Sulfonated polyarylene sulfone polymers (sP) having at least a bimodal molecular weight distribution

Abstract

The present invention relates to a sulfonated polyarylenesulfone polymer (sP) having an at least bimodal molecular weight distribution, to a method for producing said sulfonated polyarylenesulfone polymer (sP), to a membrane (M) comprising said sulfonated polyarylenesulfone polymer (sP), to a method for producing said membrane (M) and to a membrane (M) obtainable by said method.

Description

[Technical field]

[0001] The present invention relates to a sulfonated polyarylenesulfone polymer (sP) having an at least bimodal molecular weight distribution, to a method for producing said sulfonated polyarylenesulfone polymer (sP), to a membrane (M) comprising said sulfonated polyarylenesulfone polymer (sP), to a method for producing said membrane (M) and to a membrane (M) obtainable by said method. [Background technology]

[0002] Politics, society and industry aim to reduce CO2 emissions by decarbonizing industry and mobility. In this regard, green hydrogen plays a strategic role, since it can replace hydrocarbons for chemical and industrial processes, energy conversion and the propulsion of fuel cells in mobility applications. Renewable electricity can be used to run electrolysis cells to produce green and sustainable hydrogen.

[0003] The essential components in electrolysis and electrodialysis cells are the so-called polymer electrolyte membranes (PEMs), which must fulfill several requirements: they must separate the gases hydrogen and oxygen while being ionically conductive. Furthermore, the membranes must be robust and stable for long-term operation and lifetime at constant performance.

[0004] Prior art membranes are mainly based on fluorinated polymers with sulfonic acid side chains (PFSA), known for example under the trade name Nafion®. Due to the complexity of manufacturing PFSA, these polymers are still very expensive. Furthermore, the toxicity and persistence of fluorinated chemicals poses several problems for the manufacture, use and recycling of these materials. Therefore, science and industry are trying to develop more sustainable solutions to replace PFSA membranes.

[0005] One promising class of materials for these applications are polyarylenesulfone polymers, which belong to a group of high-performance polymers that have high heat resistance, chemical resistance, excellent mechanical properties, and durability (E.M. Koch, H.-M. Walter, Kunststoffe 80(1990)1146; E. Doering, Kunststoffe 80,(1990)1149; N. Inchaurondo-Nehm, Kunststoffe 98,(2008)190).

[0006] In addition to their use as engineering plastics, polyarylene sulfone polymers are also used as materials for membranes for water treatment (US Pat. No. 9,199,205).

[0007] Polyarylene sulfone polymers can be formed, inter alia, via the hydroxide process, in which a salt is first formed from a dihydroxy moiety and a hydroxide, or via the carbonate process.

[0008] General information regarding the formation of polyarylene sulfone polymers by the hydroxide method is found, inter alia, in RN Johnson et.al., J. Polym. Sci. A-15 (1967) 2375, while the carbonate method is described in JE McGrath et.al., Polymer 25 (1984) 1827.

[0009] Methods for forming polyarylene sulfone polymers from aromatic bishalogen compounds and aromatic bisphenols or their salts in aprotic solvents in the presence of one or more alkali metal or ammonium carbonates or bicarbonates are known to those skilled in the art and are described, for example, in EP-A 297363 and EP-A 135130.

[0010] High performance thermoplastics, such as polyarylene sulfone polymers, are formed by polycondensation reactions typically carried out at high reaction temperatures in polar aprotic solvents such as DMF (dimethylformamide), DMAc (dimethylacetamide), sulfolane, DMSO (dimethylsulfoxide) and NMP (N-methylpyrrolidone).

[0011] For use as a membrane material in water electrolysis, electrodialysis or fuel cells, the polymer must exhibit ionic conductivity, which can be achieved by functionalizing the polyarylene sulfone polymer with sulfonic acid groups.

[0012] Sulfonated polyarylene sulfone polymers have been known for many years. While direct sulfonation of polyarylene sulfone polymers leads to side reactions and allows only limited control of the degree of sulfonation, the use of disulfonated aromatic dihalogen sulfones, such as sulfonated dichlorodiphenyl sulfone (sDCDPS), as comonomers allows the synthesis of well-defined sulfonated polyarylene sulfone polymers.

