Poly (arylene ether sulfone) polymer films

Abstract

The present invention relates to a film comprising two different poly (arylene ether sulfone) polymers (P1) and (P2) and a copolymer (CP) wherein the copolymer (CP) comprises at least one poly (arylene ether sulfone) (A) block and at least one polyalkylene oxide (PAO) block, as well as a method of preparation and use thereof.

Description

[0001] The present invention relates to a membrane, a method for preparing the membrane and its use, the membrane comprising two different poly(arylene ether sulfone) polymers (P1) and (P2) and a copolymer (CP), wherein the copolymer (CP) comprises at least one poly(arylene ether sulfone) (A) block and at least one polyepoxide (PAO) block.

[0002] Membrane technology has garnered significant attention over the past few decades. In several application areas, membranes are used for the energy-efficient separation of mixtures. In particular, membranes are widely used in water purification (J.-C. Schrotter, B. Bozkaya-Schrotter, “Membranes for Water Treatment,” edited by K.-V. Peinemann and S. Pereira Nunes, Wiley-VCH, Vol. 4, 2010). Another important application area for specific membranes is blood purification, particularly hemodialysis (hemodiafiltration) or hemofiltration dialysis therapy, which is necessary for treating people with renal diseases (CRRonco, WR Clark, Nature Reviews Nephrology, 14, 2018, 394).

[0003] To be suitable for membrane applications, polymeric materials need to exhibit specific mechanical properties, thermal stability, and chemical resistance. One promising class of materials for membrane applications is polyarylene sulfone. They belong to the group of high-performance polymers with high heat resistance, chemical resistance, excellent mechanical properties, and durability (EMKoch, H.-M. Walter, Kunststoffe 80 (1990) 1146; E. Dbring, Kunststoffe 80, (1990) 1149; N. Inchaurondo-Nehm, Kunststoffe 98, (2008) 190). For example, they are generally suitable as materials for forming dialysis and ultrafiltration (UF) membranes (NA Hoenich, KP Katapodis, Biomaterials 23 (2002) 3853; S. Savariar, GS Underwood, EM Dickinson, PJ Schielke, AS Hay, Desalination 144 (2002) 15). Membrane materials for medical purposes must meet certain standards, and the quality standards for membranes used in medical applications are particularly high. For example, membranes often need to be sterilized, which usually means subjecting them to higher temperatures. Therefore, membrane materials need to be heat-resistant within the required temperature range.

[0004] Another challenge in membrane technology is tuning the appropriate pore size, particularly for specific membranes such as dialysis membranes. Both of these problems have been addressed using non-solvent-induced phase separation (NIPS) methods and by utilizing hydrophilic pore-forming agents (such as polyvinylpyrrolidone (PVP)) and corresponding film-forming polymers. DE 19817364 relates to a method for preparing a hydrophilic membrane with high porosity using a first hydrophobic polymer and a second hydrophilic polymer, wherein, for example, the first polymer is polysulfone and the hydrophilic polymer is polyvinylpyrrolidone. Specifically, DE 19817364 uses two polyvinylpyrrolidones with different molecular weights to produce membranes with increased porosity. In EP 2113298, the same method is used to prepare polyethersulfone-based dialysis membranes.

[0005] EP3180113 relates to a method for preparing films using copolymers of polyarylene ethers and polyepoxide units and polyethersulfone polymers.

[0006] PVP can be used for membrane pore formation and to enhance the hydrophilicity of membranes. However, it is also known that PVP can leach from the membrane. During the treatment of hemodialysis patients with PVP-containing membranes, PVP may accumulate in the patient's blood, especially after several years of treatment (K. Sakai et al., J. Artificial Organs (2012) 15, p. 185), which is a drawback of this type of membrane.

[0007] EP0344581 describes a method for producing ultrafiltration membranes via the NIPS process without using pore-forming components. EP0344581 uses a coating solution containing polyarylate and polysulfone as membrane polymers. However, a drawback of the method described in the examples of EP0344581 is that the polyarylate polymer results in limited solubility, and the components are unstable in solvents commonly used in membrane manufacturing, such as N-methyl-2-pyrrolidone (NMP), leading to turbidity of the solution. Furthermore, polyarylates are polyesters with limited stability under long-term use in aqueous environments. Therefore, the applicability of this method in ultrafiltration membrane technology is very limited.

[0008] There is a need for membranes, particularly ultrafiltration membranes, that exhibit excellent selectivity, high membrane productivity, and good mechanical properties, making them especially suitable for medical applications such as dialysis. Specifically, there is a need for ultrafiltration membranes that simultaneously possess low molecular weight cutoff and high water permeability.

[0009] Furthermore, it is undesirable for the membrane to release residues of components used in membrane production. In particular, it is undesirable to contain pore-forming additives that leach out over time. On the other hand, the polymer material needs to have good viscosity characteristics to be suitable for forming a stable membrane. Additionally, the membrane material should exhibit a certain degree of hydrophilicity so that the membrane can be wetted by the liquid that needs to pass through it. Pore size is also a key parameter, as the pores need to be wide enough to allow a high flow rate (PWP = pure water permeability) through the membrane while possessing selective retention characteristics. Specifically, in the case of dialysis, the molecular weight cutoff should be below 100 kD to prevent proteins from passing through as well. Furthermore, the pores need to be interconnected to generate high permeate flux. Another potential objective of this invention is to provide stable polymer solutions for membrane production, particularly for the NIPS process, and thus effectively for the preparation of ultrafiltration membranes.

[0010] These objectives are successfully achieved by the membrane (M) of the present invention, which comprises poly(aryl ether sulfone) polymers (P1) and (P2) and a copolymer (CP), wherein the copolymer (CP) comprises at least one poly(aryl ether sulfone) (A) block and at least one polyepoxide (PAO) block, and wherein (P1) and (P2) each comprise at least one repeating unit having general formula (I):

[0011]

[0012] The symbols t, q, Q, T, Y, Ar, and Ar 1 The definition is as follows:

[0013] t and q are independent of each other and can be 0, 1, 2 or 3;

[0014] Q, T, and Y are independent chemical bonds or selected from -O-, -S-, -SO2-, S=O, C=O, -N=N-, and -CR. a R b - groups, where R a and R b Each is an independent hydrogen atom, (C1-C) 12 )alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkyl or (C6-C 18 ) aryl group, wherein at least one of Q, T and Y is present and is -SO2-; and

[0015] Ar and Ar 1 They are independent of each other (C6-C) 18 )triaryl;

[0016] At least one structural repeating unit of (P2) is different from at least one structural repeating unit of (P1).

[0017] The membranes according to the invention exhibit excellent selectivity and efficiency, particularly low molecular weight cutoff and high pure water permeability.

[0018] In the context of this invention, the term "membrane" refers to a semi-permeable structure that acts as a selective barrier, allowing some particles, substances, or chemicals to pass through while retaining others. Generally, membranes are used for various liquid and gas separation applications. Membranes can have various geometries, such as flat sheets, spiral wound structures, pillow blocks, tubular structures, single-pore hollow fibers, or multi-pore hollow fibers.

[0019] For example, the membrane (M) can be a nanofiltration (NF) membrane, a microfiltration (MF) membrane, and an ultrafiltration (UF) membrane. These membrane types are well known in the art.

[0020] Nanofiltration (NF) membranes are typically well-suited for removing both multivalent and large monovalent ions. Generally, NF membranes function through solution / diffusion and / or filtration mechanisms. NF membranes are commonly used in cross-flow filtration methods. Nanofiltration membranes typically comprise charged polymers containing sulfonic acid groups, carboxylic acid groups, and / or ammonium groups.

[0021] Microfiltration (MF) membranes typically have an average pore size of 0.05 µm to 10 µm, preferably 1.0 µm to 5 µm, and are generally suitable for removing particles with a size of 0.1 µm and larger. Microfiltration can be performed using a pressurized system, but pressure is not required. MF membranes can be made of hollow fibers, capillaries, flat sheets, tubular structures, spiral wounds, pillows, hollow microfibers, or track etched. They are porous and allow water, monovalent substances (Na+, Cl-), dissolved organic matter, small colloids, and viruses to pass through, but retain particles, sediments, algae, or large bacteria.

[0022] UF membranes are generally suitable for removing suspended solid particles and high molecular weight solutes (e.g., above 100,000 Da). UF membranes are particularly suitable for removing bacteria and viruses. Typically, UF membranes have an average pore size of 0.5 nm to 50 nm, preferably 1 nm to 40 nm, and more preferably 5 nm to 20 nm.

[0023] The membrane (M) of the present invention can be used in any method of using membranes known to those skilled in the art.

[0024] Generally speaking, technicians are familiar with membrane fabrication. It is known that solvent exchange during membrane fabrication often results in asymmetric membrane structures.

[0025] The membrane (M) can be a porous membrane. Porous membranes typically contain pores, which, as determined by filtration experiments using solutions containing different PEGs with molecular weights ranging from 300 g / mol to 1,000,000 g / mol, typically have diameters in the range of 1 nm to 10,000 nm, preferably 2 nm to 500 nm, and particularly preferably 5 nm to 250 nm. The retention of each molecular weight of the membrane can be determined by comparing the GPC trace amounts of the feed and filtrate. The molecular weight at which the membrane exhibits 90% retention under given conditions is considered the molecular weight cutoff (MWCO) of that membrane. The average pore size of the membrane can be determined using the known correlation between the Stokes diameters of PEGs and their molecular weights. Details of this method are given in the literature (Chung, J. Membr. Sci. 531 (2017) 27-37). If the membrane is prepared via a phase inversion method, a porous membrane can generally be obtained.

[0026] Dense films typically do not actually contain pores. Dense films are usually obtained through a solution casting process, in which the solvent contained in the casting solution is evaporated. The release layer is typically cast onto a support, which can be another polymer, such as polysulfone or cellulose acetate. Sometimes a polydimethylsiloxane layer is applied on top of the release layer.

[0027] In one embodiment of the invention, the membrane (M) is a dense membrane. In particular, if the membrane is a dense membrane, it is especially suitable for gas separation.

[0028] The membrane (M) of the present invention can have any thickness. For example, the thickness of the membrane can be in the range of 2µm to 350µm, preferably in the range of 3µm to 200µm, and most preferably in the range of 5µm to 100µm.

[0029] According to one embodiment of the invention, the membrane (M) of the invention is an asymmetric membrane. In another embodiment, the membrane is porous.

[0030] The membrane (M) of the present invention is particularly suitable for nanofiltration, microfiltration and / or ultrafiltration, especially if the membrane is a porous membrane.

[0031] Therefore, according to one embodiment of the invention, the membrane (M) is a nanofiltration membrane, an ultrafiltration (UF) membrane, and / or a microfiltration membrane. Typical nanofiltration, ultrafiltration, and microfiltration methods are known to those skilled in the art.

[0032] According to one specific embodiment, the membrane of the present invention is an ultrafiltration membrane.

[0033] In another specific embodiment, the membrane (M) of the present invention is a UF membrane, which is a spiral wound membrane, a pillow block membrane, or a flat sheet membrane. In another embodiment, the membrane (M) of the present invention is a UF membrane, which is a tubular membrane.

[0034] In yet another embodiment, the membrane (M) is a hollow fiber membrane, which can be a monopore hollow fiber or a porous hollow fiber membrane. In the hollow fiber membrane, the semi-permeable barrier is in the form of hollow fibers.

[0035] Multichannel membranes, also known as porous membranes, include more than one longitudinal channel, also referred to as a "channel" or "pore".

[0036] The number of channels is typically 2 to 19. In one embodiment, the porous hollow fiber membrane includes two or three channels. In another embodiment, the porous hollow fiber membrane includes 5 to 9 channels. In one specific embodiment, the porous hollow fiber membrane includes seven channels. In yet another embodiment, the porous hollow fiber membrane includes 20 to 100 channels.

[0037] The shape of one or more holes can vary. Typically, according to the invention, the membrane has a substantially circular, elliptical, or rectangular diameter. Preferably, according to the invention, the membrane is substantially circular, i.e., the holes have a substantially circular diameter.

