / or interfaces comprises a catalyst.

[26] 26. The membrane of any one of 1 to 25, wherein the first polymer and the fourth polymer comprise anionic groups and the second and third polymer comprise cationic groups.

[27] 1. A method for preparing a membrane, comprising the steps of: (i) providing a second, third, and fourth curable composition, and optionally a first curable composition, each comprising a curable compound having an ionic group; a) the ionic group of the curable compound present in the second curable composition has the same polarity as the ionic group of the curable compound present in the third curable composition; b) the ionic group of the curable compound present in the fourth curable composition has a polarity opposite to that of the ionic group of the curable compound present in the third curable composition; c). When a first curable composition is provided, the ionic groups of the curable compounds present in the first curable composition have a polarity opposite to that of the ionic groups of the curable compounds present in the third curable composition; Steps and (ii) impregnating the porous support with a third curable composition; (iii) curing the third curable composition present within the porous support by a process comprising phase separation of a third polymer from the third curable composition, wherein the third polymer comprises ionic groups and a network of pores, thereby providing a base layer comprising the porous support and the third polymer, the base layer having a first side and a second side opposite the first side; (iv) contacting the first side of the substrate with a fourth curable composition such that at least a portion of the fourth curable composition enters at least some of the pores of the third polymer, optionally providing a layer of the fourth curable composition on the first side of the substrate; (v) contacting the second side of the substrate with the second curable composition such that the second curable composition enters all remaining pores of the third polymer to provide a layer of the second curable composition on the second side of the substrate; (vi) if the step of contacting the first side of the substrate with the fourth curable composition does not provide a layer of the fourth curable composition on the first side of the substrate, contacting the first side of the substrate with the first curable composition so as to provide a layer of the first curable composition on the first side of the substrate; (vii) curing, in any order or simultaneously, the layers of the curable composition present on each side of the base layer and the layer of the curable composition present within the pores of the third polymer; a first layer a) comprising a first polymer or a fourth polymer in each case having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; a second layer b) comprising a second polymer having ionic groups of the same polarity as the polarity of the ionic groups of the third polymer; a third layer c) comprising a bicontinuous polymer network of (i) a third polymer having ionic groups and (ii) a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer and present within the network of pores of the third polymer; forming a Layer c) is sandwiched between layers a) and b), and A method comprising:

[28] 28. The method of claim 27, wherein in step (i) no first curable composition is provided, and wherein in step (vi), contacting the first side of the substrate with a fourth curable composition provides a layer of the fourth curable composition on the first side of the substrate.

[29] 29. The method of claim 27 or 28, wherein the membrane is as defined in any one of claims 1 to 26.

[30] 30. The method of any one of claims 27 to 29, wherein the first and fourth curable compositions each comprise a curable compound having an anionic group, and the second and third curable compositions both comprise a curable compound having a cationic group.

[31] 31. The method of any one of claims 27 to 30, wherein step (ii) further comprises placing the porous support impregnated with the third composition between transparent foils to obtain a sandwich of the impregnated porous support and two foils, and then squeezing the sandwich to remove any excess third curable composition.

[32] 32. The method of claim 31, wherein after the curing step (iii) the transparent foil is removed before carrying out step (iv).

[33] 33. The method of any one of 27 to 32, wherein curing the third curable composition in step (iii) is carried out under an inert atmosphere.

Claims

1. a) a first layer comprising a first polymer having ionic groups of opposite polarity to the polarity of the ionic groups of a third polymer; b) a second layer comprising a second polymer having ionic groups of the same polarity as the ionic groups of the third polymer; c) a third layer comprising a bicontinuous polymer network of (i) a third polymer having a network of ionic groups and voids, and (ii) a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; A membrane comprising: a third layer c) is sandwiched between the first layer a) and the second layer b), and the third polymer is obtainable by a process comprising phase separation of the third polymer from a curable composition used to prepare the third polymer; The bicontinuous polymer network comprises two distinct, continuous polymer domains, one carrying an anionic charge and the other carrying a cationic charge, one of the polymer domains being phase separated, and at least a third layer c) comprising a porous support; film.

2. The membrane of claim 1 , wherein the phase separation comprises photopolymerization-induced phase separation.

3. A membrane described in claim 1 or 2, wherein the chemical composition of the first polymer is identical to the chemical composition of the fourth polymer.

4. 4. The membrane of claim 1, wherein the co-continuous polymer network comprises a third polymer and a fourth polymer, the third polymer providing a network of pores and the fourth polymer residing within the network of pores.