[0013] Although sulfonated polyarylenesulfone polymers show some interesting properties for use as ion-conducting membranes in fuel cells, electrodialysis cells or for electrolysis, a major problem that still needs to be solved is their preparation method itself. One problem is the extremely long reaction times, especially when large amounts of disulfonated monomers are used, and the extensive work-up and isolation of such copolymers. The condensation leads to a polymer suspension containing the sulfonated copolymer (sulfonated polyarylenesulfone polymer) and salts. After separating the salts, a precipitation, usually in isopropanol, is performed to isolate the sulfonated polyarylenesulfone polymer, which results in a huge solvent mixture that must be reprocessed or discarded. Moreover, some of the product does not completely precipitate, which can lead to clogging of filters during the subsequent separation. Moreover, the sulfonated copolymer must be dissolved again to produce the membrane. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] U.S. Patent No. 9,199,205 [Patent Document 2] European Patent Application Publication No. 297363 [Patent Document 3] European Patent Application Publication No. 135130 [Non-patent literature]

[0015] [Non-Patent Document 1] E.M.Koch, H.-M.Walter, Kunststoffe 80(1990)1146 [Non-Patent Document 2] E.Doering, Kunststoffe 80,(1990)1149 [Non-Patent Document 3] N.Inchaurondo-Nehm, Kunststoffe 98,(2008)190 [Non-Patent Document 4] RNJohnson et.al., J.Polym.Sci. A-15(1967)2375 [Non-Patent Document 5] JEMcGrath et.al., Polymer 25(1984)1827 Summary of the Invention [Problem to be solved by the invention]

[0016] The object of the present invention is therefore to provide a sulfonated polyarylene sulfone polymer (sP) and a method for producing said sulfonated polyarylene sulfone polymer (sP), which does not have the disadvantages of the prior art or only has them in a reduced form. The method should be easy to carry out. The sulfonated polyarylene sulfone polymer (sP) should be suitable for the production of membranes, in particular membranes capable of separating hydrogen from hydrogen-containing gas mixtures. [Means for solving the problem]

[0017] This problem is solved by a sulfonated polyarylene sulfone polymer (sP) having an at least bimodal molecular weight distribution with at least one first peak (P1) and at least one second peak (P2), wherein the maximum point of said first peak (P1) is in the relative molecular weight range of 800 to 5000 g / mol and the maximum point of said second peak (P2) is in the relative molecular weight range of 8000 to 300000 g / mol, said relative molecular weights being determined by gel permeation chromatography using dimethylacetamide as solvent and narrowly distributed poly(methyl methacrylate) as standard.

[0018] Surprisingly, it has been found that sulfonated polyarylenesulfone polymers (sP) having at least a bimodal molecular weight distribution are suitable for the manufacture of membranes (M). Membranes (M) containing sulfonated polyarylenesulfone polymers (sP) having at least a bimodal molecular weight distribution exhibit improved conductivity compared to membranes (M) comprising sulfonated polyarylenesulfone polymers having a monomodal molecular weight distribution.

[0019] The invention is described in more detail below.

[0020] Sulfonated polyarylene sulfone polymer (sP) The sulfonated polyarylene sulfone polymer (sP) according to the invention has an at least bimodal molecular weight distribution.

[0021] In the context of the present invention, the term "at least bimodal molecular weight distribution" means that the molecular weight distribution in the sulfonated polyarylene sulfone polymer (sP) according to the present invention may be bimodal, trimodal, tetramodal or pentamodal, or it may contain more than one mode.However, in a preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) is bimodal.

[0022] The molecular weight distribution peak of the sulfonated polyarylene sulfone polymer (sP) according to the present invention can be identified by the number of peaks in a GPC chart.

[0023] Unless otherwise indicated, the peaks are identified in the respective sulfonated polyarylene sulfone polymer (sP) gel permeation chromatography (GPC) charts. GPC measurements are performed using dimethylacetamide (DMAc) as the solvent and narrowly distributed poly(methyl)methacrylate (PMMA) as the standard. Preferably for GPC, the polymer (sulfonated polyarylene sulfone polymer (sP)) is dissolved in DMAc at a concentration of 4 mg / ml, and the solution is then filtered using a 0.2 μm filter. 100 μl of this solution is injected into the system. The flow rate is usually set at 1 ml / min, and four columns kept at a temperature of 40° C. are used for separation. As a detector, an RI detector is used. The system is calibrated from 800 to 2200200 g / mol. The solvent used may also contain a small amount of salt, preferably LiBr.

[0024] Only peaks that contribute more than 0.3 area % to the total area of ​​the peaks in the GPC chart, preferably more than 0.4 area %, are considered for the identification of the respective peak numbers. In the context of the present invention, the term "GPC chart" refers to a chart obtained by GPC showing peak intensities on the y-axis over the relative molar masses on the x-axis.

