Method for producing a membrane (M) comprising a sulfonated poly(arylene ether sulfone) polymer (sP) and a non-sulfonated poly(arylene sulfone) polymer (P)

Abstract

The present invention relates to a method for producing a membrane (M) comprising a sulfonated poly(arylene ether sulfone) polymer (sP) and a non-sulfonated poly(arylene sulfone) polymer (P), to the membrane (M) obtained by said method, and to the use of the membrane (M) as an ultrafiltration membrane and / or for hemodialysis applications.

Description

[Technical field]

[0001] The present invention relates to a method for producing a membrane (M) comprising a sulfonated poly(arylene ether sulfone) polymer (sP) and a non-sulfonated poly(arylene sulfone) polymer (P), the membrane (M) obtained by said method, and the use of the membrane (M) as an ultrafiltration membrane and / or for hemodialysis applications.

[0002] Poly(arylene ether sulfone) polymers are high-performance thermoplastics characterized by high heat resistance, good mechanical properties and inherent flame retardancy (EM Koch, H.-M. Walter, Kunststoffe 80 (1990) 1146; E. Doering, Kunststoffe 80, (1990) 1149, N. Inchaurondo-Nehm, Kunststoffe 98, (2008) 190). Due to their high biocompatibility, they are used as materials to form dialysis membranes (NA Hoenich, KP Katapodis, Biomaterials 23 (2002) 3853) and ultrafiltration (UF) membranes. Ultrafiltration membranes (UF) are considered to have an active filtration layer with a molecular weight cutoff of 10-100 kDa, corresponding to a pore size of 10-30 nm, for efficient removal of yeasts, bacteria, viruses and macromolecules from water.

[0003] Poly(arylene ether sulfone) membranes are usually manufactured by a method including two steps: in the first step, a solution is provided, which contains poly(arylene ether sulfone), a pore-forming additive, and a solvent. In the second step, the pore-forming additive and the solvent are separated from the solution to obtain a poly(arylene ether sulfone) membrane. Water-soluble poly(vinylpyrrolidone) is also often added to the poly(arylene ether sulfone) solution as a pore-forming additive to improve the viscosity of the solution (S. Munari et al., Desalination 70 (1988) 265). Furthermore, in hemodialysis (HD) applications, the amount of poly(vinylpyrrolidone) remaining in the active filtration layer inhibits the adhesion of serum proteins and platelets to the membrane surface.

[0004] WO 2017 / 220363 discloses the use of a membrane M comprising at least one sulfonated polyarylene ether A for removing arsenic compounds AS from an aqueous system, said membrane M being an ultrafiltration or microfiltration membrane with a molecular weight cut-off of at least 2,500 Da.

[0005] US Patent Application Publication No. 2018 / 0345230 discloses a transport membrane that includes a nanoporous polyethersulfone / polyvinylpyrrolidone blend support membrane, a hydrophilic polymer within the nanopores of the support membrane, a hydrophilic polymer coating layer on a surface of the support membrane, and a metal salt in the hydrophilic polymer coating layer and in the hydrophilic polymer within the nanopores of the support membrane.

[0006] U.S. Pat. No. 5,246,582 discloses a synthetic hydrophilic membrane in the form of a hollow fiber or flat sheet membrane, the membrane comprising a mixture in a monolayer of polysulfone and sulfonated polysulfone, the mixture comprising a range of about 65 to about 95% by weight of sulfonated polysulfone and about 5 to about 35% by weight of non-sulfonated polysulfone to provide dialysis and / or ultrafiltration properties.

[0007] In the paper “Effect of Molecular Weight of Sulfonated Poly(ether sulfone) (SPES) on the Mechanical Strength and Antifouling Properties of Poly(ether sulfone) / SPES Blend Membranes” by L.-F. Fang et al. (Ind. Eng. Chem. Res., 2017, 56, 11302), the effect of the molecular weight of sulfonated poly(ether sulfone) on the performance of poly(ether sulfone) / SPES blend membranes is investigated. With an increase in the molecular weight of SPES, the mechanical strength of the membrane increases.

[0008] A. Rahimpour et al.'s paper "The influence of sulfonated polyethersulfone (SPES) on surface nano-morphology and performance of polyethersulfone (PES) membrane" (Appl. Surf. Sci., 2010, 256, 1825) describes the sulfonation of polyethersulfone (PES) and the preparation of polyethersulfone (PES) / sulfonated polyethersulfone (SPES) blend membranes by the immersion precipitation method, in which PVP was added as a pore-forming agent.

[0009] However, due to its water solubility, poly(vinylpyrrolidone) is easily dissolved / leached out of the membrane, thereby reducing the biocompatibility of the dialyzer membrane and compromising patient safety during HD treatment (M. Miyata et al., ASAIO Journal (2015) 468).

[0010] It was therefore an object of the present invention to provide an improved poly(arylene ether sulfone) membrane that exhibits reduced leaching of poly(vinylpyrrolidone). The membrane desirably also exhibits a low molecular weight cut-off and high water permeability. The method of manufacture of the membrane desirably is relatively low cost and easy to carry out.

[0011] The purpose of this is to (A) a sulfonated poly(arylene ether sulfone) polymer (sP); (B) a non-sulfonated poly(arylene sulfone) polymer (P); A method for producing a membrane (M) comprising: The method comprises at least steps a) and b): a) providing a solution (S) comprising a sulfonated poly(arylene ether sulfone) polymer (sP) according to component (A), a non-sulfonated poly(arylene sulfone) polymer (P) according to component (B), at least one pore-forming additive (C), and at least one solvent (D), wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone); b) separating the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) to obtain a membrane (M); This is achieved by a method comprising:

[0012] The purpose of this is to (A) a sulfonated poly(arylene ether sulfone) polymer (sP); (B) a non-sulfonated poly(arylene sulfone) polymer (P); A method for producing a membrane (M) comprising: The method comprises at least steps a) and b): a) providing a solution (S) comprising a sulfonated poly(arylene ether sulfone) polymer (sP) according to component (A), a non-sulfonated poly(arylene sulfone) polymer (P) according to component (B), at least one pore-forming additive (C), and at least one solvent (D), wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone); b) separating the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) to obtain a membrane (M); wherein the solution (S) of step a) comprises 0.5-20 wt. % of the sulfonated poly(arylene ether sulfone) polymer (sP), 0.5-20 wt. % of the non-sulfonated poly(arylene sulfone) polymer (P), 3-20 wt. % of at least one pore-forming additive (C), and 40-96 wt. % of at least one solvent (D), each relative to the total weight of the solution (S).

[0013] Surprisingly, the membrane (M) produced by the method of the present invention and comprising the sulfonated poly(arylene ether sulfone) polymer (sP) has a poly(vinylpyrrolidone) (PVP) content (PVP 全体 and PVP 表面 It was found that the membrane (M) of the present invention exhibited an increase in the solubility of 50 kg / (hm2). This means that the membrane (M) of the present invention retains poly(vinylpyrrolidone) in the membrane matrix, thus preventing the leaching of poly(vinylpyrrolidone) from the membrane matrix. Furthermore, all of the membranes (M) of the present invention exhibited an increase in the solubility of 50 kg / (hm2). 2 It exhibits high pure water permeability of over 100 bar and a molecular weight cut-off (MWCO) of 11.2 to 30 kDa.

[0014] The present invention will now be described in further detail.

[0015] [Membrane (M) manufacturing method] The method of the present invention, which comprises at least steps a) and b), produces a membrane (M).

[0016] In the context of the present invention, the term "membrane" refers to a semi-permeable structure capable of separating two fluids or separating molecular and / or ionic components or particles from a liquid. Thus, membranes act as selective barriers, allowing some particles, substances or chemicals to pass and retaining others. Membranes can have a variety of geometric shapes, such as flat sheets, spirals, pillows, tubes, single-hole hollow fibers or multi-hole hollow fibers.

[0017] Preferred are flat sheet membranes and hollow fiber membranes.

[0018] The membrane (M) is prepared by at least steps a) and b): a) providing a solution (S) comprising a sulfonated poly(arylene ether sulfone) polymer (sP) according to component (A), a non-sulfonated poly(arylene sulfone) polymer (P) according to component (B), at least one pore-forming additive (C), and at least one solvent (D), wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone); b) separating the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) to obtain a membrane (M); The present invention is produced by a method comprising the steps of:

[0019] Process a) In step a), a) a solution (S) is provided comprising a sulfonated poly(arylene ether sulfone) polymer (sP) according to component (A), a non-sulfonated poly(arylene sulfone) polymer (P) according to component (B), at least one pore-forming additive (C), and at least one solvent (D), wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone).

[0020] "At least one pore-forming additive" in the context of the present invention means exactly one pore-forming additive and also a mixture of two or more pore-forming additives.