[0038] In another embodiment, the aperture has a substantially elliptical diameter. In yet another embodiment, the channel has a substantially rectangular diameter. In some cases, the actual shape of the channel may deviate from the idealized circular, elliptical, or rectangular form.

[0039] Typically, such a channel has an outer diameter of 0.05 mm to 3 mm, preferably 0.5 mm to 2 mm, more preferably 0.9 mm to 1.5 mm (for a substantially circular diameter), a smaller outer diameter (for a substantially elliptical diameter), or a smaller external feed size (for a substantially rectangular diameter). In another preferred embodiment, such a channel has an outer diameter ranging from 0.2 mm to 0.9 mm (for a substantially circular diameter), a smaller outer diameter (for a substantially elliptical diameter), or a smaller external feed size (for a substantially rectangular diameter).

[0040] According to the present invention, in a preferred embodiment, the hollow fiber membrane has an outer diameter of 2 mm to 10 mm, preferably 3 mm to 8 mm, more preferably 4 mm to 6 mm (for a substantially circular diameter), a smaller outer diameter (for a substantially elliptical diameter), or a smaller external feed size (for a substantially rectangular diameter).

[0041] In another preferred embodiment of the invention, the hollow fiber membrane has an outer diameter of 2 mm to 4 mm (for a substantially circular diameter), a smaller outer diameter (for a substantially elliptical diameter), or a smaller external feed size (for a substantially rectangular diameter).

[0042] Hollow fiber membranes can have any thickness. For example, the membrane thickness is in the range of 20µm to 150µm, preferably in the range of 20µm to 100µm, and most preferably in the range of 30µm to 60µm. This can be particularly suitable for dialysis membranes.

[0043] If the porous hollow fiber membrane comprises channels having a substantially rectangular shape, these channels can be arranged in a row. If the channels in the porous hollow fiber membrane have a substantially circular shape, these channels are preferably arranged such that a central channel is surrounded by the other channels. In a preferred embodiment, the membrane comprises a central channel and, for example, four, six, or eighteen additional channels arranged in a ring around the central channel. The wall thickness of such a multichannel membrane is typically 0.02 mm to 1 mm at its thinnest point, preferably 30 μm to 500 μm, and more preferably 100 μm to 300 μm.

[0044] In formula (I) of the repeating structural units (P1) and (P2) given above, if Q, T or Y are chemical bonds under the above premise, this means that the adjacent groups on the left and the adjacent groups on the right are directly connected to each other by chemical bonds.

[0045] According to a preferred embodiment, t and q are independently 0 or 1.

[0046] According to another preferred embodiment, Q, T, and Y in formula (I) are independently selected from chemical bonds, -O-, -SO2-, and -CR. a R b -, provided that at least one of Q, T, and Y exists and is -SO2-. Furthermore, if R a and R b Individually hydrogen or (C1-C4) alkyl groups may be preferred.

[0047] In -CR a R b -in, R a and R b Preferably, it is independently selected from hydrogen, (C1-C) 12 )alkyl, (C1-C 12 )alkoxy and (C6-C 18 Aryl.

[0048] (C1-C 12 Alkyl groups refer to straight-chain or branched saturated hydrocarbon groups having 1 to 12 carbon atoms. This specifically includes (C1-C6)alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2-methylpentyl, or 3-methylpentyl, and (C7-C6)alkyl groups. 12 Alkyl groups, such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their monobranched or multibranched analogs.

[0049] The term "C1-C" 12 "-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 12 carbon atoms bonded via oxygen at any position in an alkyl group, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy.

[0050] (C3-C 12Cycloalkyl refers to a monocyclic saturated hydrocarbon radical having 3 to 12 carbon ring members and particularly includes (C3-C8) cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclopentylpentyl, cyclopentylhexyl, cyclohexylmethyl, cyclohexyldimethyl and cyclohexyltrimethyl.

[0051] Ar and Ar 1 They are independent of each other (C6-C) 18 Ar-aryl group. Preferably, according to the specific embodiment, Ar 1 For unsubstituted (C6-C) 12 ) aryl group.

[0052] Ar and Ar are preferred. 1 Independently selected from phenylene, bisphenylene, and naphthylene, as well as aryl groups derived from anthracene, phenanthrene, or naphthonaphthalene. For example, Ar and Ar 1 It is independently selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 2,7-dihydroxynaphthylene, and 4,4'-biphenylene.

[0053] In particular, Ar and Ar are preferred. 1 Independently selected from phenylene and naphthyl groups, such as independently selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, and 2,7-naphthylene, more specifically independently selected from 1,4-phenylene, 1,3-phenylene, and naphthylene. Furthermore, according to another embodiment of the invention, Ar and Ar 1 The aryl group is independently selected from anthracene, phenanthrene, or naphthonaphthalene. According to yet another embodiment, Ar and Ar... 1 It is independently selected from 2,7-dihydroxynaphthalene and 4,4'-bis(phenylene).

[0054] According to one embodiment, in the membrane (M) of the present invention, at least one repeating structural unit of (P1) and (P2) is preferably selected from units 1a to 1s, respectively:

[0055]

[0056] Where x is between 0.05 and 1 and n is 1;

[0057]

[0058] Where x is between 0.05 and 1 and n is 1;

[0059]

[0060] Where x is between 0.05 and 1 and n is 1;

[0061] At least one structural repeating unit of (P2) is different from at least one structural repeating unit of (P1).

[0062] According to one embodiment, in the membrane (M) of the present invention, at least one repeating structural unit of (P1) and (P2) is preferably selected from units 1a to 1o and 1s, respectively.

[0063] According to another embodiment, in the membrane (M) of the present invention, at least one repeating structural unit of (P1) and (P2) is preferably selected from units 1a to 1o, respectively:

[0064] According to yet another embodiment, in the membrane (M) of the present invention, at least one repeating structural unit of (P1) and (P2) is preferably selected from units 1a, Ig, Ik, Ip and Is, and more specifically from units 1a, Ig, Ik and Is.

[0065] In another embodiment of the membrane (M) according to the invention, at least one repeating structural unit of (P1) and (P2) is preferably selected from units 1a, 1g and 1k, respectively.

[0066] Poly(arylene ether sulfone) containing repeating structural units of formula 1a is also known as polysulfone (PSU).

[0067] Poly(arylene ether sulfone) containing repeating structural units of formula Ig is also known as polyphenylene sulfone (PPSU).

[0068] Poly(arylene ether sulfone) containing repeating structural units of the formula Ik is also known as polyether sulfone (PESU or PES).

[0069] For the purposes of this disclosure, abbreviations such as PSU, PPSU, PESU (PES) conform to DIN EN ISO 1043-1:2001.

[0070] According to a specific implementation, (P1) contains unit 1a as a structural repeating unit, and (P2) contains unit 1g.

[0071] According to another specific implementation, (P1) includes unit 1a as a structural repeating unit, and (P2) includes unit Ik.

[0072] According to yet another specific implementation, (P1) contains unit Ig as a structural repeating unit, and (P2) contains unit Ik.

[0073] According to another specific embodiment of the present invention, (P1) includes unit 1a as a structural repeating unit, and (P2) includes unit Ip.

[0074] According to another specific implementation, (P1) contains unit Ig as a structural repeating unit, and (P2) contains unit Ip.

[0075] According to another specific implementation, (P1) contains unit Ik as a structural repeating unit, and (P2) contains unit Ip.

[0076] According to another specific embodiment of the present invention, (P1) includes unit 1a as a structural repeating unit, and (P2) includes unit Is.

[0077] According to yet another specific implementation, (P1) contains unit Ig as a structural repeating unit, and (P2) contains unit Is.

[0078] According to another specific implementation, (P1) contains unit Ik as a structural repeating unit, and (P2) contains unit Is.

[0079] In addition to at least one unit selected from units 1a to Is that may be present in (P1) or (P2), the other repeating units are repeating units in which one or more 1,4-phenylene units derived from hydroquinone have been replaced by 1,3-phenylene units derived from resorcinol or by naphthylene units derived from dihydroxynaphthalene.

[0080] The weight-average molar mass M of poly(aryl ether sulfone) polymers (P1) and (P2) w Preferably, the concentration is in the range of 10,000 g / mol to 180,000 g / mol, more preferably in the range of 15,000 g / mol to 150,000 g / mol, and particularly preferably in the range of 20,000 g / mol to 125,000 g / mol, determined by gel permeation chromatography using a narrowly distributed polymethyl methacrylate as a standard in dimethylacetamide as a solvent. More specifically, M w The concentration is from 10,000 g / mol to 100,000 g / mol, more specifically from 10,000 g / mol to 95,000 g / mol, particularly from 12,000 g / mol to 93,000 g / mol, and especially preferably from 14,000 g / mol to 90,000 g / mol, determined by gel permeation chromatography using a narrowly distributed polymethyl methacrylate as a standard in dimethylacetamide as a solvent.

[0081] The viscosity numbers (VN) of poly(aryl ether sulfone) polymers (P1) and (P2) were determined at 25°C in the form of a 1% N-methylpyrrolidone solution. The viscosity number (VN) is preferably in the range of 60 ml / g to 120 ml / g.

[0082] According to one embodiment, it is preferred that the poly(aryl ether sulfone) polymers (P1) and / or (P2) used in the membrane (M) of the present invention have high purity, particularly regarding the content of cyclic oligomers. "Cyclic dimers" are unwanted byproducts that can form during polycondensation in the preparation of the polymer. This impurity can be measured by the turbidity of the polymer product in a solution using DMF, DMAc, or NMP as a solvent. Methods for measuring turbidity are well known to those skilled in the art.

[0083] The production method of the above-mentioned poly(arylene ether sulfone) polymer is known to those skilled in the art and is described by way of example in Herman F. Mark, “Encyclopedia of Polymer Science and Technology”, 3rd edition, Vol. 4, 2003, chapter “Polysulfones”, pp. 2-8, and Hans R. Kricheldorf, “Aromatic Polyethers”, Handbook of Polymer Synthesis, 2nd edition, 2005, pp. 427-443.

[0084] The synthesis of poly(arylene ether sulfone) polymers can usually be carried out by polycondensation of suitable monomers in a dipolar aprotic solvent at elevated temperatures.

[0085] Overviews of the preparation of poly(aryl ether sulfone) polymers using hydroxide and carbonate methods are provided, for example, in RN Johnson et al., J. Polym. Sci. A-1 5 (1967) 2375 and JEMcGrath et al., Polymer 25 (1984) 1827. Furthermore, the production of polyaryl ether sulfone polymers is described in patent applications US4870153, EP113112, EP297363, and EP135130, all of which are incorporated herein by reference. In these patent applications, suitable precipitates, catalysts, solvents, and ratios of the components used, as well as reaction times and temperatures, can be found.

[0086] In the carbonate process, aromatic dihydroxy compounds react with aromatic dihalogen compounds in the presence of carbonates, preferably potassium carbonate. Generally, N,N-dimethylacetamide, DMF, N-ethylpyrrolidone, or NMP are preferably used as solvents, and toluene or chlorobenzene is added as an azeotropic agent to remove water. A method without an azeotropic agent is preferred.

[0087] Compared to the hydroxide method, the carbonate method has the advantage that the excess potassium carbonate can be varied over a relatively wide range without reducing the molecular weight of the resulting polymer. Thus, reaction control is simplified compared to the hydroxide method. According to the present invention, poly(aryl ether sulfone) polymers produced by any method can be used.

[0088] Particularly preferred is the reaction between at least one aromatic compound having two halogen substituents and at least one aromatic compound having two functional groups reactive to the aforementioned halogen substituents, in an aprotic polar solvent and in the presence of anhydrous alkali metal carbonates, particularly sodium carbonate, potassium carbonate, calcium carbonate, or mixtures thereof, and very particularly preferred is potassium carbonate. A particularly suitable combination is N-methyl-2-pyrrolidone as a solvent and potassium carbonate as a base.