[0025] In other words, rather small peaks in the baseline that have a very low signal to noise ratio are not considered as peaks in identifying the peak numbers of each polymer.

[0026] For purposes of the present invention, the term "relative molecular weight" refers to the molecular weight of a sulfonated polyarylene sulfone polymer (sP) as determined by GPC relative to the molecular weight of a narrowly distributed poly(methyl) methacrylate standard of known molecular weight.

[0027] The sulfonated polyarylene sulfone polymer (sP) generally has an at least bimodal molecular weight distribution having at least one first peak (P1) and at least one second peak (P2).

[0028] The relative mass of the first peak (P1) is lower than the relative mass of the second peak (P2).

[0029] The maximum point of the first peak (P1) is in the range of relative molecular weight 800-5000 g / mol, preferably in the range of 1000-4500 g / mol, and more preferably in the range of 1250-4000 g / mol, said relative molecular weight being determined by gel permeation chromatography as described above using dimethylacetamide as the solvent and narrowly distributed poly(methyl methacrylate) as the standard.

[0030] The maximum point of the second peak (P2) is in the range of relative molecular weight 8000-300000 g / mol, preferably in the range of 9000-275000 g / mol, and more preferably in the range of 10000-270000 g / mol, said relative molecular weight being determined by gel permeation chromatography as described above using dimethylacetamide as solvent and narrowly distributed poly(methyl methacrylate) as standard.

[0031] To identify the relative molecular weights of the maxima of the peaks (P1 and P2), a perpendicular line is dropped from each maximum onto the x-axis of the GPC chart.

[0032] The maximum of the first peak (P1) preferably exhibits a lower intensity than the maximum of the second peak (P2).

[0033] The ratio of the first intensity (I1) to the second intensity (I2) is generally in the range of 1:8 to 1:100, preferably in the range of 1:8 to 1:50, and more preferably in the range of 1:8 to 1:40.

[0034] At present, the term intensity is preferably understood to mean the height of the maximum of a peak in a GPC chart.

[0035] FIG. 1 shows a preferred embodiment of a GPC chart of a sulfonated polyarylene sulfone polymer (sP) having a bimodal molecular weight distribution. Intensity is shown on the y-axis. Relative molecular weight is shown on the x-axis. The maximum of the first peak (P1) is at a lower relative molecular weight than the maximum of the second peak (P2). To identify the relative molecular weight of the maximum of the first peak (P1), a perpendicular line (shown as I1 in FIG. 1) is dropped from the maximum of the first peak (P1) to the x-axis. The relative molecular weight of the maximum of the second peak is identified accordingly.

[0036] The heights of the peaks (P1) and (P2) are measured to identify the intensities at the maximum points of the peaks.

[0037] Therefore, another object of the present invention is a sulfonated polyarylene sulfone polymer (sP), wherein the maximum of the first peak (P1) exhibits a first intensity (I1) and the maximum of the second peak (P2) exhibits a second intensity (I2), and the ratio of said first intensity (I1) to the second intensity (I2) is in the range of 1:10 to 1:1000.

[0038] The sulfonated polyarylene sulfone polymers (sP) generally have a mass average molecular weight (M) in the range of 20,000 to 250,000 g / mol, preferably in the range of 30,000 to 225,000 g / mol, and more preferably in the range of 40,000 to 200,000 g / mol. W), and the mass average molecular weight (M W ) are characterized by gel permeation chromatography as described above using dimethylacetamide as the solvent and narrowly distributed poly(methyl methacrylate) as the standard.

[0039] Therefore, another object of the present invention is to provide a method for producing a sulfonated polyarylenesulfone polymer (sP) having a mass average molecular weight (M W ), and the mass average molecular weight (M W ) is a sulfonated polyarylene sulfone polymer (sP) characterized by gel permeation chromatography using dimethylacetamide as the solvent and narrowly distributed poly(methyl methacrylate) as the standard.

[0040] In a preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) contains at least one -SO3X in the range of 15 to 80 mol%, preferably in the range of 20 to 70 mol%, and more preferably in the range of 25 to 65 mol%, based on the total amount of the sulfonated polyarylene sulfone polymer (sP). 3 wherein the sulfonated repeat unit comprises a group, where X 3 is hydrogen or one cation equivalent.

[0041] A repeating unit is preferably understood to mean a unit derived from one aromatic dihalogen sulfone and one aromatic dihydroxy compound, for example a repeating unit may be derived from one 4,4'-dihydroxybiphenyl and one 4,4'-dichlorodiphenyl sulfone leading to a non-sulfonated repeating unit, or a repeating unit may be derived from one 4,4'-dihydroxybiphenyl and one 4,4'-dichlorodiphenyl sulfone-3,3'-disulfonic acid leading to a sulfonated repeating unit.