[0021] "At least one pore-forming additive, which at least one pore-forming additive (C) comprises poly(vinylpyrrolidone)" in the context of the present invention means that the pore-forming additive can consist of poly(vinylpyrrolidone) or can comprise poly(vinylpyrrolidone) and at least one further pore-forming additive.

[0022] Another subject of the invention is therefore also a process for the manufacture of a membrane (M), in which the at least one pore-forming additive (C) consists of poly(vinylpyrrolidone).

[0023] "At least one solvent" in the context of the present invention means exactly one solvent and also mixtures of two or more solvents.

[0024] The solution (S) in step a) can be provided by any method known to those skilled in the art. For example, the solution (S) can be provided in step a) in a conventional vessel, which may include a stirring device and preferably a temperature control device. Preferably, the solution (S) is provided by dissolving the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P) and at least one pore-forming additive (C) in at least one solvent (D), where the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone).

[0025] Dissolving the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P) and the at least one pore-forming additive (C) in the at least one solvent (D) to provide a solution (S) is preferably carried out under stirring, wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone).

[0026] Step a) is preferably carried out at elevated temperatures, in particular in the range from 20 to 100° C., more preferably in the range from 40 to 80° C. The person skilled in the art will select the temperature depending on the at least one solvent (D).

[0027] The solution (S) preferably comprises the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P) and at least one pore-forming additive (C) completely dissolved in at least one solvent (D), where the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone). This means that the solution (S) preferably does not comprise solid particles of the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P) and at least one pore-forming additive (C), where the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone). Thus, the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P) and the at least one pore-forming additive (C) preferably cannot be separated by filtration from the at least one solvent (D), wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone).

[0028] The solution (S) may comprise 0.5 to 25 wt % of the sulfonated poly(arylene ether sulfone) polymer (sP), 0.5 to 25 wt % of the non-sulfonated poly(arylene sulfone) polymer (P), 3 to 30 wt % of at least one pore-forming additive (C), and 20 to 96 wt % of at least one solvent (D), each based on the total weight of the solution (S).

[0029] Preferably, the solution (S) comprises 0.5 to 20 wt % of the sulfonated poly(arylene ether sulfone) polymer (sP), 0.5 to 20 wt % of the non-sulfonated poly(arylene sulfone) polymer (P), 3 to 20 wt % of at least one pore-forming additive (C), and 40 to 96 wt % of at least one solvent (D), each relative to the total weight of the solution (S).

[0030] Another subject of the invention is therefore also a method for producing a membrane (M), in which the solution (S) of step a) comprises from 0.5 to 20% by weight of a sulfonated poly(arylene ether sulfone) polymer (sP), from 0.5 to 20% by weight of a non-sulfonated poly(arylene sulfone) polymer (P), from 3 to 20% by weight of at least one pore-forming additive (C) and from 40 to 96% by weight of at least one solvent (D), each relative to the total weight of the solution (S).

[0031] As the at least one solvent (D), any solvent known to those skilled in the art for the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P) and the at least one pore-forming additive (C) is suitable. Preferably, the at least one solvent (D) is soluble in water. Thus, 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-dimethylacetamide, dimethylsulfoxide, dimethylformamide, N,N-dimethyl-2-hydroxypropanamide, N,N-diethyl-2-hydroxypropanamide, γ-valerolactone, dihydrolevoglucosenone, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate and sulfolane. Particularly preferred are N-alkyl-2-pyrrolidone, γ-valerolactone and N,N-dimethyl-2-hydroxypropanamide. Most preferred as the at least one solvent (D) is N-methylpyrrolidone.

[0032] Another subject of the invention is therefore also a process for the preparation of a membrane (M), in which 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,N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, N,N-dimethyl-2-hydroxypropanamide, N,N-diethyl-2-hydroxypropanamide, γ-valerolactone, dihydrolevoglucosenone, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate and sulfolane.

[0033] The solution (S) can contain, for example, at least one solvent (D) in a range of 20 to 96% by weight, preferably in a range of 40 to 96% by weight, more preferably in a range of 50 to 70% by weight, based on the total weight of the solution (S).

[0034] The solution (S) provided in step a) further comprises at least one pore-forming additive (C) for the production of a membrane, wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone).

[0035] Further suitable pore-forming additives (C) are poly(alkylene oxides) and alcohols.

[0036] Examples of suitable poly(alkylene oxides) are poly(ethylene oxide), poly(propylene oxide) and poly(ethylene oxide)-poly(propylene oxide) copolymers. Examples of suitable alcohols are dihydric or trihydric alcohols, such as glycerol.

[0037] As further pore-forming additives (C) alcohols, especially glycerol, are preferred.

[0038] Another subject of the invention is therefore also a process for the manufacture of a membrane (M), in which the at least one pore-forming additive (C) also comprises at least one alcohol, preferably glycerol.

[0039] Preferably, the at least one pore-forming additive (C) comprises in the range of 17-75% by weight of poly(vinylpyrrolidone) and in the range of 25-83% by weight of at least one alcohol, preferably glycerol.

[0040] More preferably, the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone) in the range of 31.25 to 43.75 wt. % and at least one alcohol, preferably glycerol, in the range of 56.25 to 68.75 wt. %.

[0041] In one preferred embodiment, the at least one pore-forming additive (C) consists of poly(vinylpyrrolidone) and at least one alcohol, preferably glycerol.

[0042] The solution (S) may contain at least one pore-forming additive (C), for example in an amount of 3 to 30% by weight, preferably 3 to 20% by weight, relative to the total weight of the solution (S).

[0043] In a preferred embodiment, the solution (S) comprises 3 to 15% by weight of poly(vinylpyrrolidone) and 5 to 15% by weight of at least one alcohol, relative to the total weight of the solution (S).

[0044] In a more preferred embodiment, the solution (S) comprises 5 to 7% by weight of poly(vinylpyrrolidone) and 9 to 11% by weight of at least one alcohol, relative to the total weight of the solution (S).

[0045] It will be apparent to those skilled in the art that the weight percentages of the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P), the at least one pore-forming additive (C) and the at least one solvent (D) contained in the solution (S) typically total 100% by weight.

[0046] The duration of step a) can vary within wide limits. The duration of step a) is preferably in the range of 10 minutes to 48 hours, in particular in the range of 10 minutes to 24 hours, more preferably in the range of 15 minutes to 12 hours. The skilled person will select the duration of step a) so as to obtain a homogeneous solution of the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P) and the at least one pore-forming additive (C) in the at least one solvent (D).

[0047] Step b) In step b), the at least one pore-forming additive (C) and the at least one solvent (D) are separated from the solution (S) to obtain a membrane (M).

[0048] Before separating the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) in step b), the solution (S) provided in step a) can be filtered to obtain a filtered solution (fS). The following embodiments and preferences regarding the separation of the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) apply equally to the separation of the at least one pore-forming additive (C) and the at least one solvent (D) from the filtered solution (fS).

[0049] Furthermore, before separating at least one pore-forming additive (C) and at least one solvent (D) from the solution (S) in step b), it is possible to degas the solution (S) in step a) to obtain a degassed solution (dS). This embodiment is preferred. The following embodiments and preferences regarding the separation of at least one pore-forming additive (C) and at least one solvent (D) from the solution (S) also apply to the separation of at least one pore-forming additive (C) and at least one solvent (D) from the degassed solution (dS).

[0050] The degassing of solution (S) in step a) can be carried out by any method known to the person skilled in the art, for example by vacuum or by leaving solution (S) to stand.

[0051] The separation of the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) can be carried out by any method known to the skilled artisan that is suitable for separating pore-forming additives and solvents from polymers.

[0052] Preferably, the separation of the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) is carried out by a phase inversion process.

[0053] Another subject of the invention is therefore also a process for the manufacture of a membrane (M), in which the separation of at least one pore-forming additive (C) and at least one solvent (D) in step b) is carried out through a phase inversion process.

[0054] When the separation of the at least one pore-forming additive (C) and the at least one solvent (D) is carried out through a phase inversion process, the resulting membrane (M) is typically a porous membrane.

[0055] Another subject of the invention is therefore a membrane (M), which is a porous membrane (M).

[0056] As those skilled in the art know, a porous membrane (M) usually has a top layer and a bottom support structure, and the top layer is an active filtration layer.The top layer and the support structure typically contain pores, and the pore size distribution of the top layer is actually the only determining factor for the properties of the membrane.In general, the pore size of the top layer is smaller than that of the bottom support structure.

[0057] Preferably, the pore size of the membrane (M) increases from the top layer used for the separation towards the bottom of the membrane (M), therefore such a membrane (M) is also called an asymmetric membrane (M).

[0058] A further subject of the invention is therefore a membrane (M), wherein the membrane (M) is asymmetric.