[0089] Preferably, the poly(aryl ether sulfone) polymers (P1) and / or (P2) have halogenated end groups (especially chlorinated end groups) or etherified end groups, particularly alkyl ether end groups, which can be obtained by reacting OH or phenolic salt end groups with suitable etherifying agents, respectively. Examples of suitable etherifying agents are functional alkyl or aryl halogens, such as C1-C6-alkyl chlorides, C1-C6-alkyl bromides, or C1-C6-alkyl iodides, preferably methyl chlorides, or benzyl chlorides, benzyl bromides, or benzyl iodides, or mixtures thereof. For the purposes of the polyaryl (ether) sulfone of component A), preferred end groups are halogenated, particularly chlorinated, alkoxy, particularly methoxy, aryloxy, particularly phenoxy, or benzyloxy.

[0090] Based on the total weight of the membrane (M), the combined weight percentage of the poly(aryl ether sulfone) polymers (P1) and (P2) contained in the membrane (M) of the present invention is preferably at least 50% by weight, more preferably at least 60% by weight, and more specifically at least 70% by weight. According to one embodiment, it may be preferred if the combined weight percentage of the poly(aryl ether sulfone) polymers (P1) and (P2) contained in the membrane (M) of the present invention is at least 75% by weight, more specifically at least 80% by weight, and even more specifically at least 85% by weight, based on the total weight of the membrane (M).

[0091] According to one embodiment, based on the total weight of the membrane (M), the combined amount of poly(arylene ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein is 40% to 95% by weight, more specifically 45% to 90% by weight, even more specifically 50% to 90% by weight, even more specifically 60% to 90% by weight.

[0092] In the membrane (M) of the present invention, the ratio of the poly(aryl ether sulfone) polymer (P1) to (P2), as defined herein and preferably as defined herein, can be any possible weight ratio, such as 1:10 to 10:1, particularly 1:9 to 9:1, more particularly 1:8 to 8:1, and even more particularly 1:7 to 7:1. According to a specific embodiment, the ratio can be 1:6 to 6:1 or 1:5 to 5:1, particularly 1:4 to 4:1, more particularly 1:3 to 3:1, and even more particularly 1:2 to 2:1. According to a very specific embodiment of the invention, (P1) and (P2) can be present in equal or nearly equal amounts (1:1). In this context, "nearly equal amounts" means that the difference in the amounts of (P1) and (P2) is only negligible.

[0093] The copolymer (CP) in the membrane of the present invention comprises at least one poly(arylene ether sulfone) (A) block and at least one polyepoxyalkylene PAO block.

[0094] According to one embodiment, at least one poly(arylene ether sulfone) (A) block in the copolymer (CP) is selected from polyether sulfone, polysulfone and polyphenylene sulfone, or copolymers or mixtures thereof.

[0095] Suitable poly(aryl ether sulfone) (A) blocks in copolymers (CP) are known to those skilled in the art. They are preferably formed from poly(aryl ether sulfone) units having the general formula (II):

[0096]

[0097] The symbols t, q, Q, T, Y, Ar, and Ar 1 The definition is as follows (see also, as defined herein with respect to equation (I), and preferably as defined herein with respect to equation (I), which also applies independently to equation (II)):

[0098] t and q are independent of each other and can be 0, 1, 2 or 3;

[0099] Q, T, and Y are independent chemical bonds or selected from -O-, -S-, -SO2-, S=O, C=O, -N=N-, and -CR. a R b - groups, where R a and Rb Each is an independent hydrogen atom, (C1-C) 12 )alkyl, (C1-C 12 )alkoxy or (C6-C 18 ) aryl group, wherein at least one of Q, T and Y is not O and at least one of Q, T and Y is -SO2-;

[0100] Ar and Ar 1 They are independent of each other (C6-C) 18 ) aryl; and

[0101] D represents a chemical bond or -O-.

[0102] According to one embodiment, if D is directly bonded to another aryl ether unit, then D is an oxygen atom -O-. According to another embodiment, if D is directly bonded to a polyoxyalkylene block, then D is a chemical bond.

[0103] Under the above conditions, if Q, T, or Y are chemical bonds, it means that the adjacent groups on the left and the adjacent groups on the right are directly connected to each other by chemical bonds.

[0104] According to a preferred embodiment, t and q are independently 0 or 1.

[0105] According to a preferred embodiment, Q, T, and Y in formula (II) are independently selected from chemical bonds, -O-, -SO2-, and -CR. a R b -, provided that at least one of Q, T, and Y exists and is -SO2-. Furthermore, if R a and R b Individually hydrogen or (C1-C4) alkyl groups may be preferred.

[0106] In -CR a R b -in, R a and R b Preferably, it is independently selected from hydrogen, (C1-C) 12 )alkyl, (C1-C 12 )alkoxy and (C6-C 18 Aryl.

[0107] (C1-C 12 Alkyl groups refer to straight-chain or branched saturated hydrocarbon groups having 1 to 12 carbon atoms. This specifically includes (C1-C6)alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2-methylpentyl, or 3-methylpentyl, and (C7-C6)alkyl groups. 12Alkyl groups, such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their monobranched or multibranched analogs.

[0108] The term "C1-C" 12 "-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 12 carbon atoms bonded via oxygen at any position in an alkyl group, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy.

[0109] (C3-C 12 Cycloalkyl refers to a monocyclic saturated hydrocarbon radical having 3 to 12 carbon ring members and particularly includes (C3-C8) cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclopentylpentyl, cyclopentylhexyl, cyclohexylmethyl, cyclohexyldimethyl and cyclohexyltrimethyl.

[0110] Ar and Ar 1 They are independent of each other (C6-C) 18 Ar-aryl group. Preferably, according to the specific embodiment, Ar 1 For unsubstituted (C6-C) 12 ) aryl group.

[0111] Ar and Ar are preferred. 1 Independently selected from phenylene, bisphenylene, and naphthylene, as well as aryl groups derived from anthracene, phenanthrene, or naphthonaphthalene. For example, Ar and Ar 1 It is independently selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 2,7-dihydroxynaphthylene, and 4,4'-biphenylene.

[0112] In particular, Ar and Ar are preferred. 1 Independently selected from phenylene and naphthyl groups, such as independently selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, and 2,7-naphthylene, more specifically independently selected from 1,4-phenylene, 1,3-phenylene, and naphthylene. Furthermore, according to another embodiment of the invention, Ar and Ar 1 The aryl group is independently selected from anthracene, phenanthrene, or naphthonaphthalene. According to yet another embodiment, Ar and Ar... 1 It is independently selected from 2,7-dihydroxynaphthalene and 4,4'-bis(phenylene).

[0113] Preferably, the units present in the poly(arylene ether sulfone) (A) of the copolymer (CP) comprise at least one of the following repeating structural units IIa to IIo, wherein D has the same meaning as defined above:

[0114]

[0115] According to another embodiment of (A), there may be one or more of the 1,4-dihydroxyphenyl units that are replaced by resorcinol or dihydroxynaphthalene units.

[0116] Particularly preferred units having general formula (II) are units IIa, IIg, and IIk. Also particularly preferred is that the poly(arylene ether sulfone) block is formed essentially of one of the units having general formula (II), especially of one selected from IIa, IIg, and IIk.

[0117] In one specific embodiment, Ar = 1,4-phenylene, t = 1, q = 0, T = SO2, and Y = SO2. This poly(arylene ether sulfone) is called polyether sulfone (PESU).

[0118] In another specific embodiment, Ar is 1,4-phenylene, t is 1, q is 0, T is a chemical bond, and Y is SO2. This poly(arylene ether sulfone) is called polyphenylene sulfone (PPSU).

[0119] A suitable poly(aryl ether sulfone) block (A) preferably has an average molecular weight Mn (number average) in the range of 1000 g / mol to 70000 g / mol, more preferably in the range of 2000 g / mol to 40000 g / mol, and particularly preferably in the range of 2500 g / mol to 30000 g / mol. The average molecular weight of the poly(aryl ether sulfone) block (A) can be controlled and calculated by the ratio of the monomers forming the poly(aryl ether sulfone) block, as described in H.G. Elias, “An Introduction to Polymer Science”, V.C. Weinheim, 1997, page 125.

[0120] Poly(arylene ether sulfone) (A) is typically prepared by polycondensation of a suitable starting compound in a dipolar aprotic solvent at elevated temperatures (see, for example, RN Johnson et al., J. Polym. Sci. A-1 5 (1967) 2375, JE McGrath et al., Polymer 25 (1984) 1827). See also above for polymers (P1) and (P2).

[0121] Suitable poly(aryl ether sulfone) blocks (A) can be formed by oxidizing at least one of the following structures in the presence of a solvent (L) and a base (B): 1 -Ar-Y 1 The starting compound (M1) and at least one HO-Ar structure 1 The -OH starting compound (M2) is provided by the reaction, in which

[0122] Y 1 Halogen atoms,

[0123] X 1 Selected from halogen atoms and OH, preferably selected from halogen atoms, especially selected from F, Cl and Br, and

[0124] Ar and Ar 1 They are independent of each other (C6-C) 18 )Asyl.

[0125] Suitable starting compounds are known to those skilled in the art and are not limited in any way, provided that the substituents mentioned are sufficiently reactive to nucleophilic aromatic substitutions.

[0126] Preferred starting compounds are bifunctional. "Bifunctional" means that each starting compound has two reactive groups in nucleophilic aromatic substitution. Another criterion for suitable bifunctional starting compounds is sufficient solubility in solvents, as explained in detail below.

[0127] The preferred starting compound is the monomer, which means that the reaction preferably begins with the monomer rather than with the prepolymer.

[0128] The starting compound (M1) used is preferably a dihalodiphenyl sulfone. The starting compound (M2) used is preferably a dihydroxydiphenyl sulfone.

[0129] Suitable starting compounds (M1) are especially dihalodiphenyl sulfones, such as 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 4,4'-dibromodiphenyl sulfone, bis(2-chlorophenyl) sulfone, 2,2'-dichlorodiphenyl sulfone and 2,2'-difluorodiphenyl sulfone, with 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone being particularly preferred.

[0130] Therefore, the preferred compound (M2) is a compound having two phenolic hydroxyl groups.

[0131] The phenolic OH group preferably reacts in the presence of a base to increase its reactivity to the halogen substituents of the starting compound (M1).

[0132] The preferred starting compound (M2) having two phenolic hydroxyl groups is selected from the following compounds:

[0133] -Dihydroxybenzene, especially hydroquinone and resorcinol;

[0134] -Dihydroxynaphthalene, especially 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene;

[0135] -Dihydroxybiphenyl, especially 4,4'-biphenyl and 2,2'-biphenyl;

[0136] -Diphenyl ethers, especially bis(4-hydroxyphenyl) ethers and bis(2-hydroxyphenyl) ethers;

[0137] -Diphenylpropane, especially 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane;

[0138] -Diphenylmethane, especially bis(4-hydroxyphenyl)methane;

[0139] -Diphenyl sulfone, especially bis(4-hydroxyphenyl) sulfone;

[0140] - Diphenyl sulfides, especially bis(4-hydroxyphenyl) sulfides;

[0141] -Diphenyl ketones, especially bis(4-hydroxyphenyl) ketones;

[0142] -Diphenylhexafluoropropane, especially 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)hexafluoropropane; and

[0143] -Bisphenylfluorene, especially 9,9-bis(4-hydroxyphenyl)fluorene;

[0144] -1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bisphenol TMC).

[0145] If the aforementioned aromatic dihydroxy compound (M2) is used, it is preferable to prepare a dipotassium salt or disodium salt by adding a base (B) and reacting it with the starting compound (M1). The aforementioned compound can be used alone or in combination of two or more of the aforementioned compounds.

[0146] Hydroquinone, resorcinol, dihydroxynaphthalene, especially 2,7-dihydroxynaphthalene, bisphenol A, dihydroxydiphenyl sulfone and 4,4'-bisphenol are particularly preferred as starting compounds (M2).