[0042] The term repeat unit is known to those skilled in the art and is also referred to as a repeat unit.

[0043] Another object of the present invention is therefore to provide a sulfonated polyarylenesulfone polymer (sP) which is composed of from 15 to 80 mol % of at least one -SO3X based on the total amount of the sulfonated polyarylenesulfone polymer (sP). 3 wherein the sulfonated repeat unit comprises a group, where X 3 is hydrogen or one cation equivalent, sulfonated polyarylenesulfone polymer (sP).

[0044] Preferred sulfonated polyarylene sulfone polymers (sP) have the general formula I: [ka] wherein: t and q are each independently 0, 1, 2 or 3; Q 1 , T and Y 1 are each independently a chemical bond or -O-, -S-, -SO2-, -S(=O)-, -C(=O)-, -N=N- and -CR a R b - selected from R a and R b are each independently a hydrogen atom or a C1-C 12 -Alkyl, C1-C 12 -Alkoxy or C6-C 18 -aryl group, and at least one of Q, T and Y is -SO2-; Ar and Ar 1 are each independently C6 to C 18 -aryl, 18 -Aryl is unsubstituted or C1-C 12 -Alkyl, C1-C 12 -Alkoxy, C6~C 18 -substituted with at least one substituent selected from aryl, halogen and -SO3X; p, m, n and k are each independently 0, 1, 2, 3 or 4, with the proviso that the total of p, m, n and k is equal to or greater than 1; and X 3is hydrogen or one cation equivalent.

[0045] Another object of the present invention is therefore to provide a sulfonated polyarylenesulfone polymer (sP) having the general formula I: [ka] In the formula, t and q are each independently 0, 1, 2 or 3; Q 1 , T and Y 1 are each independently a chemical bond or -O-, -S-, -SO2-, -S(=O)-, -C(=O)-, -N=N- and -CR a R b - selected from R a and R b are each independently a hydrogen atom or a C1-C 12 -Alkyl, C1-C 12 -Alkoxy or C6-C 18 -aryl group, and at least one of Q, T and Y is -SO2-; Ar and Ar 1 are each independently C6 to C 18 -aryl, 18 -Aryl is unsubstituted or C1-C 12 -Alkyl, C1-C 12 -Alkoxy, C6~C 18 -substituted with at least one substituent selected from aryl, halogen and -SO3X; p, m, n and k are each independently 0, 1, 2, 3 or 4, with the proviso that the total of p, m, n and k is equal to or greater than 1; and X 3 is hydrogen or one cation equivalent, It is a sulfonated polyarylene sulfone polymer (sP).

[0046] In a preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) comprises at least 80% by weight of repeat units of general formula (I), based on the total weight of the sulfonated polyarylene sulfone polymer (sP).

[0047] Under the above preconditions, Q 1 , T or Y 1 is a chemical bond, this means that the left adjacent group and the right adjacent group are directly attached to each other by a chemical bond.

[0048] R a and R b are each independently hydrogen or C1-C 12 -alkyl.

[0049] Preferred C1-C 12 -Alkyl groups include linear and branched, saturated alkyl groups of 1 to 12 carbon atoms. The following moieties are particularly suitable: C1-C6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, 2- or 3-methylpentyl, or longer chain moieties, such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their branched analogues.

[0050] Used C1~C 12 The alkyl moiety in the alkoxy group comprises an alkyl group as defined above having 1 to 12 carbon atoms. Preferably used cycloalkyl moieties are in particular C3-C 12 -Cycloalkyl moieties include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, -propyl, -butyl, -pentyl, -hexyl, -cyclohexylmethyl, -dimethyl, -trimethyl.

[0051] Ar and Ar 1 are each independently C6~C 18Starting from the starting materials described below, Ar is preferably derived from an aromatic substance that is highly susceptible to electrophilic attack and is preferably selected from the group consisting of sulfonated or non-sulfonated hydroquinone, resorcinol, dihydroxynaphthalene, in particular 2,7-dihydroxynaphthalene. 1 is preferably unsubstituted C6 or C 12 -arylene group.

[0052] Ar and Ar in preferred embodiments of formula (I) 1 are each preferably independently selected from sulfonated or non-sulfonated 1,4-phenylene, 1,3-phenylene, naphthylene, especially 2,7-dihydroxynaphthalene.