[0059] The minimum pore size of the membrane (M) is preferably less than 10 nm.

[0060] The support structures may have a diameter of up to 10 μm.

[0061] Phase inversion process in the context of the present invention means a process in which dissolved sulfonated poly(arylene ether sulfone) polymer (sP) and undissolved non-sulfonated poly(arylene sulfone) polymer (P) are solidified. Therefore, phase inversion process can also be described as a precipitation process. According to step b), phase inversion is carried out by separation of at least one pore-forming additive (C) and at least one solvent (D) from sulfonated poly(arylene ether sulfone) polymer (sP) and non-sulfonated poly(arylene sulfone) polymer (P). Suitable phase inversion processes are known to those skilled in the art.

[0062] The phase inversion process can be carried out, for example, by cooling the solution (S). During this cooling, the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the solution (S) precipitate. Another way to carry out the phase inversion process is to contact the solution (S) with a vapor that is non-soluble in the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P). Then, the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) precipitate. Suitable vapors that are non-soluble in the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) are, for example, the protic polar solvents in the gaseous state described below. Another phase inversion process which is preferred in the context of the present invention is the phase inversion by immersion of the solution (S) in at least one protic polar solvent.

[0063] Thus, in one embodiment of the present invention, in step b), the at least one pore-forming additive (C) and the at least one solvent (D) contained in the solution (S) are separated from the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the solution (S) by immersing the solution (S) in at least one protic polar solvent.

[0064] That is, a membrane (M) is formed by immersing a solution (S) in at least one protic polar solvent.

[0065] Suitable at least one protic polar solvent is known to those skilled in the art. The at least one protic polar solvent is preferably non-soluble in the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P).

[0066] The at least one protic polar solvent is preferably water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, glycerol, ethylene glycol and mixtures thereof. Preferably, the at least one protic polar solvent is an aqueous coagulation bath.

[0067] Another subject of the invention is therefore a process for the production of a membrane (M), in which at least one protic polar solvent is an aqueous coagulation bath.

[0068] Preferably, the aqueous coagulation bath also contains further components besides water, such as the same solvent (D) as that contained in the solution (S) or an alcohol, in particular glycerol.

[0069] Step b) usually comprises providing a solution (S) in a form that corresponds to the form of the membrane (M) obtained in step b).

[0070] Thus, in one embodiment of the present invention, step b) comprises casting the solution (S) to obtain a film of the solution (S).

[0071] Thus, in one preferred embodiment of the present invention, step b) comprises the following steps: b-1) casting the solution (S) provided in step a) to obtain a film of the solution (S); b-2) immersing the film of solution (S) in at least one protic polar solvent, during which the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the film of solution (S) are at least partially separated from the at least one pore-forming additive (C) and the at least one solvent (D) contained in the film of solution (S) to obtain a membrane (M1) in the form of a film; b-3) washing the membrane (M1) with water, during which the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the membrane (M1) are substantially completely separated from the at least one pore-forming additive (C) and the at least one solvent (D) contained in the membrane (M1) to obtain a membrane (M); Includes.

[0072] Another subject of the invention is therefore a method for producing a membrane (M), in which step b) comprises the following steps: b-1) casting the solution (S) provided in step a) to obtain a film of the solution (S); b-2) immersing the film of solution (S) in at least one protic polar solvent, during which the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the film of solution (S) are at least partially separated from the at least one pore-forming additive (C) and the at least one solvent (D) contained in the film of solution (S) to obtain a membrane (M1) in the form of a film; b-3) washing the membrane (M1) with water, during which the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the membrane (M1) are substantially completely separated from the at least one pore-forming additive (C) and the at least one solvent (D) contained in the membrane (M1) to obtain a membrane (M); The method includes:

[0073] The term "at least partially" in the context of the present invention means that preferably at least 50 wt. %, more preferably at least 60 wt. %, of the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P), based on the total weight of the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the film of solution (S), is separated from the at least one pore-forming additive (C) and the at least one solvent (D).

[0074] The term "substantially completely" in the context of the present invention means that preferably at least 90 wt. %, more preferably at least 95 wt. %, of the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the membrane (M1), based on the total weight of the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P), is separated from the at least one pore-forming additive (C) and the at least one solvent (D).

[0075] In a preferred embodiment, the membrane (M) has a poly(vinylpyrrolidone) (PVP) content (PVP 全体 and PVP 表面 ), which means that the membrane (M) of the present invention retains poly(vinylpyrrolidone) in the membrane matrix, thus preventing the leaching of poly(vinylpyrrolidone) from the membrane matrix.

[0076] Preferably, the membrane (M) has a poly(vinylpyrrolidone) content (PVP) ranging from 0.8 to 5% by weight relative to the total weight of the membrane (M). 全体 has.

[0077] In step b-1), the solution (S) can be provided by any method known to those skilled in the art. Usually, the solution (S) is cast using a casting knife heated to a temperature in the range of 20 to 100°C, preferably in the range of 40 to 80°C.

[0078] Another subject of the invention is therefore a process for the preparation of a membrane (M), in which step b-1) is carried out at a temperature in the range from 40 to 80°C.

[0079] The solution (S) is typically cast onto a substrate that does not react with the sulfonated poly(arylene ether sulfone) polymer (sP), the non-sulfonated poly(arylene sulfone) polymer (P), the at least one pore-forming additive (C), or the at least one solvent (D) contained in the solution (S).

[0080] Suitable substrates are known to those skilled in the art and may be selected, for example, from glass plates, polymeric films, polymeric fabrics, such as non-woven materials.

[0081] In step b-2), the film of solution (S) is preferably immersed in at least one protic polar solvent at a temperature in the range of 20-80°C, more preferably at a temperature in the range of 20-60°C.

[0082] In step b-3), the membrane (M1) is preferably washed at a temperature in the range of 20 to 80°C, more preferably at a temperature in the range of 20 to 60°C.

[0083] The membrane (M) obtained in step b-3) is preferably a flat sheet-like membrane.

[0084] The membrane (M) can be used as an ultrafiltration membrane and / or a hemodialysis membrane.

[0085] A further subject of the invention is therefore also the use of the membrane (M) as an ultrafiltration membrane and / or in hemodialysis applications.

[0086] In order to obtain a dense membrane, the separation in step b) can be carried out by evaporation of at least one solvent (D) contained in the solution (S).

[0087] When producing single-bore hollow fibers, step b) can be carried out by extruding the solution (S) through an extrusion nozzle with the required number of hollow needles. A coagulation liquid is then injected into the extruded polymer through the hollow needles during extrusion, so that parallel continuous flow channels extending in the extrusion direction are formed in the extruded polymer. Preferably, the pore size of the outer surface of the extruded membrane is controlled by contacting the outer surface after leaving the extrusion nozzle with a mild coagulant to ensure that there is no active layer on the outer surface and the shape is fixed, and then contacting the membrane with a strong coagulant.

[0088] [Membrane (M)] A further subject of the invention is a membrane produced by the method according to the invention as described above.

[0089] The membrane comprises a sulfonated poly(arylene ether sulfone) polymer (sP) and a non-sulfonated poly(arylene sulfone) polymer (P).

[0090] Preferably, the membrane (M) comprises 5 to 90% by weight, more preferably 7.5 to 80% by weight, of the sulfonated poly(arylene ether sulfone) polymer (sP) relative to the total weight of the membrane (M).

[0091] A further subject of the present invention is therefore a membrane (M), which comprises from 5 to 90% by weight of sulfonated poly(arylene ether sulfone) polymer (sP), relative to the total weight of the membrane (M).

[0092] The membrane (M) also preferably comprises from 10 to 95% by weight, more preferably from 20 to 92.5% by weight, of non-sulfonated poly(arylene sulfone) polymer (P) relative to the total weight of the membrane (M).

[0093] Thus, in one preferred embodiment, the membrane (M) comprises 5 to 90 wt. % of the sulfonated poly(arylene ether sulfone) polymer (sP) and 10 to 95 wt. % of the non-sulfonated poly(arylene sulfone) polymer (P), relative to the total weight of the membrane (M).

[0094] The membrane (M) preferably has a viscosity of 50 kg / (hm2) measured at 23° C. and 1 bar water pressure using ultrapure water (unsalted water filtered with a Millipore UF-system) using a pressure cell with a diameter of 74 mm. 2 The pure water permeability (PWP) is calculated as follows (Equation (1)):

number

[0095] PWP: Pure water permeability [kg / bar hm 2 ] m: mass of permeated water [kg] A: Membrane area [m 2 ] P: Pressure [bar] t: time of permeation experiment [h].

[0096] A further subject of the invention is therefore a membrane (M) having a melting point of 50 kg / hm 2 It has a pure water permeability of over bar.

[0097] In a preferred embodiment, the membrane (M) has a molecular weight cut-off in the range of 10 to 30 kDa.