[0147] Trifunctional compounds can also be used to produce branched structures. If a trifunctional starting compound (M2) is used, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

[0148] The appropriate ratio of reactants can be derived from the stoichiometry of the polycondensation reaction, which can be determined by those skilled in the art in a known manner.

[0149] In a preferred embodiment, the ratio of halogen end groups to phenol end groups is adjusted by controlling the excess of the dihalogen starting compound (M1) relative to the bifunctional compound (M2) and the polyepoxide PAO, which are used as starting compounds.

[0150] According to one embodiment, the (M1) / (M2) molar ratio is 1.001 to 1.7, even more preferably 1.003 to 1.5, particularly preferably 1.005 to 1.3, and most preferably 1.01 to 1.1.

[0151] Alternatively, a starting compound (M1) can be used, wherein X 1 =halogen and Y 1 =OH. In this case, the ratio of the halogen used to the OH terminal group is preferably 1.001 to 1.7, more preferably 1.003 to 1.5, especially 1.005 to 1.3, and most preferably 1.01 to 1.251.

[0152] Preferably, the conversion rate during polycondensation is at least 0.9, which ensures a sufficiently high molecular weight.

[0153] In the context of this invention, the preferred solvent (L) is an organic solvent, particularly an aprotic polar solvent. Suitable solvents also have a boiling point at atmospheric pressure in the range of 80°C to 320°C, particularly in the range of 100°C to 280°C, and preferably in the range of 150°C to 250°C. Suitable aprotic polar solvents include, for example, high-boiling-point ethers, esters, ketones, asymmetric halogenated hydrocarbons, anisoles, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone, and / or N-ethyl-2-pyrrolidone. Mixtures of these solvents may also be used.

[0154] The preferred solvent (L) is N-methyl-2-pyrrolidone and / or N-ethyl-2-pyrrolidone, especially N-methyl-2-pyrrolidone.

[0155] Preferably, the starting compounds (M1) and (M2) react with the polyepoxide PAO in the aforementioned aprotic polar solvent (L), particularly in N-methyl-2-pyrrolidone.

[0156] The suitable polyepoxide PAO block in the copolymer (CP) contains at least one polymerized alkylene oxide.

[0157] Examples of alkylene oxides include ethylene oxide (EO), propylene oxide (PO), butane oxide (BO), styrene oxide (SO), and tetrahydrofuran (THF).

[0158] Preferably, the at least one alkylene oxide is selected from ethylene oxide, propylene oxide, butane oxide, and tetrahydrofuran, and especially preferably EO and PO.

[0159] Specifically, according to one embodiment, the polyepoxide (PAO) comprises ethylene oxide units -(CH2)2-O- and / or propylene oxide units -CH2-CH(CH3)-O- as major components. More advanced alkylene oxide units (i.e., alkylene oxide units having more than 3 carbon atoms) are typically present only in small amounts. This allows for appropriate tuning of the polymer properties.

[0160] Preferably, the polyepoxide (PAO) comprises an ethylene oxide unit -(CH2)2-O- as the main component. More advanced alkylene oxide units (i.e., alkylene oxide units having more than two carbon atoms) are typically present only in small amounts. This allows for appropriate tuning of the polymer properties.

[0161] The polyepoxide (PAO) block can be a random copolymer, gradient copolymer, alternating copolymer, or block copolymer comprising units selected from ethylene oxide and propylene oxide units. The amount of higher alkylene oxide units having more than 3 carbon atoms generally does not exceed 10% by weight, preferably not more than 5% by weight.

[0162] Polyepoxide (PAO) blocks can be obtained in ways known to those skilled in the art, for example, by polymerization of alkylene oxides and / or cyclic ethers having at least three carbon atoms, along with optional additional components. They can also be prepared by polycondensation of diols and / or polyols, suitable starting materials, and optional additional monomer components.

[0163] Suitable alkylene oxides as monomers for poly(alkylene oxide) (PAO) blocks include ethylene oxide, propylene oxide, 1-epoxybutane, 2,3-epoxybutane, 2-methyl-1,2-epoxypropane (isobutylene oxide), 1-epoxypentane, 2,3-epoxypentane, 2-methyl-1,2-epoxybutane, 3-methyl-1,2-epoxybutane, 2,3-epoxyhexane, 3,4-epoxyhexane, 2-methyl-1,2-epoxypentane, 2-ethyl-1,2-epoxybutane, 3-methyl-1,2-epoxypentane, decane oxide, 4-methyl-1,2-epoxypentane, and styrene oxide. Examples of suitable cyclic ethers include tetrahydrofuran. Mixtures of different alkylene oxides can also be used. Those skilled in the art make appropriate selections from monomers and additional components based on the desired properties of the block.

[0164] Polyepoxide (PAO) blocks can also be branched or star-shaped. These blocks can be obtained using starter molecules with at least three arms. Examples of suitable starters include glycerol, trimethylolpropane, pentaerythritol, and ethylenediamine.

[0165] According to one embodiment, the polyepoxide block PAO is a homopolymer of an alkylene oxide (preferably ethylene oxide).

[0166] In another embodiment, the suitable polyoxyethylene PAO block comprises only ethylene oxide and propylene oxide, and the number-average molar ratio of propylene oxide to ethylene oxide is 200:1 to 1:200. In one specific embodiment, the number-average molar ratio of propylene oxide to ethylene oxide is 150:1 to 1.5:1, more preferably 100:1 to 2:1, and particularly preferably 50:1 to 5:1. In another embodiment, the number-average molar ratio of propylene oxide to ethylene oxide is 40:1 to 10:1 or 35:1 to 20:1. According to another embodiment, the number-average molar ratio of ethylene oxide to propylene oxide is 150:1 to 1.5:1, more preferably 100:1 to 2:1, and particularly 50:1 to 5:1.

[0167] The synthesis of alkylene oxide blocks is known to those skilled in the art. Details are given, for example, in "Polyoxyalkylenes" in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, electronic version.

[0168] According to one embodiment, a suitable polyepoxide PAO block is end-capped on one side with an alkyl or aryl group to obtain a block copolymer comprising individual polymer molecules having the general formula PAO-A or PAO-A-PAO. If the polyepoxide block is end-capped on one side with an alkyl or aryl group, then at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%, and even more preferably at least 95 mol% of all individual polymer molecules comprising the polyepoxide block in the block copolymer according to the invention typically have the general formula PAO-A or PAO-A-PAO.

[0169] In a preferred embodiment, a suitable polyepoxide PAO block has OH groups at both end positions, resulting in a block copolymer that may contain multiple polyepoxide blocks in a single polymer molecule.

[0170] Suitable polyepoxides can be linear or branched. Branching of polyepoxides can be achieved, for example, by including monomers with epoxide groups and OH or chlorine moieties within the polyepoxide. Preferably, suitable polyepoxides are linear.

[0171] Suitable polyepoxide PAO blocks typically contain 2.1 to 600 alkylene oxide units. Preferably, suitable polyepoxides contain 3 to 300, more preferably 5 to 150, and even more preferably 10 to 100 alkylene oxide units.

[0172] The copolymer (CP) comprises a polyepoxide (PAO) block and a poly(aryl ether sulfone) (A) block. Preferably, at least 80 mol% of the polyepoxide (PAO) block, more preferably at least 90 mol%, and even more preferably at least 95 mol%, is covalently bonded to the poly(aryl ether sulfone) block (A). In a preferred embodiment, substantially all of the polyepoxide (PAO) block is covalently bonded to the poly(aryl ether sulfone) block (A). Typically, the polyepoxide (PAO) block is covalently bonded to the poly(aryl ether sulfone) block (A) via an -O- group (ether group).

[0173] The content of polyepoxide (PAO) in the copolymer (CP) is, for example, 30% to 90% by weight, preferably 35% to 70% by weight, and even more preferably 35% to 55% by weight.

[0174] Preferably, the copolymer (CP) comprises 30% to 90% by weight, preferably 35% to 70% by weight, even more preferably 35% to 55% by weight of a polyepoxide (e.g., such as polyethylene oxide), and 70% to 10% by weight, preferably 65% ​​to 30% by weight, and even more preferably 65% ​​to 45% by weight of at least one poly(arylene ether sulfone) (A).

[0175] According to one embodiment, a suitable block copolymer comprises individual polymer molecules having the general formula PAO-A or PAO-A-PAO. Typically, at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%, and even more preferably at least 95 mol% of all individual polymer molecules comprising polyoxyalkylene blocks contained in a suitable block copolymer have the general formula PAO-A or PAO-A-PAO.

[0176] Typically, the average molecular weight Mw of the block copolymer (CP) (determined by GPC according to the procedure given in the experimental section) is from 5000 g / mol to 150,000 g / mol, preferably from 7500 g / mol to 100,000 g / mol, and more preferably from 0,000 g / mol to 50,000 g / mol.

[0177] Suitable block copolymers preferably have a polydispersity (Mw / Mn) of 1.5 to 5, more preferably 2 to 4 (determined by GPC according to the procedure given in the experimental section).

[0178] According to one embodiment, the copolymer (CP) has two glass transition temperatures. For example, the copolymer (CP) may have one glass transition temperature in the range of -80°C to -20°C and one glass transition temperature in the range of 100°C to 225°C (determined by differential scanning calorimetry (DSC) as described in the experimental section).

[0179] According to another embodiment, the copolymer (CP) has a glass transition temperature. According to yet another embodiment, the copolymer (CP) has a glass transition temperature of -50°C to 200°C, preferably -40°C to 150°C.

[0180] According to the present invention, the copolymer (CP) can be prepared from its components in a solvent (L).

[0181] In a preferred embodiment of the preparation of the copolymer (CP), starting compounds (M1) and (M2) react with a polyepoxide in the presence of a solvent (L) and preferably in the presence of a base (B) to obtain a suspension. A suitable base (B) is, for example, an anhydrous alkali metal and / or alkaline earth metal carbonate, preferably sodium carbonate, potassium carbonate, calcium carbonate, or mixtures thereof, more specifically potassium carbonate, especially potassium carbonate with a volume-weighted average particle size of less than 200 micrometers, determined by a particle size analyzer in the N-methyl-2-pyrrolidone suspension.

[0182] A particularly preferred combination is N-methyl-2-pyrrolidone as the solvent (L) and potassium carbonate as the base (B).

[0183] The reaction of the corresponding starting compounds (M1) and (M2) with polyepoxides is generally preferably carried out at a temperature of 80°C to 250°C, preferably 100°C to 220°C, wherein the upper limit of the temperature can be determined by the boiling point of the solvent.

[0184] The reaction can occur over time intervals of 2 to 12 hours, especially 3 to 8 hours.

[0185] If the molar ratio of (M1) / (M2 + polyepoxide PAO) is 1.000 to 1.25, more preferably 1.005 to 1.2, it may be preferred.

[0186] In particular, suitable starting materials, bases, solvents, ratios of all participating components, reaction times and reaction parameters (such as temperature and pressure), and suitable processing procedures are disclosed, for example, in US 4,870,153, column 4, line 11 to column 17, line 64; EP 113 112, page 6, line 1 to page 9, line 14; EP-A 297 363, page 10, line 38 to page 11, line 24; and EP-A 135 130, page 1, line 37 to page 4.

[0187] If desired, the resulting suspension can be modified before, during, or after the preparation of the copolymer (CP) by adding or removing an additional solvent.

[0188] After preparing the copolymer (CP), it can be advantageous to remove any inorganic components present in the mixture. Such inorganic components are, for example, sodium chloride or residues formed during the reaction, such as sodium carbonate or sodium hydroxide. Such inorganic components can be removed, for example, by filtration. Preferably, after filtration, particles with an average particle size greater than 10 µm, preferably greater than 5 µm, are not detectable by light scattering.

[0189] According to one embodiment, the membrane (M) contains at least 5% by weight, more specifically at least 10% by weight, of copolymer (CP) based on the total weight of the membrane (M). In particular, it is likely preferred if the membrane (M) contains 5% to 60% by weight, more specifically 5% to 55% by weight, or even more specifically 5% to 50% by weight, of copolymer (CP) based on the total weight of the membrane (M). Furthermore, it is likely preferred if the membrane (M) contains 10% to 60% by weight, more specifically 10% to 55% by weight, or even more specifically 10% to 50% by weight, of copolymer (CP) based on the total weight of the membrane (M).