[0053] The following structural units (Ia)-(Io): [ka]

[0054] [ka]

[0055] [ka] Preferred are sulfonated polyarylene sulfone polymers (sP) having one or more of the following formulae: l, k, m, n, o, and p are each independently 0, 1, 2, 3, or 4, with the proviso that the sum of l, k, m, n, o, and p is ≧1; and X 3 is hydrogen or one cation equivalent.

[0056] In the context of the present invention, "one cation equivalent" means one cation with a single positive charge, or one charge equivalent of a cation with two or more positive charges, e.g. Li, Na, K, Mg, Ca, NH4, preferably Na, K.

[0057] In addition to the preferred building blocks (Ia) to (Io), also preferred are structural units in which one or more sulfonated or non-sulfonated 1,4-dihydroxyphenyl units are replaced by resorcinol or dihydroxynaphthalene.

[0058] Copolymers consisting of a combination of various structural units, or sulfonated and non-sulfonated structural units, are also useful.

[0059] The structural units (Ia), (Ib), (Ig) and (Ik) or copolymers thereof are particularly preferably used as repeating units of the general formula (I).

[0060] In one particularly preferred embodiment, Ar is 1,4-phenylene, t is 1, T is a chemical bond, and Y 1 is -SO2-, q is 0, p is 0, m is 0, n is 1, and k is 1. A sulfonated polyphenylsulfone composed of repeating units of this listed structure is represented as sPPSU.

[0061] In a particularly preferred embodiment, Ar is 1,4-phenylene, t is 0, Y is -SO2-, q is 0, n is 0, and k is 0. Polyarylene sulfones composed of repeating units of the above listed structures are referred to as sulfonated polyether ether sulfones (sPESUs).

[0062] In one advantageous embodiment, the sulfonated polyarylene sulfone polymer (sP) is represented by the formula (1) [ka] and a non-sulfonated repeating unit of formula (2) [ka] The sulfonated repeating unit comprises:

[0063] In particular, the sulfonated polyarylenesulfone polymer (sP) consists exclusively of non-sulfonated repeat units of formula (1) and sulfonated repeat units of formula (2).

[0064] In a highly advantageous embodiment, the sulfonated polyarylene sulfone polymer (sP) has the formula (1a) [ka] and non-sulfonated repeating units of formula (2a) [ka] The sulfonated repeating unit comprises:

[0065] In particular, the sulfonated polyarylenesulfone polymer (sP) consists exclusively of non-sulfonated repeat units of formula (1a) and sulfonated repeat units of formula (2a).

[0066] method The sulfonated polyarylene sulfone polymer (sP) according to the present invention is preferably prepared by reacting a reaction mixture (R G In a preferred embodiment, the reaction mixture (R G ) contains at least one aprotic polar solvent.

[0067] The aromatic dihalogen sulfone component is also referred to as component (A). In the present invention, the terms aromatic dihalogen sulfone component and component (A) are used synonymously and therefore have the same meaning.

[0068] The at least one aromatic dihydroxy compound is also referred to as component (B). The terms at least one aromatic dihydroxy compound and component (B) in the present invention are used synonymously and therefore have the same meaning.

[0069] The at least one carbonate compound is also referred to as component (C). In the present invention, the terms at least one carbonate compound and component (C) are used synonymously and therefore have the same meaning.

[0070] The at least one aprotic polar solvent is also referred to as component (D). The terms at least one aprotic polar solvent and component (D) in the present invention are used synonymously and therefore have the same meaning.

[0071] Another object of the present invention is therefore a method for the preparation of a sulfonated polyarylenesulfone polymer (sP), comprising the steps of: G i) converting said reaction mixture (R G ) is a component, (A) an aromatic dihalogen sulfone component comprising at least one sulfonated aromatic dihalogen sulfone (component (A1)) and at least one non-sulfonated aromatic dihalogen sulfone (component (A2)); (B) at least one aromatic dihydroxy compound, and (C) at least one carbonate compound The method comprises:

[0072] Another subject of the present invention is therefore a reaction mixture (R G ) further comprises at least one aprotic polar solvent (component (D)).

[0073] The reaction mixture (R G ) is the mixture provided to form the sulfonated polyarylene sulfone polymer (sP). Thus, the reaction mixture (R G All components referred to in (R ) refer to the mixture present prior to polycondensation. The polycondensation is carried out by reacting the reaction mixture (R G ) into the target product, sulfonated polyarylene sulfone polymer (sP), by polycondensation of components (A) and (B).

[0074] In step i), components (A) and (B) enter into a polycondensation reaction. Component (C) acts as a base to deprotonate the hydroxyl groups of component (B). Component (D), if present, acts as a solvent.