[0098] A further subject of the present invention is therefore a membrane (M), which has a molecular weight cut-off in the range of 10 to 30 kDa.

[0099] Component (A) The solution (S) comprises a sulfonated poly(arylene ether sulfone) polymer (sP) as component (A), in which case the terms “sulfonated poly(arylene ether sulfone) polymer (sP)” and “component (A)” are used synonymously and therefore have the same meaning.

[0100] The term "sulfonated poly(arylene ether sulfone) polymer (sP)" in this case is understood to mean exactly one sulfonated poly(arylene ether sulfone) polymer (sP) and mixtures of two or more sulfonated poly(arylene ether sulfone) polymers (sP).

[0101] In a preferred embodiment, the sulfonated poly(arylene ether sulfone) polymer (sP) has the formula (I): [ka] [In the formula, t and q are each independently 0, 1, 2 or 3; Q, T and Y each independently represent a chemical bond or -O-, -S-, -SO2-, -S(=O)-, -(C=O)-, -N=N- and -CR a R b -, Here, R a and R b are each independently a hydrogen atom or a C1 to C 12 Alkyl groups, C1-C 12 Alkoxy group or C6-C 18 an aryl group, and at least one of Q, T and Y is -SO2-; Ar and Ar 1 are each independently an arylene group having 6 to 18 carbon atoms; At least one unit (I) comprises an arylene group substituted with at least one -SO2X group, where X is selected from the group consisting of Cl and O. - and one cation equivalent, wherein the cation equivalent is H+ , Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 + It is.

[0102] Another subject of the present invention is therefore the sulfonated poly(arylene ether sulfone) polymer (sP) having the formula (I) [ka] [In the formula, t and q are each independently 0, 1, 2 or 3; Q, T and Y each independently represent a chemical bond or -O-, -S-, -SO2-, -S(=O)-, -(C=O)-, -N=N- and -CR a R b -, Here, R a and R b are each independently a hydrogen atom or a C1 to C 12 Alkyl groups, C1-C 12 Alkoxy group or C6-C 18 an aryl group, and at least one of Q, T and Y is -SO2-; Ar and Ar 1 are each independently an arylene group having 6 to 18 carbon atoms; At least one unit (I) comprises an arylene group substituted with at least one -SO2X group, where X is selected from the group consisting of Cl and O. - and one cation equivalent, wherein the cation equivalent is H + , Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 + That is, the method.

[0103] In the above condition, when Q, T or Y is a chemical bond, it is understood that this means that the adjacent group on the left side and the adjacent group on the right side are directly bonded to each other through a chemical bond. It is easy to understand that at least one of the group consisting of Q, T and Y is -SO2- means that at least one of Q, T and Y in formula (I) is -SO2-. As a result, for example, when q is =0, at least one of T and Y is -SO2-; for example, when t is =0, at least one of Q and Y is -SO2-, and when q=0 and t=0, Y is SO2.

[0104] Q, T or Y is -CR a R b -If R a and R b are each independently a hydrogen atom or a C1 to C 12 Alkyl groups, C1-C 12 Alkoxy group or C6-C 18 It is an aryl group.

[0105] Preferred C1-C 12 Alkyl groups include linear and branched saturated alkyl groups having 1 to 12 carbon atoms. In particular, the following groups should be mentioned: C1-C6 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2- or 3-methylpentyl, longer chain groups, such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their mono- or polybranched analogues.

[0106] The previously mentioned usable C1 to C 12 Useful alkyl groups in the alkoxy group include linear and branched saturated alkyl groups having 1 to 12 carbon atoms as defined above. Advantageously usable cycloalkyl groups are in particular C3-C 12Cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclopentylpentyl, cyclopentylhexyl, cyclohexylmethyl, cyclohexyldimethyl, and cyclohexyltrimethyl.

[0107] Ar and Ar 1 are each independently C6 to C 18 Ar is an arylene group. Proceeding from the starting materials described below, Ar is preferably derived from an electron-rich aromatic substance that is readily subject to electrophilic attack, preferably selected from the group consisting of hydroquinone, resorcinol, dihydroxynaphthalene, in particular 2,7-dihydroxynaphthalene and 4,4'-bisphenol. Preferably, Ar 1 is unsubstituted C6 or C 12 It is an arylene group.

[0108] Useful C6~C 18 The arylene groups Ar and Ar 1 include in particular phenylene groups, such as the 1,2-, 1,3- and 1,4-phenylene groups, naphthylene groups, such as the 1,6-, 1,7-, 2,6- and 2,7-naphthylene groups, and arylene groups derived from anthracene, phenanthrene and naphthacene.

[0109] Preferably, Ar and Ar in the preferred embodiments of formula (I) 1 are each independently selected from the group consisting of 1,4-phenylene, 1,3-phenylene, naphthylene, in particular 2,7-dihydroxynaphthylene and 4,4'-bisphenylene.

[0110] Preferred sulfonated poly(arylene ether sulfone) polymers (sP) include the following units Ia to Io: [ka] [ka] wherein at least one unit (I) comprises an arylene group substituted with at least one -SO2X group, where X is selected from the group consisting of Cl and O. - and one cation equivalent, wherein the cation equivalent is H + , Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 + It is.

[0111] In addition to the preferred units Ia to Io, also preferred are units in which one or more 1,4-phenylene units derived from hydroquinone are replaced by 1,3-phenylene units derived from resorcinol or naphthylene units derived from dihydroxynaphthalene.

[0112] Particularly preferred units of general formula (I) are units Ia, Ig and Ik. It is also particularly preferred if the sulfonated poly(arylene ether sulfone) polymer of component (A) is formed substantially from one type of unit of general formula (I), in particular from units selected from Ia, Ig and Ik.

[0113] In one particularly preferred embodiment, Ar=1,4-phenylene, t=1, q=0, T=chemical bond, and Y=SO2. A particularly preferred sulfonated poly(arylene ether sulfone) polymer (A) formed from the aforementioned repeat units is referred to as sulfonated polyphenylene sulfone (PPSU) (Formula Ig).

[0114] In a further particularly preferred embodiment, Ar=1,4-phenylene, t=1, q=0, T=C(CH3)2, and Y=SO2. A particularly preferred sulfonated poly(arylene ether sulfone) polymer (A) formed from the aforementioned repeat units is referred to as sulfonated polysulfone (PSU) (Formula Ia).

[0115] In a further particularly preferred embodiment, Ar=1,4-phenylene, t=1, q=0, and T=Y=SO2. A particularly preferred sulfonated poly(arylene ether sulfone) polymer (A) formed from the aforementioned repeat units is referred to as sulfonated poly(ether sulfone) (PESU) (Formula Ik).

[0116] The abbreviations PPSU, PESU, PSU etc. in the context of the present invention are in accordance with DIN EN ISO 1043-1 (Plastics - Symbols and abbreviated terms - Part 1: Basic polymers and their special characteristics (ISO 1043-1:2001); German version EN ISO 1043-1:2002).

[0117] In one preferred embodiment, the sulfonated poly(arylene ether sulfone) polymer (sP) according to component (A) is a copolymer formed from poly(ether sulfone) (PESU) units and poly(phenylene sulfone) (PPSU) units, where at least one unit contains an arylene group substituted with at least one -SOX group, where X is selected from the group consisting of Cl and O. - and one cation equivalent, wherein the cation equivalent is H + , Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 + The copolymer may be, for example, a random copolymer or a block copolymer. Random copolymers formed from poly(ether sulfone) (PESU) and poly(phenylene sulfone) (PPSU) are preferred because they result in a more homogeneous material that exhibits little or no phase separation in the solution or solid state.

[0118] When the sulfonated poly(arylene ether sulfone) polymer (sP) made of component (A) is a copolymer formed from poly(ether sulfone) (PESU) units and poly(phenylene sulfone) (PPSU) units, the sulfonated poly(arylene ether sulfone) polymer (sP) contains 1 to 20 mol % of poly(phenylene sulfone) (PPSU) units and 80 to 99 mol % of poly(ether sulfone) (PESU) units, respectively, relative to the sum of all repeating units of component (A).

[0119] In one particularly preferred embodiment, the sulfonated poly(arylene ether sulfone) polymer (sP) has the formula (III): [ka] Includes units of.

[0120] A further subject of the present invention is therefore that the sulfonated poly(arylene ether sulfone) polymer (sP) has the formula (III) [ka] It is a method including units of.

[0121] In a preferred embodiment, the sulfonated poly(arylene ether sulfone) polymer (sP) has the formula (V): [ka] Including units of i) Number average molecular weight (M) of 10,000 to 35,000 g / mol N ) and / or ii) an arylene group substituted with at least one -SO3X group, where X is H + , Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 + is selected from the group of cation equivalents of iii) x is in the range of 0.01 to 1, preferably in the range of 0.02 to 0.5, and more preferably in the range of 0.04 to 0.4, and x+k is 1.