5. 5. The membrane of claim 1, comprising a seamless interface at the junction of the third polymer and the fourth polymer, wherein the interface is not an interface between a polymer and a fused / compressed fiber, bead, or particle.

6. 6. The membrane of claim 1, comprising a first interface at the junction of the first layer a) and the third layer c), a second interface at the junction of the third layer c) and the second layer b), and a third interface within the third layer c) at the junction of the third polymer and the fourth polymer, wherein the first interface, the second interface, and the third interface are uninterrupted, and there are no gaps and / or spaces between the first layer a) and the third layer c), and there are no gaps and / or spaces between the third layer c) and the second layer b), and there are no gaps and / or spaces between the third polymer and the fourth polymer.

7. each of the first and fourth polymers independently being (a1) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group; (b1) 1 to 88 wt % of a curable compound comprising at least two ethylenically unsaturated groups and an ionic group; (c1) 0 to 10 wt % of a radical initiator; (d1) 0 to 55 wt % of a solvent; and wherein the composition is obtainable by a method comprising the step of curing a composition comprising The second polymer is (a2) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group; (b2) 1 to 88 wt % of a curable compound comprising at least two ethylenically unsaturated groups and an ionic group; (c2) 0 to 10 wt % of a radical initiator; (d2) 0 to 55 wt % of a solvent; and wherein the composition is obtainable by a method comprising the step of curing a composition comprising a third polymer (a3) 0 to 60 wt % of a curable compound having one ethylenically unsaturated group and an ionic group; (b3) 1 to 70 wt % of a curable compound containing at least two ethylenically unsaturated groups and an ionic group; (c3) 0 to 10 wt % of a radical initiator; (d3) 20 to 98 wt % of a solvent; 7. A film according to any one of claims 1 to 6, obtainable by a process comprising the step of curing a composition comprising:

8. 8. The membrane of claim 1, which is a bipolar membrane.

9. 1. A method for preparing a membrane, comprising the steps of: (i) providing first, second, third, and fourth curable compositions, each comprising a curable compound having an ionic group; a) the ionic group of the curable compound present in the second curable composition has the same polarity as the ionic group of the curable compound present in the third curable composition; b) the ionic groups of the curable compound present in the fourth curable composition have a polarity opposite to that of the ionic groups of the curable compound present in the third curable composition; c) the ionic groups of the curable compounds present in the first curable composition have a polarity opposite to that of the ionic groups of the curable compounds present in the third curable composition; Steps and (ii) impregnating the porous support with a third curable composition; (iii) curing the third curable composition present within the porous support by a process comprising phase separation of the third polymer from the third curable composition, wherein the third polymer comprises ionic groups and a network of pores, thereby providing a base layer comprising the porous support and the third polymer, the base layer having a first side and a second side opposite the first side; (iv) contacting the first side of the substrate with a fourth curable composition such that at least a portion of the fourth curable composition enters at least some of the pores of the third polymer to provide a layer of the fourth curable composition on the first side of the substrate; (v) contacting the second side of the substrate with a second curable composition such that the second curable composition enters all remaining pores of the third polymer to provide a layer of the second curable composition on the second side of the substrate; (vi) contacting a first side of the substrate with a first curable composition such that a layer of the first curable composition is provided on the first side of the substrate; (vii) curing, in any order or simultaneously, the layers of curable composition present on each side of the base layer and the layer of curable composition present within the pores of the third polymer; a) a first layer comprising a first polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer; a second layer b) comprising a second polymer having ionic groups of the same polarity as the polarity of the ionic groups of the third polymer; a third layer c) comprising a bicontinuous polymer network of (i) a third polymer having ionic groups and (ii) a fourth polymer having ionic groups of opposite polarity to the polarity of the ionic groups of the third polymer and present within the network of pores of the third polymer; forming a a third layer c) sandwiched between the first layer a) and the second layer b); A method comprising:

10. 10. The method of claim 9, wherein the membrane is as defined in any one of claims 1 to 8.

11. The method of claim 9 or 10, wherein the chemical composition of the first polymer is identical to the chemical composition of the fourth polymer.

12. 12. The method of any one of claims 9 to 11, wherein the first and fourth curable compositions each comprise a curable compound having an anionic group, and the second and third curable compositions both comprise a curable compound having a cationic group.

13. 13. The method of any one of claims 9 to 12, wherein step (ii) further comprises placing the porous support impregnated with the third composition between transparent foils to obtain a sandwich of the impregnated porous support and two foils, and then squeezing the sandwich to remove any excess third curable composition.

14. 14. The method of any one of claims 9 to 13, wherein curing the third curable composition in step (iii) is carried out under an inert atmosphere.

Images