[0190] The membrane of the present invention may further comprise at least one hydrophilic polymer additive (AD). Specifically, the at least one additive (AD) is selected from poly(epoxyalkylene), polyvinylpyrrolidone (PVP), and sulfonated poly(aryl ether sulfone) polymers (SP). According to one specific embodiment, the membrane (M) contains no additive (AD).

[0191] According to one embodiment, based on the total weight of the membrane (M), the membrane (M) of the present invention contains 0.1 wt% to 10 wt%, more specifically 0.5 wt% to 7 wt%, and even more specifically 1 wt% to 5 wt% of additives (AD). According to another embodiment, based on the total weight of the membrane (M), the membrane (M) of the present invention contains 0.1 wt% to 5 wt%, more specifically 0.2 wt% to 3 wt%, and even more specifically 0.3 wt% to 2 wt% of additives (AD). In particular, AD may be present in an amount of 0.1 wt% to 1 wt%, more specifically 0.3 wt% to 1 wt%.

[0192] Polyvinylpyrrolidone is commercially available, for example, from Luvitec of BASF SE. ® According to one embodiment, PVP has a solution viscosity characterized by a K value of at least 12 (PVP K12), at least 30 (PVP K30), or at least 85 (PVP K85). If PVP has a solution viscosity characterized by a K value of at least 80 (PVP K80), such as Luvitec... ® K80 is likely preferred. In another preferred embodiment, PVP has a solution viscosity characterized by a K value of at least 85 (PVP K85), such as, for example, Luvitec. ® K85. If PVP has a solution viscosity characterized by a K value of at least 90 (PVP K90), such as Luvitec... ® K90 may also be a preferred option.

[0193] The solution viscosity was determined according to Fikentscher’s method (Fikentscher, Cellu-losechemie 13, 1932(58)).

[0194] The sulfonated poly(arylene ether sulfone) polymer preferably comprises a unit having formula (III):

[0195]

[0196] The symbols t, q, Q, T, Y, Ar, and Ar 1 The definition is as follows:

[0197] t and q are independent of each other and can be 0, 1, 2 or 3;

[0198] Q, T, and Y are independent chemical bonds or selected from -O-, -S-, -SO2-, S=O, C=O, -N=N-, and -CR. a R b - groups, where R a and R b Each is an independent hydrogen atom, (C1-C) 12 )alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkyl or (C6-C 18 ) aryl group, wherein at least one of Q, T and Y is present and is -SO2-; and

[0199] Ar and Ar 1 They are independent of each other (C6-C) 18 )triaryl;

[0200] And among them

[0201] At least one unit (III) comprises an aryl group substituted with at least one -SO2X group, wherein X is selected from the group consisting of Cl and O- bonded to a cationic equivalent, wherein the cationic equivalent is H + Li + Na + K + Mg 2+ Ca 2+ or NH4 + .

[0202] In the above conditions, if Q, T, or Y are chemical bonds, this should be understood as meaning that the adjacent groups on the left and the adjacent groups on the right are directly bonded to each other via chemical bonds. It will be readily understood that at least one of the groups composed of Q, T, and Y being -SO2- means that at least one group in formula (I) is -SO2-. Therefore, when q=0, at least one of T and Y is -SO2-; when, for example, t=0, at least one of Q and Y is -SO2-; and when q=0 and t=0, then Y is SO2.

[0203] According to a preferred embodiment, t and q are independently 0 or 1.

[0204] According to a preferred embodiment, Q, T, and Y in formula (I) are independently selected from chemical bonds, -O-, -SO2-, and -CR. a R b -, provided that at least one of Q, T, and Y exists and is -SO2-. Furthermore, if R a and R b Individually hydrogen or (C1-C4) alkyl groups may be preferred.

[0205] In -CR a R b -in, R a and R b Preferably, it is independently selected from hydrogen, (C1-C) 12 )alkyl, (C1-C 12 )alkoxy and (C6-C 18 Aryl.

[0206] (C1-C 12 Alkyl groups refer to straight-chain or branched saturated hydrocarbon groups having 1 to 12 carbon atoms. This specifically includes (C1-C6)alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2-methylpentyl, or 3-methylpentyl, and (C7-C6)alkyl groups. 12 Alkyl groups, such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their monobranched or multibranched analogs.

[0207] The term "C1-C" 12 "-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 12 carbon atoms bonded via oxygen at any position in an alkyl group, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy.

[0208] (C3-C 12Cycloalkyl refers to a monocyclic saturated hydrocarbon radical having 3 to 12 carbon ring members and particularly includes (C3-C8) cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclopentylpentyl, cyclopentylhexyl, cyclohexylmethyl, cyclohexyldimethyl and cyclohexyltrimethyl.

[0209] Ar and Ar 1 They are independent of each other (C6-C) 18 Ar-aryl group. Preferably, according to the specific embodiment, Ar 1 For unsubstituted (C6-C) 12 ) aryl group.

[0210] Ar and Ar are preferred. 1 Independently selected from phenylene, bisphenylene, and naphthylene, as well as aryl groups derived from anthracene, phenanthrene, or naphthonaphthalene. For example, Ar and Ar 1 Selected independently from:

[0211] 1,2-Phenylidene, 1,3-Phenylidene, 1,4-Phenylidene, 1,6-Naphthylene, 1,7-Naphthylene, 2,6-Naphthylene, 2,7-Naphthylene, 2,7-Dihydroxynaphthylene, and 4,4'-Biphenylene.

[0212] In particular, Ar and Ar are preferred. 1 Independently selected from phenylene and naphthyl groups, such as independently selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, and 2,7-naphthylene, more specifically independently selected from 1,4-phenylene, 1,3-phenylene, and naphthylene. Furthermore, according to another embodiment of the invention, Ar and Ar 1 The aryl group is independently selected from anthracene, phenanthrene, or naphthonaphthalene. According to yet another embodiment, Ar and Ar... 1 It is independently selected from 2,7-dihydroxynaphthalene and 4,4'-bis(phenylene).

[0213] Preferred sulfonated poly(aryl ether sulfone) polymers are those that, as defined herein and preferably as defined herein, include at least one of units 1a to 1o as repeating structural units, wherein at least one unit of units 1a to 1o comprises an aryl group substituted with at least one -SO2X group, wherein X is selected from the group consisting of Cl and O- bonded to a cationic equivalent, wherein the cationic equivalent is H. + Li + Na + K+ Mg 2+ Ca 2+ or NH4 + :

[0214] According to one embodiment, the sulfonated poly(arylene ether sulfone) polymer comprises at least one unit selected from units 1a, 1g, and 1k as repeating structural units, wherein at least one of the units comprises an arylene group substituted with at least one -SO2X group, wherein X is selected from the group consisting of Cl and O- bonded to a cationic equivalent, wherein the cationic equivalent is H. + Li + Na + K + Mg 2+ Ca 2+ or NH4 + :

[0215] According to one embodiment, the sulfonated poly(arylene ether sulfone) polymer comprises a repeating structural unit having the formula 1a and is also referred to as sulfonated polysulfone (sPSU). The unit 1a comprises an arylene group substituted with at least one -SO2X group, wherein X is selected from the group consisting of Cl and O- bonded to a cationic equivalent, wherein the cationic equivalent is H. + Li + Na + K + Mg 2+ Ca 2+ or NH4 + :

[0216] According to another embodiment, the sulfonated poly(aryl ether sulfone) polymer comprises a repeating structural unit having the formula Ig and is also referred to as sulfonated polyphenylene sulfone (sPPSU). Unit Ig comprises an aryl group substituted with at least one -SO2X group, wherein X is selected from the group consisting of Cl and O- bonded to a cationic equivalent, wherein the cationic equivalent is H. + Li + Na + K + Mg 2+ Ca 2+ or NH4 + :

[0217] According to yet another embodiment, the sulfonated poly(arylene ether sulfone) polymer comprises a repeating structural unit having the formula Ik and is also referred to as sulfonated polyether sulfone (sPESU or sPES). Unit Ik comprises an arylene group substituted with at least one -SO2X group, wherein X is selected from the group consisting of Cl and O- bonded to a cationic equivalent, wherein the cationic equivalent is H.+ Li + Na + K + Mg 2+ Ca 2+ or NH4 + :

[0218] Sulfonated poly(aryl ether sulfone) polymers have been known for decades (A. Noshay, LM Robeson, J. Appl. Polym. Sci. 20 (1976) 1885). While direct sulfonation of poly(aryl ether sulfone) polymers introduces side reactions and allows only limited control over the degree of sulfonation, the use of disulfonated dichlorodiphenyl sulfone (sDCDPS) as a comonomer allows for the synthesis of well-defined sulfonated poly(aryl ether sulfone) polymers (lleda et al., J. Polym. Sci. A, Polym. Chem. 31 (1993) 853; JEMcGrath et al., Macromol. Symp. 175 (2001) 387). Further details regarding the synthesis of high molecular weight sulfonated poly(aryl ether sulfone) polymers can be found in PCT / EP2023 / 064280.

[0219] According to one embodiment, the additive (AD) preferably comprises polyvinylpyrrolidone (PVP).

[0220] More preferably, the hydrophilic polymer additive (AD) comprises at least 50% by weight, preferably at least 60% by weight, and particularly at least 70% by weight, of PVP relative to the amount of additive (AD) in the membrane. In a preferred embodiment, the hydrophilic polymer additive (AD) consists of polyvinylpyrrolidone as defined herein, and preferably as defined herein. In one embodiment, the membrane (M) comprises PVP as defined herein, and preferably as defined herein.

[0221] If present, based on the total weight of the membrane, the amount of PVP in the membrane (M) of the present invention, as defined herein and preferably as defined herein, is preferably 0.1 wt% to 5 wt%, more specifically 0.2 wt% to 3 wt%, and even more specifically 0.3 wt% to 2 wt%. In another embodiment, the amount of PVP in the membrane of the present invention is 0.4 wt% to 1.5 wt%, more specifically 0.5 wt% to 1.3 wt%, and even more specifically 0.6 wt% to 1.2 wt%. In yet another embodiment, the amount of PVP is 0.7 wt% to 1.1 wt%. In particular, PVP may be present in an amount of 0.1 wt% to 1 wt%, more specifically 0.3 wt% to 1 wt%.

[0222] According to another specific embodiment of the invention, the membrane (M) of the invention is substantially free of PVP. In the context of the invention, "substantially free of" means, based on the total weight of the membrane, that the membrane contains at most 0.05% by weight, preferably at most 0.04% by weight, and particularly preferably at most 0.03% by weight, more specifically at most 0.01% by weight of PVP. According to a very specific embodiment, the membrane (M) of the invention contains no PVP whatsoever.

[0223] According to yet another embodiment, the additive (AD) preferably comprises a sulfonated poly(aryl ether sulfone) polymer (SP). Preferably, the hydrophilic polymer additive (AD) comprises at least 50% by weight, preferably at least 60% by weight, and particularly at least 70% by weight of the sulfonated poly(aryl ether sulfone) polymer (SP), relative to the amount of additive (AD) in the membrane. In a preferred embodiment, the hydrophilic polymer additive (AD) consists of at least one sulfonated poly(aryl ether sulfone) polymer (SP) as defined herein and preferably as defined herein. In one embodiment, the membrane (M) comprises at least one sulfonated poly(aryl ether sulfone) polymer (SP) as defined herein and preferably as defined herein.

[0224] If present, the amount of sulfonated poly(aryl ether sulfone) polymer (SP) in the membrane (M) of the present invention is preferably 0.1 wt% to 5 wt%, more specifically 0.2 wt% to 3 wt%, and even more specifically 0.3 wt% to 2 wt%, based on the total weight of the membrane. In another embodiment, the amount of sulfonated poly(aryl ether sulfone) polymer (SP) in the membrane of the present invention is 0.4 wt% to 1.5 wt%, more specifically 0.5 wt% to 1.3 wt%, and even more specifically 0.6 wt% to 1.2 wt%. In yet another embodiment, the amount of sulfonated poly(aryl ether sulfone) polymer (SP) is 0.7 wt% to 1.1 wt%. In particular, the sulfonated poly(aryl ether sulfone) polymer (SP) may be present in an amount of 0.1 wt% to 1 wt%, more specifically 0.3 wt% to 1 wt%.