[0122] The sum of "x" and "k" is equal to 1.

[0123] In a further particularly preferred embodiment, the sulfonated poly(arylene ether sulfone) polymer (sP) has the formula (V): [ka] Includes units of.

[0124] A further subject of the present invention is therefore that the sulfonated poly(arylene ether sulfone) polymer (sP) has the formula (V) [ka] It is a method including units of.

[0125] It is also possible for the sulfonated poly(arylene ether sulfone) polymer (sP) to comprise units of formula (III) and / or formula (IV) and / or formula (V).

[0126] The sulfonated poly(arylene ether sulfone) polymers (sP) preferably have a number average molecular weight (M) of 10,000 to 35,000 g / mol, determined by gel permeation chromatography in dimethylacetamide as solvent against narrow distribution polymethyl methacrylate as standard. N ).

[0127] A further subject of the present invention is therefore that the sulfonated poly(arylene ether sulfone) polymer (sP) has a number average molecular weight (M N ) is a method.

[0128] Furthermore, the sulfonated poly(arylene ether sulfone) polymer (sP) preferably has a free acid content of less than 3 mg KOH / g sulfonated poly(arylene ether sulfone) polymer (sP) as determined by titration with a 0.1 mol / l tetrabutylammonium hydroxide solution (TBAH, in methanol / toluene) against a Solvotrode 30 electrode (Metrohm).

[0129] A further subject of the present invention is therefore a process, wherein the sulfonated poly(arylene ether sulfone) polymer (sP) has a free acid content of less than 3 mg KOH / g sulfonated poly(arylene ether sulfone) polymer (sP).

[0130] The sulfonated poly(arylene ether sulfone) polymer (sP) can be prepared by any method known to those skilled in the art.

[0131] Preferably, the sulfonated poly(arylene ether sulfone) polymer (sP) is prepared by treating a non-sulfonated poly(arylene ether sulfone) polymer with at least one sulfonating agent. The at least one sulfonating agent is suitably any compound known to those skilled in the art capable of introducing at least one SO2X group into the aromatic ring of the non-sulfonated poly(arylene ether sulfone) polymer, where X is Cl or O - and one cation equivalent, where the cation equivalent is H + , Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 +The SO2X group is preferably a sulfonic acid group (-SO3H) or a group capable of reacting with water to form a sulfonic acid group. Such groups are known to those skilled in the art and include, for example, a chlorosulfonyl group (-SO2Cl). Thus, the SO2X group is more preferably a sulfonic acid group (-SO3H) or a chlorosulfonyl group (-SO2Cl), and most preferably the SO2X group is a sulfonic acid group (-SO3H).

[0132] Preferably, the reaction of the unsulfonated poly(arylene ether sulfone) polymer with at least one sulfonating agent at least partially sulfonates at least one of the aromatic rings of the unsulfonated poly(arylene ether sulfone) polymer.

[0133] The mechanism of the sulfonation reaction itself is known to those skilled in the art. Therefore, in the sulfonation reaction, it is particularly preferred to replace the hydrogen atom of the aromatic ring with a sulfonic acid group (-SO3H).

[0134] Typically, 0.001 to 1, preferably 0.005 to 0.1, more preferably 0.01 to 0.08 SO2X groups are introduced per aromatic ring in the non-sulfonated poly(arylene ether sulfone) polymer. Thus, the sulfonated poly(arylene ether sulfone) polymer (sP) typically has 0.001 to 1, preferably 0.005 to 0.1, more preferably 0.01 to 0.08 sulfonic acid groups per aromatic ring.

[0135] The number of SO2X groups per aromatic ring is determined by taking the average over all aromatic rings of the sulfonated poly(arylene ether sulfone) polymer (sP). For this purpose, the number of SO2X groups in the sulfonated poly(arylene ether sulfone) polymer (sP) is divided by the number of aromatic rings in the sulfonated poly(arylene ether sulfone) polymer (sP). Methods for determining the number of SO2X groups and the number of aromatic rings in the sulfonated poly(arylene ether sulfone) polymer (sP) are known to those skilled in the art. The number of SO2X groups can be determined, for example, by acid-base titration, or H1 The ratio of sulfonated to non-sulfonated aromatic rings can be determined by spectroscopic methods such as NMR spectroscopy or IR spectroscopy (infrared spectroscopy). Sulfonated aromatic polymers with SO2X groups on the aromatic rings show characteristic peaks and bands, which allow the number of SO2X groups per aromatic ring in the sulfonated poly(arylene ether sulfone) polymer (sP) to be determined. The ratio of sulfonated to non-sulfonated aromatic rings can be determined by these methods, especially by H 1 It can also be determined by NMR spectroscopy.

[0136] When the unsulfonated poly(arylene ether sulfone) polymer has aromatic rings with different degrees of substitution, this is usually the case where the most nucleophilic aromatic ring is preferentially sulfonated.

[0137] Ingredient (B) The solution (S) comprises a non-sulfonated poly(arylene sulfone) polymer (P) as component (B), in which case the terms "non-sulfonated poly(arylene sulfone) polymer (P)" and "component (B)" are used synonymously and therefore have the same meaning.

[0138] The term "non-sulfonated poly(arylene sulfone) polymer (P)" in this case is understood to mean exactly one non-sulfonated poly(arylene sulfone) polymer (P), as well as mixtures of two or more non-sulfonated poly(arylene sulfone) polymers (P).

[0139] "Non-sulfonated" in the context of the present invention means that the non-sulfonated poly(arylene sulfone) polymer (P) does not contain -SO2X groups, where X is selected from the group consisting of Cl and O. - and one cation equivalent.

[0140] By "one cation equivalent" in the context of the present invention is meant one cation having one positive charge, or one charge equivalent of a cation having two or more positive charges, e.g., H + , Li +, Na + , K + , Mg 2+ , Ca 2+ or NH4 + Examples include:

[0141] Preferably, the non-sulfonated poly(arylene sulfone) polymer (P) has the formula (II): [ka] [In the formula, t and q are each independently 0, 1, 2 or 3; Q, T and Y each independently represent a chemical bond or -O-, -S-, -SO2-, -(S=O)-, -(C=O)-, -N=N- and -CR a R b -, Here, R a and R b are each independently a hydrogen atom or a C1 to C 12 Alkyl groups, C1-C 12 Alkoxy group or C6-C 18 an aryl group, and at least one of Q, T and Y is -SO2-; Ar, Ar 1 are each independently an arylene group having 6 to 18 carbon atoms.

[0142] A further subject of the present invention is therefore that the non-sulfonated poly(arylene sulfone) polymer (P) has the formula (II) [ka] [In the formula, t and q are each independently 0, 1, 2 or 3; Q, T and Y each independently represent a chemical bond or -O-, -S-, -SO2-, -(S=O)-, -(C=O)-, -N=N- and -CR a R b -, Here, R aand R b are each independently a hydrogen atom or a C1 to C 12 Alkyl groups, C1-C 12 Alkoxy group or C6-C 18 an aryl group, and at least one of Q, T and Y is -SO2-; Ar, Ar 1 are each independently an arylene group having 6 to 18 carbon atoms.

[0143] In the above proviso, when Q, T or Y is a chemical bond, this is understood to mean that the left adjacent group and the right adjacent group are directly bonded to each other through a chemical bond. However, preferably, Q, T and Y in formula (II) are each independently selected from -O- and -SO2-, with the proviso that at least one of the group consisting of Q, T and Y is -SO2-.

[0144] Q, T or Y is -CR a R b -If R a and R b are each independently a hydrogen atom or a C1 to C 12 Alkyl groups, C1-C 12 Alkoxy group or C6-C 18 It is an aryl group.

[0145] Preferred C1-C 12 Alkyl groups include linear and branched saturated alkyl groups having 1 to 12 carbon atoms. In particular, the following groups should be mentioned: C1-C6 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2- or 3-methylpentyl, longer chain groups, such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their mono- or polybranched analogues.

[0146] The previously mentioned available C1 to C 12Useful alkyl groups in the alkoxy group include linear and branched saturated alkyl groups having 1 to 12 carbon atoms as defined above. Advantageously usable cycloalkyl groups are in particular C3-C 12 Cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclopentylpentyl, cyclopentylhexyl, cyclohexylmethyl, cyclohexyldimethyl, and cyclohexyltrimethyl.

[0147] Ar and Ar 1 are each independently C6 to C 18 Ar is an arylene group. Proceeding from the starting materials described below, Ar is preferably derived from an electron-rich aromatic substance that is readily subject to electrophilic attack, preferably selected from the group consisting of hydroquinone, resorcinol, dihydroxynaphthalene, in particular 2,7-dihydroxynaphthalene and 4,4'-bisphenol. Preferably, Ar 1 is unsubstituted C6 or C 12 It is an arylene group.