[0075] The mixture obtained after polycondensation and containing the sulfonated polyarylene sulfone polymer (sP) target product is called the product mixture (P G ) is also called the product mixture (P G ) preferably further comprises a halide compound, and preferably at least one aprotic polar solvent (component (D)). The halide compound is G During the conversion, component (C) first reacts with component (B) to deprotonate it. The deprotonated component (B) then reacts with component (A) to form a halide compound. This process is known to those skilled in the art.

[0076] The reaction mixture (R G The components of (a) are preferably reacted simultaneously. The individual components can be mixed in an upstream step and reacted subsequently. It is also possible for the individual components to be fed to a reactor, where they are mixed and then reacted.

[0077] In the process according to the invention, the reaction mixture (R G The individual components of (A) are preferably reacted simultaneously in step i). The reaction is preferably carried out in one step. This means that the deprotonation of component (B) and also the condensation reaction between components (A) and (B) are carried out in a single reaction step without isolation of intermediate products, e.g. the deprotonated species of component (B).

[0078] The reaction mixture (R G It is further preferred that the reaction mixture (R) does not contain toluene or monochlorobenzene. G It is particularly preferred that the solvent does not contain any substances that form azeotropes with water.

[0079] The ratio of components (A) and (B) is essentially derived from the stoichiometric ratios of the polycondensation reaction which proceeds with the theoretical removal of hydrogen chloride and is established in a known manner by those skilled in the art.

[0080] Preferably, the ratio of halogen end groups derived from component (A) to phenol end groups derived from component (B) is adjusted by establishing a controlled excess of component (A) relative to component (B) as starting compound.

[0081] Preferably, the conversion in the polycondensation reaction is at least 0.9.

[0082] The process step i) for preparing the sulfonated polyarylene sulfone polymer (sP) is preferably carried out under the conditions of the so-called "carbonate process". G ) react under the conditions of the so-called "carbonate process". The polycondensation reaction is generally carried out at temperatures in the range of 80 to 250°C, preferably in the range of 100 to 220°C. The upper temperature limit is preferably determined by the boiling point of the at least one aprotic polar solvent (component (D)) at standard pressure (1013.25 mbar). The reaction is generally carried out at standard pressure. The reaction is preferably carried out over a time interval in the range of 0.5 to 14 hours, in particular in the range of 1 to 12 hours.

[0083] In a preferred embodiment in step i), The reaction mixture (R G ) relative to the total molar amount of the aromatic dihalogen sulfone component (component (A)) in X 1 % by mole of at least one sulfonated aromatic dihalogen sulfone (component (A1)), and X 2 % by mole of at least one non-sulfonated aromatic dihalogen sulfone (component (A2)) where X 1 is in the range of 15 to 80, and X 2 is in the range of 20 to 85, X moles of an aromatic dihalogen sulfone component (component (A)), Y moles of at least one aromatic dihydroxy compound (component (B)); Z moles of at least one carbonate compound (component (C)) Including, The ratio of X to Y is in the range of 0.95 to 1.05; and Z is in the range of P to Q, P has the formula: P = Y × (1.05 + X 1 / 100×1.05) and Q is calculated by the following formula: Q = Y × (1.05 + X 1 / 100×1.4) It is calculated by The reaction mixture (R G ) is converted.

[0084] More preferably, the molar ratio of component (A) to component (B) is from 0.95 to 1.05, particularly from 0.96 to 1.04, and most preferably from 0.97 to 1.03.

[0085] In a preferred embodiment, the ratio of X to Y is between 0.95 and 1.05, in particular between 0.96 and 1.04, most preferably between 0.97 and 1.03.

[0086] In a preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) obtained in step i) is G ) is not separated from the

[0087] In a preferred embodiment, the product mixture (P G ) is further worked up by steps ii) and iii) described below.

[0088] Thus, in a preferred embodiment, after step i), a product mixture (P) is obtained comprising the sulfonated polyarylene sulfone polymer (sP), at least one aprotic polar solvent, and at least one inorganic halide compound. G), the method further comprising: ii) adding said at least one inorganic halide to the product mixture (P G ) to obtain a solution (S) comprising the sulfonated polyarylene sulfone polymer (sP) and at least one aprotic polar solvent; and iii) separating said at least one aprotic polar solvent from the solution (S) by evaporation to obtain a sulfonated polyarylene sulfone polymer (sP). Includes.

[0089] After step iii), the sulfonated polyarylene sulfone polymer (sP) may be further processed, for example by extraction with a solvent, preferably a polar protic solvent, for example water.