[0225] According to one specific embodiment of the invention, the membrane (M) of the invention is substantially free of sulfonated poly(aryl ether sulfone) polymer (SP). In the context of the invention, "substantially free" means, based on the total weight of the membrane, that the membrane contains at most 0.05% by weight, preferably at most 0.04% by weight, and particularly preferably at most 0.03% by weight, more specifically at most 0.01% by weight of sulfonated poly(aryl ether sulfone) polymer (SP). According to a very specific embodiment, the membrane (M) of the invention contains no sulfonated poly(aryl ether sulfone) polymer (SP).

[0226] According to another embodiment of the invention, the membrane (M) comprises polyvinylpyrrolidone (PVP) as defined above and preferably as defined above, and sulfonated poly(arylene ether sulfone) polymer (SP) as defined above and preferably as defined above.

[0227] According to yet another embodiment, at least one additive (AD) comprises poly(epoxide), particularly selected from poly(ethylene oxide), poly(propylene oxide), and poly(ethylene oxide)-poly(propylene oxide) copolymers.

[0228] According to another embodiment of the invention, the membrane (M) comprises poly(epoxyalkane), selected from poly(ethylene oxide), poly(propylene oxide), and poly(ethylene oxide)-poly(propylene oxide) copolymer.

[0229] If present, the amount of poly(epoxide) in the membrane (M) of the present invention is preferably 0.1 wt% to 5 wt%, more specifically 0.2 wt% to 3 wt%, and even more specifically 0.3 wt% to 2 wt%, based on the total weight of the membrane. In another embodiment, the amount of poly(epoxide) in the membrane of the present invention is 0.4 wt% to 1.5 wt%, more specifically 0.5 wt% to 1.3 wt%, and even more specifically 0.6 wt% to 1.2 wt%. In yet another embodiment, the amount of poly(epoxide) is 0.7 wt% to 1.1 wt%. In particular, poly(epoxide) may be present in an amount of 0.1 wt% to 1 wt%, more specifically 0.3 wt% to 1 wt%.

[0230] As will be self-evident to those skilled in the art, the total weight of all components of the membrane (M) is 100%.

[0231] The membrane (M) can be prepared by any method used for membrane preparation. Another object of the present invention is a method for preparing a membrane (M), the method comprising the steps of:

[0232] a) Provide a composition (C) comprising a poly(aryl ether sulfone) polymer (P1) and (P2) as defined herein and preferably as defined herein, a copolymer (CP) as defined herein and preferably as defined herein, and at least one solvent (D), wherein the copolymer (CP) comprises at least one poly(aryl ether sulfone) (A) block and at least one polyoxyalkylene (PAO) block;

[0233] b) Separate the at least one solvent (D) from the composition (C) to obtain the membrane (M).

[0234] The composition (C) in step a) comprises (P1) and (P2) as defined herein and preferably as defined herein. It may be preferred if the combined amount of the poly(aryl ether sulfone) polymers (P1) and (P2) is 10% by weight or more based on the total weight of the composition (C). According to another embodiment, the combined amount of the poly(aryl ether sulfone) polymers (P1) and (P2) is 11% by weight or more, more specifically 12% by weight or more, based on the total weight of the composition (C). According to a specific embodiment, the combined amount of the poly(aryl ether sulfone) polymers (P1) and (P2) is 13% by weight or more based on the total weight of the composition (C).

[0235] In one embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein, based on the total weight of composition (C), is 14% by weight or more. According to another embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein, based on the total weight of composition (C), is 15% by weight or more, more specifically 16% by weight or more. According to yet another embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein, based on the total weight of composition (C), is 17% by weight or more.

[0236] Furthermore, according to the invention, it may be preferred if the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 18% by weight or more, as defined herein and preferably as defined herein. According to yet another embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 19% by weight or more, more specifically 20% by weight or more. According to yet another specific embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 21% by weight or more, as defined herein and preferably as defined herein. According to one embodiment, it may be further preferred if the combined amount of the poly(arylene ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein is 22% by weight or more, more specifically 23% by weight or more, even more specifically 24% by weight or more, even more specifically 25% by weight or more, based on the total weight of the composition (C).

[0237] According to one embodiment, based on the total weight of the composition (C), the combined amount of the poly(arylene ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein is 10% to 30% by weight, more specifically 13% to 25% by weight, or even more specifically 15% to 23% by weight or more.

[0238] The ratio of poly(aryl ether sulfone) polymer (P1) to (P2) in composition (C) as defined herein, and preferably as defined herein, can be any possible weight ratio, such as 1:10 to 10:1, particularly 1:9 to 9:1, more particularly 1:8 to 8:1, and even more particularly 1:7 to 7:1. According to a specific embodiment, the ratio can be 1:6 to 6:1 or 1:5 to 5:1, particularly 1:4 to 4:1, more particularly 1:3 to 3:1, and even more particularly 1:2 to 2:1. According to a very specific embodiment of the invention, (P1) and (P2) can be present in composition (C) in equal or nearly equal amounts (1:1). In this context, "nearly equal amounts" means that the difference in the amounts of (P1) and (P2) is only negligible.

[0239] The composition (C) in step a) further comprises a copolymer (CP), wherein the copolymer (CP) comprises at least one poly(arylene ether sulfone) (A) block and at least one polyepoxide (PAO) block, as defined herein and preferably as defined herein.

[0240] According to one embodiment, based on the total weight of composition (C), composition (C) contains at least 0.1% by weight, more specifically at least 1% by weight of copolymer (CP).

[0241] Specifically, it is preferable if, based on the total weight of composition (C), composition (C) contains 0.1% to 30% by weight, more specifically 0.5% to 25% by weight, or even more specifically 0.7% to 20% by weight of copolymer (CP). Furthermore, it is preferable if, based on the total weight of composition (C), composition (C) contains 0.8% to 15% by weight, more specifically 0.9% to 15% by weight, or even more specifically 1% to 10% by weight of copolymer (CP).

[0242] According to another embodiment, based on the total weight of composition (C), composition (C) contains 0.1% to 10% by weight, more specifically 0.5% to 7% by weight, or even more specifically 1% to 5% by weight of copolymer (CP).

[0243] In the context of this invention, "at least one solvent" means exactly one solvent, and also means a mixture of two or more solvents.

[0244] Preferably, the at least one solvent (D) is an aprotic polar solvent. In particular, the at least one solvent (D) is soluble in water.

[0245] According to one embodiment, the at least one solvent (D) is preferably selected from the group consisting of: N-alkyl-2-pyrrolidone, preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone and N-tert-butyl-2-pyrrolidone, 2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, dimethylformamide, N,N-dimethyl-2-hydroxypropaneamide, N,N-diethyl-2-hydroxypropaneamide, γ-valerolactone, dihydro-L-glucanone, methyl 5-(dimethylamino)-2-methyl-5-oxovalerate, and sulfolane. N-alkyl-2-pyrrolidone, γ-valerolactone, and N,N-dimethyl-2-hydroxypropaneamide are particularly preferred. N-methylpyrrolidone is most preferably used as the at least one solvent (D).

[0246] According to one embodiment, composition (C) comprises solvent (D) in an amount such that the total amount of all components in the composition reaches 100 by weight.

[0247] Based on the total weight of composition (C), composition (C) preferably contains at least one solvent (D) in the range of 50% to 85% by weight, more preferably in the range of 55% to 84% by weight, more preferably in the range of 60% to 83% by weight, and even more preferably in the range of 67% to 82% by weight. According to a specific embodiment, composition (C) preferably contains at least one solvent (D) in the range of 68% to 75% by weight, and even more preferably in the range of 70% to 75% by weight.

[0248] Furthermore, composition (C) may also contain a hydrophilic polymer additive (AD) as defined above with respect to membrane (M), and preferably as defined above with respect to membrane (M). According to one specific embodiment, composition (C) does not contain any additive (AD).

[0249] According to another embodiment, composition (C) may contain polyvinylpyrrolidone (PVP) as defined herein, and preferably as defined herein.

[0250] If present, the amount of PVP in composition (C) as defined herein, and preferably as defined herein, is preferably from 0.1 wt% to 8 wt%, more specifically from 0.2 wt% to 6 wt%, and even more specifically from 0.3 wt% to 5 wt%, based on the total weight of composition (C). In another embodiment, the amount of PVP in composition (C) is from 0.4 wt% to 3 wt%, more specifically from 0.5 wt% to 2.5 wt%, and even more specifically from 0.6 wt% to 2.0 wt%. In yet another embodiment, the amount of PVP is from 0.7 wt% to 1.8 wt%. In particular, PVP may be present in an amount from 0.1 wt% to 1.7 wt%, more specifically from 0.3 wt% to 1.5 wt%.

[0251] According to one specific embodiment of the invention, composition (C) is substantially free of PVP. In the context of this invention, "substantially free" means that, based on the total weight of composition (C), composition (C) contains at most 0.05% by weight, preferably at most 0.04% by weight, and particularly preferably at most 0.03% by weight, more specifically at most 0.01% by weight of PVP. According to a very specific embodiment, composition (C) contains no PVP whatsoever.

[0252] According to another embodiment, the composition (C) may comprise a sulfonated poly(arylene ether sulfone) polymer (SP) as defined above with respect to the membrane (M), and preferably as defined above with respect to the membrane (M).

[0253] If present, based on the total weight of composition (C), the amount of sulfonated poly(aryl ether sulfone) polymer (SP) in composition (C) as defined herein, and preferably as defined herein, is preferably from 0.1 wt% to 5 wt%, more specifically from 0.2 wt% to 3 wt%, and even more specifically from 0.3 wt% to 2 wt%. In another embodiment, the amount of sulfonated poly(aryl ether sulfone) polymer (SP) in composition (C) is from 0.4 wt% to 1.5 wt%, more specifically from 0.5 wt% to 1.3 wt%, and even more specifically from 0.6 wt% to 1.2 wt%. In yet another embodiment, the amount of sulfonated poly(aryl ether sulfone) polymer (SP) is from 0.7 wt% to 1.1 wt%. In particular, the sulfonated poly(aryl ether sulfone) polymer (SP) may be present in an amount from 0.1 wt% to 1 wt%, more specifically from 0.3 wt% to 1 wt%.

[0254] According to one specific embodiment of the invention, composition (C) is substantially free of sulfonated poly(aryl ether sulfone) polymer (SP). In the context of this invention, "substantially free" means that, based on the total weight of composition (C), composition (C) contains at most 0.05% by weight, preferably at most 0.04% by weight, and particularly preferably at most 0.03% by weight, more specifically at most 0.01% by weight of sulfonated poly(aryl ether sulfone) polymer (SP). According to a very specific embodiment, composition (C) contains no sulfonated poly(aryl ether sulfone) polymer (SP).

[0255] According to another embodiment of the invention, composition (C) may contain poly(epoxyalkane), selected from poly(ethylene oxide), poly(propylene oxide), and poly(ethylene oxide)-poly(propylene oxide) copolymer.

[0256] If present, the amount of poly(epoxide) in composition (C) is preferably from 0.1% to 5% by weight, more specifically from 0.2% to 3% by weight, and even more specifically from 0.3% to 2% by weight, based on the total weight of composition (C). In another embodiment, the amount of poly(epoxide) in composition (C) is from 0.4% to 1.5% by weight, more specifically from 0.5% to 1.3% by weight, and even more specifically from 0.6% to 1.2% by weight. In yet another embodiment, the amount of poly(epoxide) is from 0.7% to 1.1% by weight. In particular, poly(epoxide) may be present in an amount from 0.1% to 1% by weight, more specifically from 0.3% to 1% by weight.