[0148] Useful C6~C 18 The arylene groups Ar and Ar 1 include in particular phenylene groups, such as the 1,2-, 1,3- and 1,4-phenylene groups, naphthylene groups, such as the 1,6-, 1,7-, 2,6- and 2,7-naphthylene groups, and arylene groups derived from anthracene, phenanthrene and naphthacene.

[0149] Preferably, Ar and Ar in the preferred embodiment of formula (II) 1 are each independently selected from the group consisting of 1,4-phenylene, 1,3-phenylene, naphthylene, in particular 2,7-dihydroxynaphthylene and 4,4'-bisphenylene.

[0150] Preferred non-sulfonated poly(arylene sulfone) polymers (P) are those which contain as repeating structural units at least one of the units Ia to Io defined above.

[0151] In addition to the preferred units Ia to Io, also preferred are units in which one or more 1,4-phenylene units derived from hydroquinone are replaced by 1,3-phenylene units derived from resorcinol or naphthylene units derived from dihydroxynaphthalene.

[0152] Particularly preferred units of general formula (II) are units Ia, Ig and Ik. It is also particularly preferred when the non-sulfonated poly(arylene sulfone) polymer (P) of component (B) is substantially formed from one type of unit of general formula (II), in particular from units selected from Ia, Ig and Ik.

[0153] In one particularly preferred embodiment, Ar=1,4-phenylene, t=1, q=0, T=chemical bond, and Y=SO2. A particularly preferred non-sulfonated poly(arylene sulfone) polymer (B) formed from the aforementioned repeat units is referred to as poly(phenylene sulfone) (PPSU) (Formula Ig).

[0154] In a further particularly preferred embodiment, Ar=1,4-phenylene, t=1, q=0, T=C(CH3)2, and Y=SO2. A particularly preferred non-sulfonated poly(arylene sulfone) polymer (B) formed from the aforementioned repeat units is referred to as polysulfone (PSU) (Formula Ia).

[0155] In a further particularly preferred embodiment, Ar=1,4-phenylene, t=1, q=0, and T=Y=SO2. A particularly preferred non-sulfonated poly(arylene sulfone) polymer (B) formed from the aforementioned repeat units is referred to as poly(ether sulfone) (PESU) (Formula Ik).

[0156] Another subject of the present invention is therefore the preparation of a non-sulfonated poly(arylene sulfone) polymer (P) i) poly(ether sulfone) having the formula (lk) [ka] Contains units of, or ii) polysulfone having the formula (la) [ka] Contains units of, or iii) polyphenylene sulfone having the formula (lg) [ka] It is a method that includes units of.

[0157] The non-sulfonated poly(arylene ether sulfones) preferably have a weight average molecular weight M of 10,000 to 150,000 g / mol, in particular 15,000 to 120,000 g / mol, more preferably 18,000 to 100,000 g / mol, determined by gel permeation chromatography in dimethylacetamide as solvent against narrow distribution polymethyl methacrylate as standard. w has.

[0158] The preparation methods leading to the aforementioned non-sulfonated poly(arylene sulfone) polymers are known per se to those skilled in the art and are described, for example, in Herman F. Mark, “Encyclopedia of Polymer Science and Technology”, third edition, Volume 4, 2003, “Polysulfones” chapter p.2-8 and Hans R. Kricheldorf, “Aromatic Polyethers” in: Handbook of Polymer Synthesis, second edition, 2005, p. 427-443.

[0159] Particularly preferred is the reaction of at least one aromatic compound having two halogen substituents with at least one aromatic compound having two functional groups reactive towards said halogen substituents in the presence of anhydrous alkali metal carbonates, in particular sodium carbonate, potassium carbonate, calcium carbonate or mixtures thereof, in an aprotic polar solvent, with potassium carbonate being very particularly preferred.A particularly suitable combination is N-methyl-2-pyrrolidone as solvent and potassium carbonate as base.

[0160] The present invention will be described more specifically by the following examples, but the present invention is not limited thereto. EXAMPLES

[0161] [Ingredients used] Sulfonated poly(arylene ether sulfone) polymers: Synthesis of sulfonated polyethersulfone-polyphenylenesulfone copolymer: sP1 (component (A1)): 1) Synthesis of polyethersulfone-polyphenylenesulfone copolymer In a 4 liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 574.34 g (2.0 mol) of 4,4'-dichlorodiphenyl sulfone (DCDPS), 475.53 g (1.90 mol) of 4,4'-dihydroxydiphenyl sulfone (DHDPS), 18.621 g (0.10 mol) of 4,4'-biphenol and 297.15 g (2.15 mol) of potassium carbonate with a volume average particle size of 33.2 μm are suspended in 1050 mL of NMP (N-methyl-2-pyrrolidone; CAS 872-50-4) under a nitrogen atmosphere. The mixture is heated to 190 ° C within 1 hour. In the following, the reaction time shall be understood as the time during which the reaction mixture is maintained at 190 ° C. The water formed in the reaction is continuously removed by distillation. The evaporated solvent is returned. After a reaction time of 7 hours, the reaction is stopped by the addition of 1950 mL of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction is removed by filtration. The resulting poly(ethersulfone) solution is then precipitated in water and the resulting poly(ethersulfone) beads are isolated and then extracted with hot water (85°C) for 20 hours. The beads are then dried at 120°C under reduced pressure (<100 mbar) for 24 hours.

[0162] The presence of 4,4'-biphenol-derived units in the copolymer is confirmed by 1H-NMR spectroscopy. The glass transition temperature (T G ) is 230.8°C, viscosity number is 82.1mL / g, molecular weight M W (GPC in THF, PS standard material) is 74450g / mol, polydispersity M W / M N is 3.6.

[0163] 2) Synthesis of sulfonated polyethersulfone-polyphenylenesulfone copolymer From the reservoir, sulfuric acid (96%) is fed to the reaction vessel in an amount necessary to obtain a solution with the desired sulfonated poly(ether sulfone) concentration of 8% by weight. The temperature of the sulfuric acid is set to the sulfonation temperature. 50 kg of the poly(ether sulfone) obtained above is added to the mixture within 10 to 30 minutes. The reaction mixture is stirred for another 90 minutes to completely dissolve the poly(ether sulfone). After that, the reaction mixture is stirred for another 90 minutes. In a reservoir equipped with a stirrer and with a wall temperature of 15 °C, liquid L1 is produced from 3125 L of deionized water and nitric acid so that the concentration of nitric acid in liquid L1 is 0.27% by weight relative to liquid L1.

[0164] As dynamic in-line mixer, a one-stage rotor-stator-tooth rim disperser with a concave rotor is used (Cavitron® CD1010 with cone mixing system; Verfahrenstechnik v. Hagen & Funke GmbH, Sprockhoevel, Germany). The dynamic in-line mixer operates at a maximum rotation speed of 12000 rpm and therefore functions as a pump. It pumps liquid L1 from a reservoir, whereby the in-line mixer operates in a recirculation loop. While the three-way valve is set to the sulfuric acid reservoir, the gear pump starts and delivers sulfuric acid to the dynamic in-line mixer while flushing the piping. After purging the connecting piping with sulfuric acid, the three-way valve is opened toward the reaction vessel containing the sulfonated poly(ether sulfone) solution, which is then delivered to the dynamic in-line mixer, to feed the respective sulfonated poly(ether sulfone) solution to the dynamic in-line mixer. When each sulfonated poly(ether sulfone) solution is brought into contact with liquid L1, a suspension is obtained. The suspension is recirculated to the reservoir of liquid L1, where the solids content increases continuously. The suspension is stirred in the reservoir to avoid settling. Liquid L1 and the suspension are each passed through a dynamic in-line mixer at a rate of about 75 L / min. The temperature of the suspension in the reservoir is monitored. During the process, the temperature of the suspension increases by 30-35°C. The suspension is recirculated until the respective sulfonated poly(ether sulfone) solution is used up. The lines are then purged with sulfuric acid.

[0165] The suspension is filtered through a Nutsche, applying a pressure of 1 bar. A filter with a nominal pore size of 10 μm is used. The filter cake is washed with about 800 L of deionized water, using a temperature of about 40° C. for each wash. The washes are interrupted as soon as the pH of the filtrate is equal to or higher than 4. Typically, not more than six washes are performed. Each sulfonated poly(ether sulfone) obtained is then dried in a Nutsche under vacuum at 55-60° C. until the resulting residual water is less than 2% by weight relative to the weight of the sulfonated poly(ether sulfone).