[0090] In step ii), the inorganic halide compounds formed in step i) during the polycondensation reaction are reacted with the product mixture (P G ) to obtain a solution (S) comprising the sulfonated polyarylene sulfone polymer (sP) and at least one aprotic polar solvent (component (D)).

[0091] Inorganic halide compounds may be removed by means routinely known in the art, such as filtration, centrifugation, decantation, and the like.

[0092] Thus, the present invention relates to a process comprising the steps of: ii) The product mixture (P) obtained in step i) G ) by filtering, centrifuging and / or decanting to obtain a solution (S). Also provided is a method comprising:

[0093] In a preferred embodiment, the solution (S) obtained in step ii) does not contain solid inorganic halide compounds. In a further preferred embodiment, the solution (S) obtained in step ii) contains less than 3% by weight, more preferably less than 1.5% by weight, and particularly preferably less than 0.5% by weight of inorganic halide components relative to the total weight of the solution (S) obtained in step ii).

[0094] In a more preferred embodiment, the solution (S) obtained in step ii) is free of solid inorganic compounds.

[0095] In a further preferred embodiment, the solution (S) obtained in step ii) comprises less than 0.4% by weight, more preferably less than 0.3% by weight and particularly preferably less than 0.2% by weight of inorganic components relative to the total weight of the solution (S) obtained in step ii).

[0096] In a preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) in step ii) is not separated from the solution (S).

[0097] In a further preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) in solution (S) in step ii) remains in dissolved form before step iii) is carried out.

[0098] In a particularly preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) in the process of the invention remains dissolved until step iii) is carried out.

[0099] In a further particularly preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) is not isolated before step iii) is carried out.

[0100] The components used in the process of the present invention for producing the sulfonated polyarylene sulfone polymer (sP) are described in more detail below.

[0101] Component (A) Component (A), also referred to as the aromatic dihalogen sulfone component, comprises at least one sulfonated aromatic dihalogen sulfone and at least one non-sulfonated aromatic dihalogen sulfone.

[0102] The at least one sulfonated aromatic dihalogen sulfone is also referred to as component (A1). The terms at least one sulfonated aromatic dihalogen sulfone and component (A1) in the present invention are used synonymously and therefore have the same meaning.

[0103] The at least one non-sulfonated aromatic dihalogen sulfone is also referred to as component (A2). The terms at least one non-sulfonated aromatic dihalogen sulfone and component (A2) in the present invention are used synonymously and therefore have the same meaning.

[0104] Here, "at least one sulfonated aromatic dihalogen sulfone" means exactly one sulfonated aromatic dihalogen sulfone, and also a mixture of two or more sulfonated aromatic dihalogen sulfones. Preferably, exactly one sulfonated aromatic dihalogen sulfone is used.

[0105] Here, "at least one non-sulfonated aromatic dihalogen sulfone" means exactly one non-sulfonated aromatic dihalogen sulfone, and also a mixture of two or more non-sulfonated aromatic dihalogen sulfones. Preferably, exactly one non-sulfonated aromatic dihalogen sulfone is used.

[0106] "X" preferably refers to the reaction mixture (R G ) in which "X" preferably refers to the molar amount of component (A) in the reaction mixture (R G In other words, "X" refers to the total molar amount of aromatic dihalogen sulfone component (component (A)) preferably contained in component (A), preferably in the reaction mixture (R G The molar amount of component (A1) and component (A2) contained in the reaction mixture (R G) in which "X 1 " means the molar amount in mole percent of component (A1), and where "X 2 " means the molar amount in mole % of component (A2).

[0107] X 1 For example, each of the reaction mixtures (R G (A)) is in the range of 15 to 80 mol %, preferably in the range of 20 to 70 mol %, more preferably in the range of 25 to 65 mol %, and most preferably in the range of 27.5 to 62.5 mol %, based on the total molar amount of the aromatic dihalogen sulfone component (component (A)) in the copolymer (A).

[0108] X 2 are generally the reaction mixture (R G (A)) in the copolymer (A), the molar amount is in the range of 20 to 85 mol %, preferably in the range of 30 to 80 mol %, more preferably in the range of 35 to 75 mol %, and most preferably in the range of 37.5 to 72.5 mol %, based on the total molar amount of the aromatic dihalogen sulfone component (component (A)) in the copolymer (A).

[0109] X 1 and X 2 The amounts generally total 100 mole %.

[0110] Ingredient (A1) Component (A1) is also referred to as sulfonated aromatic dihalogen sulfone, and preferably has at least one -SO3X 3 Contains a group.