[0257] The composition (C) in step a) is preferably a solution and can be provided by any method known to those skilled in the art, such as in a conventional container that may include a stirring device and preferably a temperature control device. Preferably, the composition (C) or the solution is provided by dissolving (P1) and (P2) and the copolymer (CP) in at least one solvent (D), preferably under stirring.

[0258] Step a) is preferably carried out at an elevated temperature (especially in the range of 20°C to 120°C, more preferably in the range of 40°C to 100°C). Those skilled in the art will select the temperature based on the at least one solvent.

[0259] The composition (C) or solution preferably comprises polymers (P1) and (P2) and copolymer (CP) completely dissolved in at least one solvent (D). This means that the composition (C) preferably does not contain solid particles of polymers (P1) and (P2) and copolymer (CP), and polymers (P1) and (P2) and copolymer (CP) preferably cannot be separated from at least one solvent (D) by filtration.

[0260] The duration of step a) can vary within a wide range. The duration of step a) is preferably in the range of 10 min to 48 h, particularly in the range of 10 min to 24 h, and more preferably in the range of 15 min to 12 h. Those skilled in the art will preferably select the duration of step a) to obtain a homogeneous solution.

[0261] In step b) of the method of the present invention, at least one solvent (D) is separated from the composition (C) or the solution to obtain a membrane (M). The composition (C) or the solution provided in step a) may be filtered before separating the at least one solvent (D) to obtain a filtered solution.

[0262] Furthermore, the composition (C) or solution can be degassed separately before separating at least one solvent (D) in step b) to obtain a degassed solution. This embodiment is preferred. The following embodiments and preferred requirements for separating at least one solvent (D) separately from the composition (C) or solution also apply to separating at least one solvent (D) from the degassed solution. Degasting in step a) can be carried out by any method known to those skilled in the art, such as via vacuum or by allowing the composition (C) or solution to stand separately.

[0263] The following embodiments and preferred requirements for separating at least one solvent (D) from either the composition (C) or the solution also apply to separating at least one solvent from the filtered solution used in this embodiment of the invention. Separation of at least one solvent can be carried out by any method known to those skilled in the art suitable for separating solvents from polymers. Preferably, separation is carried out via a phase inversion method.

[0264] In the context of this invention, a phase inversion method means a method in which dissolved polymers (P1) and (P2) and copolymers (CP) are converted into a solid phase. Therefore, a phase inversion method can also be referred to as a precipitation method. Suitable phase inversion methods are known to those skilled in the art.

[0265] Phase inversion methods can be carried out, for example, by cooling a solution in which the polymers (P1) and (P2) and the copolymer (CP) contained in the solution precipitate. Another possibility for carrying out phase inversion methods is to contact the composition with a gaseous liquid that is a non-solvent for the polymers (P1) and (P2) and the copolymer (CP). The polymers (P1) and (P2) and the copolymer (CP) will then also precipitate. Suitable gaseous liquids as non-solvents for the polymers (P1) and (P2) and the copolymer (CP) are, for example, gaseous proton polar solvents as described below.

[0266] In the context of this invention, another preferred phase inversion method is a phase inversion performed by immersing the solution in at least one proton-polar solvent. Thus, in one embodiment of the invention, in step b), the at least one solvent (D) contained in the composition (C) is separated from the polymers (P1) and (P2) and the copolymer (CP) by immersing the solution in at least one proton-polar solvent. This results in the formation of a membrane. Suitable at least one proton-polar solvents are known to those skilled in the art. The at least one proton-polar solvent is preferably a non-solvent for the polymers (P1) and (P2) and the copolymer (CP). Preferred at least one proton-polar solvents are water, methanol, ethanol, n-propanol, isopropanol, glycerol, ethylene glycol, and mixtures thereof.

[0267] In step b), the composition (C) is typically treated to form a shape corresponding to the desired film shape. Therefore, in one embodiment of the invention,

[0268] Step b) includes casting the composition to obtain a thin layer of the composition or passing a solution through at least one spinneret to obtain at least one hollow fiber of the composition or solution, respectively. Therefore, in a preferred embodiment of the invention, step b) includes the following steps:

[0269] b-1) Cast the composition (C) or solution provided in step a) separately to obtain a thin layer of the composition;

[0270] b-2) Evaporate at least one solvent from the thin layer of the composition obtained in step b-1) to obtain a film in the form of a thin layer.

[0271] This means that the film is formed by evaporating at least one solvent from a thin layer of the composition. In step b-1), the composition can be cast by any method known to a person skilled in the art. Typically, the composition is cast using a casting knife heated to a temperature in the range of 20°C to 150°C, preferably in the range of 40°C to 100°C. The composition is typically cast on a substrate that does not react with the polymers (P1) and (P2) and copolymers (CP) or at least one solvent (D) contained in the solution. Suitable substrates are known to a person skilled in the art and are selected, for example, from glass plates and polymer fabrics (such as nonwoven materials). To obtain a dense film, separation in step b) is typically carried out by evaporating the at least one solvent (D) contained in the composition.

[0272] During membrane formation, the poly(aryl ether sulfone) polymers (P1) and (P2) and the copolymer (CP) are separated from at least one solvent (D). Therefore, the resulting membrane (M) of the present invention is substantially free of at least one solvent (D). In the context of the present invention, "substantially free" means, based on the total weight of the membrane, that the membrane contains at most 1% by weight, preferably at most 0.5% by weight, and particularly preferably at most 0.1% by weight of at least one solvent.

[0273] Another object of the present invention is a membrane (M) that can be obtained by the method of the present invention described above.

[0274] Another object of the present invention is a separation element, membrane assembly, membrane cartridge, or separation system comprising the membrane (M) of the present invention as described herein, and preferably as described herein.

[0275] Another object of the present invention is the use of the membrane (M) of the present invention as described herein, and preferably as described herein, in ultrafiltration.

[0276] The present invention also relates to separation elements, membrane modules, membrane cartridges, or separation systems including the membranes (M) described herein and preferably described herein for water treatment applications.

[0277] Applications include the treatment of industrial or municipal wastewater, desalination of seawater or brackish water, dialysis, plasmolysis, and / or food processing.

[0278] In particular, the present invention also relates to the use of a membrane (M) as described herein, and preferably as described herein, or a separation element, membrane assembly, membrane cartridge, or separation system including the membrane (M) of the present invention, for dialysis, particularly hemodialysis. According to one specific embodiment, the membrane (M) of the present invention is used as a dialysis membrane in a dialysis method.

[0279] Furthermore, the present invention relates to an apparatus for dialysis, the apparatus comprising a membrane (M) of the present invention as described herein and preferably as described herein, or a separation element, membrane assembly, membrane cartridge, or separation system comprising the membrane (M) of the present invention.

[0280] Another object of the present invention is a composition (C) comprising poly(arylene ether sulfone) polymers (P1) and (P2), copolymer (CP), and at least one solvent (D), wherein each of (P1) and (P2) comprises at least one repeating unit having a general formula (I), wherein at least one unit of (P2) is different from at least one unit of (P1), and wherein the copolymer (CP) comprises at least one poly(arylene ether sulfone) (A) block and at least one polyoxyalkylene (PAO) block, wherein at least one unit of (P2) is different from at least one unit of (P1).

[0281] The polymers (P1) and (P2), copolymers (CP), solvents (D), and additives (AD, if present) are as defined above and preferably as defined above, and therefore the embodiments and preferred requirements also apply independently to the compositions (C) of the present invention.

[0282] According to one embodiment of the composition (C) of the present invention, the combined amount of poly(arylene ether sulfone) polymers (P1) and (P2) in the composition (C) is 10% by weight or more, based on the total weight of the composition (C).

[0283] It may be preferred if the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 11% by weight or more, as defined herein and preferably as defined herein. According to another embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 12% by weight or more, more specifically 13% by weight or more. According to a specific embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 14% by weight or more, as defined herein and preferably as defined herein.

[0284] In one embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein, based on the total weight of composition (C), is 15% by weight or more. According to another embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein, based on the total weight of composition (C), is 16% by weight or more, more specifically 17% by weight or more. According to yet another embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein, based on the total weight of composition (C), is 18% by weight or more.

[0285] Furthermore, according to the invention, it may be preferred if the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 19% by weight or more, as defined herein and preferably as defined herein. According to yet another embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 20% by weight or more, more specifically 21% by weight or more. According to yet another specific embodiment, the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 22% by weight or more. According to one embodiment, it may be further preferred if the combined amount of poly(aryl ether sulfone) polymers (P1) and (P2) based on the total weight of composition (C) is 23% by weight or more, more specifically 24% by weight or more, and even more specifically 25% by weight or more.

[0286] According to one embodiment, based on the total weight of the composition (C), the combined amount of the poly(arylene ether sulfone) polymers (P1) and (P2) as defined herein and preferably as defined herein is 10% to 30% by weight, more specifically 13% to 25% by weight, or even more specifically 15% to 23% by weight.

[0287] The ratio of poly(aryl ether sulfone) polymers (P1) to (P2) in the composition (C) of the present invention, as defined herein and preferably as defined herein, can be any possible weight ratio, such as 1:10 to 10:1, particularly 1:9 to 9:1, more particularly 1:8 to 8:1, and even more particularly 1:7 to 7:1. According to specific embodiments, the ratio can be 1:6 to 6:1 or 5:1 to 1:5, particularly 1:4 to 4:1, more particularly 1:3 to 3:1, and even more particularly 1:2 to 2:1. In a very specific embodiment of the composition (C) according to the invention, (P1) and (P2) can be present in the composition (C) in equal or nearly equal amounts. In this context, "nearly equal amounts" means that the difference in the amounts of (P1) and (P2) is only negligible.

[0288] According to one embodiment, based on the total weight of the composition (C), the composition (C) of the present invention comprises 0.1% to 10% by weight, more specifically 0.5% to 7% by weight, or even more specifically 1% to 5% by weight of copolymer (CP).

[0289] According to one embodiment, composition (C) comprises a solvent (D) as defined herein and preferably as defined herein, in an amount such that the total amount of all components in the composition reaches 100 by weight.

[0290] Surprisingly, within the framework of this invention, the composition (C) of this invention has been found to be extremely stable even at relatively high polymer contents. The composition (C) of this invention is highly suitable for the preparation of membranes, particularly ultrafiltration membranes, especially in non-solvent-induced phase separation (NIPS) methods.

[0291] Therefore, another object of the present invention is the use of the composition (C) of the present invention in the production of membranes.

[0292] Surprisingly, specific combinations of the polymers (P1) and (P2) and copolymer (C) according to the invention allow for the preparation of selective and efficient membranes with good mechanical properties. According to the invention, the pore size and hydrophilicity of the membrane can be adjusted, avoiding known membrane drawbacks. Simultaneously, the invention avoids the use of leachable components, such as PVP. The film-forming compositions of the invention allow for high polymer content and exhibit favorable viscosity, both crucial for successful membrane formation. The membranes of the invention are particularly suitable for medical applications requiring high-quality standards, exhibiting low molecular weight cutoff, high water permeability, and good aging stability.

[0293] The invention is further illustrated by the following working examples, but the invention is not limited thereto. Example

[0294] Components and abbreviations used:

[0295] PESU-1: Polyethersulfone, VN=81ml / g (1% NMP by weight, 25℃)

[0296] PPSU: Polyphenylene sulfone, VN=66ml / g (1% NMP by weight, 25℃)

[0297] PSU: Polysulfone, VN=80ml / g (1% NMP by weight, 25℃)

[0298] PAR: Polyarylate, U-100, Unitika, Ltd.; VN=47.5ml / g (1% NMP by weight, 25℃)

[0299] PVP: Polyvinylpyrrolidone, such as K85 (BASF, SE)

[0300] PVP K85 is a polyvinylpyrrolidone with a solution viscosity characterized by a K value of 85, as determined by Fikentscher’s method (Fikentscher, Cellulosechemie 13, 1932(58)).