[0166] The sulfonated polyethersulfone polymer has a viscosity number of 86.3 mL / g and a molecular weight M W (GPC in THF, PS standard material) is 72400 g / mol, polydispersity M W / M N The molecular weight is 3.6 and the ion exchange capacity (IEC) is 0.210 meq / g.

[0167] Synthesis of sulfonated polyphenylene sulfone: sP2 (component (A2)): In a 4-liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 557.09 g (1.94 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS; CAS 80-07-9), 372.42 g (2.00 mol) of 4,4'-dihydroxydiphenylsulfone (DHDPS; CAS 92-88-6), 70.15 g (0.1428 mol) of disodium-bis-(4-chloro-3-sulfophenyl)-sulfone (sDCDPS; CAS 51698-33-0) and 317.83 g (2.3 mol) of potassium carbonate with a volume average particle size of 33.2 μm are suspended in 1250 mL of NMP (N-methyl-2-pyrrolidone; CAS 872-50-4) under a nitrogen atmosphere. The mixture is heated to 190 °C within 1 h. In the following, reaction time is to be understood as the time during which the reaction mixture is maintained at 190° C. The water formed in the reaction is continuously removed by distillation. The evaporated solvent is returned. After a reaction time of 7 hours, the reaction is stopped by adding 500 mL of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction is removed by filtration. The sulfonated poly(phenylene sulfone) solution obtained is then precipitated in water and the sPPS beads obtained are separated and then extracted with hot water (85° C.) for 20 hours. The beads are then dried at 120° C. under reduced pressure (<100 mbar) for 24 hours.

[0168] The presence of 5.3 mol% of sulfonated units in the copolymer originating from disodium-bis-(4-chloro-3-sulfophenyl)sulfone units (x=0.053) is confirmed by 1H-NMR spectroscopy. The viscosity of the resulting sulfonated polyphenylene sulfone was 62.7 mL / g, and the calculated ion exchange capacity IEC was 0.260 meq / g.

[0169] P (component (B)): Non-sulfonated poly(arylene sulfone) polymers: Poly(ether sulfone) Ultrason® E6020P; BASF SE; Viscosity number: 81 cm 3 / g (measured according to ISO 307; 0.01 g / mL in a 1:1 solution of phenol / 1,2-orthodichlorobenzene); glass transition temperature T G : 225°C (measured according to ISO 11357-1 / 2, DSC, 10°C / min); molecular weight M W :75000g / mol (measured by GPC in THF, PS standard material); Dispersity M W / M N :3.4.

[0170] Pore-forming additive (component (C1)): Poly(vinylpyrrolidone) Luvitec® K90; BASF SE; molecular weight M W >900000 g / mol; solution viscosity characterized by a K value of 90 (measured according to the method of Fikentscher (Fikentscher, Cellulosechemie 13, 1932 (58))).

[0171] Pore-forming additive (component (C2)): Glycerol; Propane-1,2,3-triol [CAS 56-81-5] Solvent (Component (D)): NMP; N-Methyl-2-pyrrolidone [CAS 872-50-4]

[0172] [General Methodology] Pure water permeability (PWP) The pure water permeability (PWP) of the membrane is tested using ultrapure water (unsalted water filtered with a Millipore UF-system) at 23° C. and 1 bar water pressure using a pressure cell with a diameter of 74 mm. The pure water permeability (PWP) is calculated as follows (Equation 1):

number

[0173] MWCO (Molecular Weight Cut Off) In subsequent tests, solutions of polyethylene oxide standards of increasing molecular weight are used as feed and filtered through the membrane at a pressure of 0.15 bar. Gel Permeation Chromatography (GPC) measurements of the feed and permeate determine the molecular weight of the permeate for each polyethylene oxide standard used. The weight average molecular weight (M W The molecular weight cut-off (MWCO) is the molecular weight of the first polyethylene oxide standard that is retained by the membrane to at least 90%. For example, a MWCO of 18400 means that at least 90% of polyethylene oxide with a molecular weight of 18400 g / mol or greater will be retained. It is desirable for the MWCO to be in the range of 5-100 kDa.

[0174] viscosity The viscosity of the polymer solutions is measured using a Brookfield viscometer DV-I Prime equipped with an RV6 spindle (Brookfield Engineering Laboratories, Inc. Middleboro, USA) at 60° C. and 20 rpm.

[0175] Turbidity The turbidity of the polymer solutions was measured at 60° C. using a turbidimeter 2100AN (Hach Lange GmbH, Duesseldorf, Germany) with an 860 nm filter and is expressed in Nephelometric Turbidity Units (NTU). Low NTU values ​​are preferred.

[0176] PVP 全体 and PVP 表面 Poly(vinylpyrrolidone) content of the membrane (PVP 全体 ) is measured by dissolving the membrane sample in N,N-dimethylformamide (DMF) and casting the solution as a film on a KRS-5 window of thallium bromoiodide. The film is dried at 160 °C and analyzed on a Nicolet 6700 FT-IR spectrometer (Thermo Fischer Scientific, Waltham, Massachusetts, USA). Together with calibration samples of known poly(vinylpyrrolidone) content, the 1680 cm -1 The adsorption band of the membrane is used to determine the total poly(vinylpyrrolidone) content of the membrane sample. 表面 ) is estimated with the same adsorption bands by attenuated infrared spectroscopy (ATR) and a reference sample.

[0177] [Membrane production] Comparative example C1-M As shown in Table 1, 19 g of non-sulfonated poly(ether sulfone) (component (B)), 6 g of poly(vinylpyrrolidone) (component (C1)), 10 g of glycerol (component (C2)) and 65 g of NMP (component (D)) are added to a three-neck flask equipped with a magnetic stirrer. The mixture is heated at 60° C. with gentle stirring until a homogeneous transparent viscous solution (S) is obtained. The solution (S) is degassed overnight at room temperature. The solution (S) is then reheated at 60° C. for 2 hours and cast on a glass plate with a casting knife (300 microns) at 60° C. using an Erichsen coating machine (Coatmaster 510, Erichsen GmbH & Co KG, Hemer, Germany) operating at a speed of 5 mm / s to obtain a film of the solution (S). The film of this solution (S) is left to stand for 30 seconds and then immersed in an aqueous coagulation bath (60% by weight water / 40% by weight glycerol) at 25°C for 10 minutes to obtain a membrane (M1). After peeling the membrane (M1) from the glass plate, the membrane (M1) is transferred to a bath containing 2000 ppm NaOCl at 60°C and pH 9.5 for 2 hours. The membrane (M1) is then washed with water at 60°C to obtain a membrane (M) and washed once with a 0.5% by weight solution of sodium bisulfite to remove active chlorine.

[0178] Examples I2-M to I5-M of the present invention In a three-neck flask equipped with a magnetic stirrer, the amounts of sulfonated poly(ether sulfone) polymer (component (A1)) and non-sulfonated poly(ether sulfone) (component (B)) shown in Table 1, 6 g of poly(vinylpyrrolidone) (component (C1)), 10 g of glycerol (component (C2)) and 65 g of NMP (component (D)) are added. The mixture is heated at 60° C. with gentle stirring until a homogeneous transparent viscous solution (S) is obtained (step a)). The solution (S) is degassed overnight at room temperature. The solution (S) is then reheated at 60° C. for 2 hours and cast on a glass plate with a casting knife (300 microns) at 60° C. using an Erichsen coating machine (Coatmaster 510, Erichsen GmbH & Co KG, Hemer, Germany) operating at a speed of 5 mm / s to obtain a film of the solution (S) (step b-1)). The film of solution (S) is left to stand for 30 seconds, then immersed in an aqueous coagulation bath (60% by weight water / 40% by weight glycerol) at 25°C for 10 minutes to obtain membrane (M1) (step b-2)). After peeling off the membrane (M1) from the glass plate, the membrane (M1) is transferred to a bath containing 2000 ppm NaOCl at 60°C and pH 9.5 for 2 hours. The membrane (M1) is then washed with water at 60°C to obtain membrane (M) (step b-3)) and washed once with a 0.5% by weight solution of sodium bisulfite to remove active chlorine.

[0179] The composition and properties of the solution (S) and the produced membrane (M) are shown in Table 1.

[0180] [Table 1]

[0181] As can be seen from Table 1, the membranes (M) of the present invention (I2-M to I5-M) all have a maximum permeability of 50 to 600 kg / hm 2 As the content of sulfonated poly(ether sulfone) polymer (component (A)) increases, the membrane (M) of the present invention exhibits a high pure water permeability of 11.2 to 30 kDa and a MWCO of 11.2 to 30 kDa. 全体 and PVP 表面), which means that the membrane of the present invention (M) retains the PVP in the membrane matrix, thus preventing the leaching of PVP from the membrane matrix.

[0182] Figure 1 shows a cross section of the membrane of Example I2-M according to the invention, and Figure 2 shows a cross section of the membrane of Comparative Example C1-M (magnification 1500 times). As can be seen, the membrane according to the invention shows a well-established nanoporous filtration layer without defects or macrovoids. The membrane according to Comparative Example C1-M shows numerous macrovoids and defects that can partially penetrate the upper filtration layer.

[0183] Examples I6-M to I8-M of the present invention In a three-neck flask equipped with a magnetic stirrer, add the sulfonated poly(phenylene sulfone) polymer (component (A2)) and non-sulfonated poly(ether sulfone) (component (B)) in the amounts shown in Table 2, 6 g of poly(vinylpyrrolidone) (component (C1)), 10 g of glycerol (component (C2)) and 65 g of NMP (component (D)). The mixture is heated at 60° C. with gentle stirring until a homogeneous transparent viscous solution (S) is obtained (step a)). The solution (S) is degassed overnight at room temperature. The solution (S) is then reheated at 60° C. for 2 hours and cast on a glass plate with a casting knife (300 microns) at 60° C. using an Erichsen coating machine (Coatmaster 510, Erichsen GmbH & Co KG, Hemer, Germany) operating at a speed of 5 mm / s to obtain a film of the solution (S) (step b-1)). The film of solution (S) is left to stand for 30 seconds, then immersed in an aqueous coagulation bath (60% by weight water / 40% by weight glycerol) at 25°C for 10 minutes to obtain membrane (M1) (step b-2)). After peeling off the membrane (M1) from the glass plate, the membrane (M1) is transferred to a bath containing 2000 ppm NaOCl at 60°C and pH 9.5 for 2 hours. The membrane (M1) is then washed with water at 60°C to obtain membrane (M) (step b-3)) and washed once with a 0.5% by weight solution of sodium bisulfite to remove active chlorine.

[0184] The composition and properties of the solution (S) and the produced membrane (M) are shown in Table 2.

[0185] [Table 2]

[0186] As can be seen from Table 2, the membranes (M) of the present invention (I6-M to I10-M) all have a melting point of 50 to 600 kg / hm 2 As the content of sulfonated poly(phenylene ether sulfone) polymer (component (A2)) increases, the membrane (M) of the present invention exhibits a high pure water permeability of 10.7 to 28 kDa and a MWCO of 10.7 to 28 kDa. 全体 and PVP 表面 ), which means that the membrane of the present invention (M) retains the PVP in the membrane matrix, thus preventing the leaching of PVP from the membrane matrix.

Claims

1. (A) Sulfonated poly(arylene ethersulfone) polymer (sP) and (B) Non-sulfonated poly(arylene sulfone) polymer (P) and A method for producing a film (M) containing, The above method includes at least steps a) and b): a) A step of providing a solution (S) comprising a sulfonated poly(arylene ether sulfone) polymer (sP) relating to component (A), a non-sulfonated poly(arylene sulfone) polymer (P) relating to component (B), at least one pore-forming additive (C), and at least one solvent (D), wherein the at least one pore-forming additive (C) comprises poly(vinylpyrrolidone), b) A step of separating the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) to obtain the film (M) Includes, The solution (S) in step a) comprises, in each case, 0.5 to 20% by weight of the sulfonated poly(arylene ether sulfone) polymer (sP), 0.5 to 20% by weight of the unsulfonated poly(arylene sulfone) polymer (P), 3 to 20% by weight of the at least one pore-forming additive (C), and 40 to 96% by weight of the at least one solvent (D), based on the total weight of the solution (S). The at least one pore-forming additive (C) comprises 17 to 75% by weight of poly(vinylpyrrolidone) and at least one alcohol in the range of 25 to 83% by weight. The separation of the at least one pore-forming additive (C) and the at least one solvent (D) from the solution (S) is carried out by a phase inversion process. method.

2. The sulfonated poly(arylene ethersulfone) polymer (sP) is of formula (I) 【Chemistry 1】 [In the formula, t and q are independently 0, 1, 2, or 3. Q, T, and Y are each independently chemically bonded, or -O-, -S-, -SO ２ -, -S(=O)-, -(C=O)-, -N=N-, and -CR ａ R ｂ - is a base selected from, Here, R ａ and R ｂ are each independently a hydrogen atom, or a C １ to C １２ alkyl group, a C １ to C １２ alkoxy group or a C ６ to C １８ aryl group, and at least one of Q, T, and Y is -SO ２ -. Ar and Ar １ Each unit independently contains an arylene group having 6 to 18 carbon atoms. At least one unit (I) is at least one -SO ２ It contains an arylene group substituted with an X group, where X is Cl and O － A combination of H and one cation equivalent is selected from the group, where the cation equivalent is H ＋ Li ＋ Na ＋ _K ＋ Mg ２＋ Ca ２＋ or NH ４ ＋ The method according to claim 1.

3. The aforementioned sulfonated poly(arylene ether sulfone) polymer (sP) i) Equation (III) 【Chemistry 2】 Includes units of and / or ii) Number average molecular weight (M) of 10,000 to 35,000 g / mol Ｎ ) has and / or iii) The method according to claim 1 or 2, having a free acid content of less than 3 mg KOH / g sulfonated poly(arylene ethersulfone) polymer (sP).

4. The sulfonated poly(arylene ethersulfone) polymer (sP) is of formula (V) 【Transformation 3】 Includes units of, x is in the range of 0.01 to 1, and x + k is 1. The method according to claim 1 or 2.

5. The non-sulfonated poly(arylene sulfone) polymer (P) is of formula (II) 【Chemistry 4】 [In the formula, t and q are independently 0, 1, 2, or 3. Q, T, and Y are each independently chemically bonded, or -O-, -S-, -SO ２ -, -(S=O)-, -(C=O)-, -N=N-, and -CR ａ R ｂ - is a base selected from, Here, R ａ and R ｂ Each of these is independently a hydrogen atom, or C １ ~C １２ Alkyl alkyl group, C １ ~C １２ Alkoxy group or C ６ ~C １８ It is an aryl group, and at least one of Q, T, and Y is -SO ２ - and Ar, Ar １ The method according to claim 1 or 2, comprising units of [each independently having 6 to 18 carbon atoms in an arylene group].

6. The non-sulfonated poly(arylene sulfone) polymer (P) is i) It is a poly(ethersulfone), and the formula is (lk) 【Transformation 5】 Includes units of, or ii) It is a polysulfone, and formula (la) 【Transformation 6】 Includes units of, or iii) Polyphenylene sulfone, formula (lg) 【Transformation 7】 The method according to claim 5, including the unit.

7. The method according to claim 1 or 2, 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,N-dimethylacetamide, dimethyl sulfoxide, dimethylformamide, N,N-dimethyl-2-hydroxypropanamide, N,N-diethyl-2-hydroxypropanamide, γ-valerolactone, dihydrolevoglucocenone, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate and sulfolane.

8. The method according to claim 1 or 2, wherein the at least one pore-forming additive (C) comprises glycerol as the at least one alcohol.

9. Step b) is the following: b-1) A step of casting the solution (S) provided in step a) to obtain a film of the solution (S), b-2) A step of immersing the film of the solution (S) in at least one protic polar solvent, thereby separating the sulfonated poly(arylene ethersulfone) polymer (sP) and the non-sulfonated poly(arylenesulfone) polymer (P) contained in the film of the solution (S) from at least one pore-forming additive (C) and at least one solvent (D) contained in the film of the solution (S) to obtain a film (M1), b-3) A step of washing the film (M1) with water, thereby substantially separating the sulfonated poly(arylene ether sulfone) polymer (sP) and the non-sulfonated poly(arylene sulfone) polymer (P) contained in the film (M1) from the at least one pore-forming additive (C) and the at least one solvent (D) contained in the film (M1) to obtain the film (M). The method according to claim 1 or 2, including the following:

10. The method according to claim 9, wherein the at least one protic polar solvent is an aqueous coagulation bath.

11. The method according to claim 9, wherein step b-1) is carried out at a temperature in the range of 40 to 80°C.

12. A membrane manufactured by the method described in claim 1 or 2, wherein the membrane (M) is a porous membrane (M) and contains poly(vinylpyrrolidone) in a range of 0.8 to 5% by weight relative to the total weight of the membrane (M). 全体 A membrane having

13. The aforementioned film (M) i) Having a molecular weight cutoff in the range of 10 to 30 kDa, and / or ii) 50kg / (h m ２ It has a pure water permeability of greater than bar, and / or iii) It is asymmetry, The film (M) according to claim 12.

14. The film (M) according to claim 12, wherein the film (M) contains 5 to 90% by weight of the sulfonated poly(arylene ethersulfone) polymer (sP) based on the total weight of the film (M).

15. Use of the membrane (M) according to claim 12 as an ultrafiltration membrane.

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