[0301] NMP: N-methylpyrrolidone, anhydrous

[0302] NTU turbidimetric unit turbidity

[0303] MWCO molecular weight cutoff

[0304] PWP pure water permeability

[0305] The viscosity number (VN) of polyarylethers and polyarylates was measured in 1% by weight NMP solution according to DIN ISO 1628-1.

[0306] The turbidity of the polymer solution was measured using an 860 nm filter at 60°C with a turbidimeter 2100AN (Hach Lange GmbH, Dusseldorf, Germany), and expressed in turbidimetric turbidity units (NTU). Preferably, the NTU value was less than 1.

[0307] PESU-PEO 1 :

[0308] In a 4-liter glass reactor equipped with a thermometer, an inlet pipe, and a Dean-Stark separator, 287.17 g of DCDPS, 225.15 g of DHDPS, 328.1 g of α-C16 / C18-alkyl, ω-hydroxy-polyethylene glycol 3100, and 145.12 g of potassium carbonate with an average particle size of 32.4 were dissolved / suspended in 527 ml of NMP under a nitrogen atmosphere.

[0309] The mixture was heated to 190°C over one hour. In the following text, reaction time should be understood as the time the reaction mixture was maintained at 190°C. Water formed during the reaction was continuously removed by distillation. NMP was added.

[0310] After a 9-hour reaction time, the reaction was stopped by adding 973 ml of NMP and cooling to room temperature (within one hour). The potassium chloride formed during the reaction was removed by filtration. The resulting polymer solution was then precipitated in 50 ml of ethanol, and the resulting polymer beads were separated and extracted with hot water (85°C) for 20 h. The beads were then dried under reduced pressure (<100 mbar) for 24 h.

[0311] PESU-PEO 2 :

[0312] In a 4-liter glass reactor equipped with a thermometer, an inlet pipe, and a Dean-Stark separator, 287.17 g of DCDPS, 226.65 g of DHDPS, 495.80 g of α-C16 / C18-alkyl, ω-hydroxy-polyethylene glycol 3100, and 145.12 g of potassium carbonate with an average particle size of 32.4 were dissolved / suspended in 527 ml of NMP under a nitrogen atmosphere.

[0313] The mixture was heated to 190°C over one hour. In the following text, reaction time should be understood as the time the reaction mixture was maintained at 190°C. Water formed during the reaction was continuously removed by distillation. NMP was added.

[0314] After a 9-hour reaction time, the reaction was stopped by adding 973 ml of NMP and cooling to room temperature (within one hour). The potassium chloride formed during the reaction was removed by filtration. The resulting polymer solution was then precipitated in 50 ml of ethanol, and the resulting polymer beads were separated and extracted with hot water (85°C) for 20 h. The beads were then dried under reduced pressure (<100 mbar) for 24 h.

[0315] PESU-PEO 3 :

[0316] In a 4-liter glass reactor equipped with a thermometer, an inlet pipe, and a Dean-Stark separator, 574.16 g of DCDPS, 485.33 g of DHDPS, 186 g of α-C16 / C18-alkyl, ω-hydroxy-polyethylene glycol 3100, and 290.24 g of potassium carbonate with an average particle size of 32.4 were dissolved / suspended in 1053 ml of NMP under a nitrogen atmosphere.

[0317] The mixture was heated to 190°C over one hour. In the following text, reaction time should be understood as the time the reaction mixture was maintained at 190°C. Water formed during the reaction was continuously removed by distillation. NMP was added.

[0318] After a 9-hour reaction time, the reaction was stopped by adding 2000 ml of NMP and cooling to room temperature (within one hour). The potassium chloride formed during the reaction was removed by filtration. The polymer was separated into beads by precipitation in water, followed by extraction with hot water (85°C) for 20 h. The beads were then dried under reduced pressure (<100 mbar) at 80°C for 24 h.

[0319] pass 1 H-NMR was used to determine the composition of the PESU-PEO copolymer and the solids content of appropriate solutions.

[0320] The Tg of the copolymer was determined by DSC using a TA DCS 2300 instrument. The heating rate was 20 kJ / min. The Tg was determined during a second heating scan running from -100 °C to 250 °C.

[0321] The properties of PESU-PEO copolymers are summarized in Table 1:

[0322] Table 1 :

[0323] VN [ml / g] PEO content [weight %] Tg [℃] PESU-PEO 1 27.7 37.7 15 PESU-PEo 2 30.2 50.7 8 PESU-PEO 3 64.7 15.7 156

[0324] Membrane preparation, general procedure

[0325] Add the formulation according to Table 1 to a three-necked flask equipped with a magnetic stirrer. Heat the mixture to 60°C with gentle stirring until a homogeneous, clear, viscous solution is obtained. Degas the solution overnight at room temperature. Then, reheat the membrane solution at 60°C for 2 hours and cast it onto a glass plate using an Erichsen coater operating at 5 mm / min with a 300 μm casting blade at 60°C. Allow the membrane film to stand for 30 seconds, then immerse it in a 25°C water / NMP 60 / 40 (by weight) bath for 10 minutes.

[0326] After separating the membrane from the glass plate, it was carefully transferred to a water bath and kept in the bath for 12 hours. The membrane was then washed three times with VE water at 75°C for 2.5 hours each time, with the water changed after each wash. The membrane was then stored wet until characterization began.

[0327] A portion of the polymer solution was used for turbidity measurement, see above.

[0328] A flat, continuous membrane with microstructural features of a UF membrane having a size of at least 10 × 15 cm is obtained. The membrane has a top thin skin layer (1 μm-10 μm) and an underlying porous layer (thickness: 100 μm-150 μm).

[0329] Membrane characterization :

[0330] The membrane's pure water permeability was tested using a pressure unit with a 60 mm diameter by filtering ultrapure water (deionized water, filtered through a Millipore UF system). In subsequent tests, solutions of different PEG standards were filtered at pressures of 0 and 15 bar. The molecular weight cutoff was determined by GPC measurements of the feed and permeate.

[0331] The content of leached components was determined by extracting the membrane in water at 80°C for 24 hours, and the weight loss of the sample was determined by measuring the weight of the membrane sample before and after the extraction step.

[0332] Table 2: Film-forming solutions and membrane properties :

[0333] M1C M2C M3C M4 M5 M6C M7C M8 PESU-1 17 12.75 8 7.5 7.5 15 - 7.5 PPSU - - 8 7.5 7.5 - - - PSU - - - - - - - 7.5 PAR (U-100) - 4.75 - - - - - - PVP K85 - - 1 - - - - - PESU-PEO 1 - - - 2 - - - - PESU-PEO 2 - - - - 2 2 - 2 PESU-PEO 3 - - - - - - 17 - NMP 83 83 83 83 83 83 83 83 Turbidity 0.38 61 0.63 0.71 0.70 0.63 0.54 0.61 [NTU] <![CDATA[PWP [l / m 2 ×h×巴]]]> <25 490 870 880 950 410 120 930 MWCO [kg / mol] nd* 1807 85 72 68 79 26 71 Weight loss [weight%] 0.1 0.4 0.85 0.12 0.12 0.13 0.13 0.12

[0334] *nd=Undetermined

[0335] **Fragile = The sample is too fragile to be tested.**

[0336] The membrane based on the novel composition without PVP exhibits higher water permeability with comparable separation performance to the reference membrane, and reduced weight loss during extraction. M1C, M2C, M3C, M6C, and M7C are comparative samples, while M4, M5, and M8 represent the present invention.

Claims

1. A membrane (M) comprising a poly(aryl ether sulfone) polymer (P1) and (P2) and a copolymer (CP), wherein the copolymer (CP) comprises at least one poly(aryl ether sulfone) (A) block and at least one polyoxyethylene (PAO) block, and wherein (P1) and (P2) each comprise at least one repeating unit having a structural formula (I): The symbols t, q, Q, T, Y, Ar, and Ar1 are defined as follows: t and q are independent of each other and can be 0, 1, 2 or 3; Q, T, and Y are independent chemical bonds or selected from -O-, -S-, -SO2-, S=O, C=O, -N=N-, and -CR. a R b - groups, where R a and R b Each is an independent hydrogen atom, (C1-C) 12 )alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkyl or (C6-C 18 ) aryl group, wherein at least one of Q, T and Y is present and is -SO2-; and Ar and Ar 1 They are independent of each other (C6-C) 18 ) aryl; wherein at least one repeating unit of (P2) is different from at least one repeating unit of (P1).

2. The membrane according to claim 1, wherein the at least one structural repeating unit of (P1) and (P2) is selected from the following units 1a to 1s: Where x is between 0.05 and 1 and n is 1; Where x is between 0.05 and 1 and n is 1; Where x ranges from 0.05 to 1 and n is 1.

3. The membrane according to claim 1 or 2, wherein the at least one structural repeating unit of (P1) and (P2) is selected from units 1a, 1g and 1k, respectively, wherein the at least one structural repeating unit of (P2) is different from the at least one structural repeating unit of (P1).

4. The membrane according to any one of claims 1 to 3, wherein the at least one structural repeating unit of (P1) is Ik(PESLI), and the at least one structural repeating unit of (P2) is PSU or PPSU, respectively comprising structural repeating units 1a or Ig.

5. The membrane according to any one of claims 1 to 4, wherein the at least one poly(arylene ether sulfone) (A) in the copolymer (CP) is selected from polyether sulfone, polysulfone and polyphenylene sulfone, or copolymers or mixtures thereof.

6. The membrane according to any one of claims 1 to 5, wherein the polyepoxide (PAO) is polyepoxide.

7. The membrane according to any one of claims 1 to 6, wherein the membrane is a nanofiltration (NF) membrane, a microfiltration (MF) membrane, or an ultrafiltration (UF) membrane.

8. The membrane according to any one of claims 1 to 7, wherein the membrane is a flat sheet membrane or a hollow fiber membrane.

9. The membrane according to any one of claims 1 to 8, wherein the membrane is a dialysis membrane.

10. A method for preparing a membrane (M), the method comprising the following steps: a) Providing a composition (C) comprising a poly(arylene ether sulfone) polymer (P1) and (P2) according to any one of claims 1 to 4, a copolymer (CP), and at least one solvent (D), wherein the copolymer (CP) comprises at least one poly(arylene ether sulfone) (A) block and at least one polyoxyethylene (PAO) block; b) Separate the at least one solvent (D) from the composition (C) to obtain the membrane (M).

11. The method according to claim 10, wherein the at least one solvent (D) is selected from the group consisting of: N-alkyl-2-pyrrolidone, preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone and N-tert-butyl-2-pyrrolidone, 2-pyrrolidone, N-dimethylacetamide, dimethyl sulfoxide, dimethylformamide, N,N-dimethyl-2-hydroxypropaneamide, N,N-diethyl-2-hydroxypropaneamide, γ-valerolactone, dihydro-L-glucanone, methyl 5-(dimethylamino)-2-methyl-5-oxovalerate and sulfolane.

12. A membrane that can be obtained by the method according to claim 10 or 11.

13. A separation element, membrane module, membrane cartridge, or separation system comprising a membrane according to any one of claims 1 to 9 or 12.

14. Use of the membrane according to any one of claims 1 to 9 or 12 in an ultrafiltration process.

15. The membrane according to any one of claims 1 to 9 or 12, or the separation element, membrane module, membrane cartridge, or separation system according to claim 13, for use in water treatment applications, treatment of industrial or municipal wastewater, desalination of seawater or brackish water, dialysis, plasmolysis, and / or food processing.

16. An apparatus for dialysis, the apparatus comprising a membrane according to any one of claims 1 to 9 or 12.

17. A composition (C) comprising poly(arylene ether sulfone) polymers (P1) and (P2), copolymer (CP), and at least one solvent (D), wherein each of (P1) and (P2) comprises at least one repeating unit having a general formula (I), wherein at least one unit of (P2) is different from at least one unit of (P1), and wherein the copolymer (CP) comprises at least one poly(arylene ether sulfone) (A) block and at least one polyoxyalkylene (PAO) block.

18. The composition (C) according to claim 17 is used in the production of membranes, particularly in a non-solvent-induced phase separation method.

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