[0111] Component (A1) preferably contains at least one -SO3X 3 In this case, "at least one -SO3X 3 The "group" is a group in which the component (A1) is exactly one -SO3X 3 Group, and two or more -SO3X 3 It means that the component (A1) may also contain two -SO3X groups. 3 Contains a group.

[0112] General formula -SO3X 3Also includes sulfonic acid functional groups and derivatives of sulfonic acid functional groups, such as sulfonates. 3 In the group, X 3 may be hydrogen and / or one cation equivalent.

[0113] In the context of the present invention, "one cation equivalent" means one cation with a single positive charge, or one charge equivalent of a cation with two or more positive charges, such as Li, Na, K, Mg, Ca, NH4, preferably Na, K. Na or K is particularly preferred.

[0114] Component (A1) is preferably selected from the group consisting of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid, and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid, and derivatives thereof.

[0115] The term "sulfonic acid" and "-SO3X 3 The terms "sulfonic acid" and "sulfonic acid group" are used interchangeably and have the same meaning. Thus, the term "sulfonic acid" in 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid is understood to mean "-SO3X 3 where X means "group" 3 is hydrogen or a cation equivalent.

[0116] In one embodiment, component (A1) preferably has the cation equivalent -SO3X 3 Particularly preferably, component (A1) is selected from the group consisting of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt.

[0117] Another subject of the present invention is therefore a process, wherein component (A1) comprises at least one compound selected from the group consisting of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt.

[0118] In one embodiment, component (A1) is a reaction mixture (R G 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 3 The compound includes at least one aromatic dihalogen sulfone component that includes a group.

[0119] In a further particularly preferred embodiment, component (A1) essentially comprises at least one -SOX selected from the group consisting of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt. 3 The aromatic dihalogen sulfone comprises at least one aromatic dihalogen sulfone containing a group.

[0120] In those embodiments, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt and 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt are particularly preferred for use as component (A1).

[0121] In a further particularly preferred embodiment, component (A1) consists of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt or 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt.

[0122] Ingredients (A2) Component (A2) is also referred to as a non-sulfonated aromatic dihalogen sulfone component and is preferably -SO3X 3 Does not contain any group.

[0123] Preferably, component (A2) is present in the reaction mixture (R G), based on the total weight of component (A2) in the composition, 80% by weight or more, preferably 90% by weight or more, and more preferably 98% by weight or more of at least one aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, where the weight percentage with respect to component (A2) further relates to the total sum of the 4,4'-dichlorodiphenyl sulfone and the 4,4'-difluorodiphenyl sulfone used.

[0124] Another object of the present invention is therefore to provide a process for the preparation of a reaction mixture (R G The component (A2) in the polymerization initiator (A1) contains at least one aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone in an amount of 80 mass% or more based on the total mass of the component (A2) in the polymerization initiator (A1).

[0125] In further particularly preferred embodiments, component (A2) consists essentially of at least one aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone. In those embodiments, 4,4'-dichlorodiphenyl sulfone is particularly preferred for use as component (A2).

[0126] Preferably, component (A2) is selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.

[0127] Ingredient (B) Component (B), also known as an aromatic dihydroxy compound, generally contains two hydroxy groups.

[0128] Here, "at least one aromatic dihydroxy compound" means exactly one aromatic dihydroxy compound, and also a mixture of two or more aromatic dihydroxy compounds. Preferably, exactly one aromatic dihydroxy compound is used.

[0129] "Y" is preferably a reaction mixture (R G ) in which "Y" preferably refers to the molar amount of component (B) in the reaction mixture (R G (B)) means the total molar amount of the aromatic dihydroxy compound (component (B)) in the mixture.

[0130] Preferably, component (B) is selected from the group consisting of 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), 4,4'-dihydroxybenzophenone, and hydroquinone. Of the above-mentioned aromatic dihydroxy components, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, and bisphenol A are preferred, while 4,4'-dihydroxybiphenyl is particularly preferred.

[0131] Thus, the present invention also provides a method, wherein component (B) is selected from the group consisting of 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, bisphenol A, 4,4'-dihydroxybenzophenone, and hydroquinone.

[0132] Preferably, component (B) is present in the reaction mixture (R G ) contains 80% by mass or more, preferably 90% by mass or more, and more preferably 98% by mass or more of 4,4'-dihydroxybiphenyl, based on the total mass of component (B) in the composition (B).

[0133] A further object of the present invention is therefore to provide a process for the preparation of a reaction mixture (R G In the method, the component (B) in the composition (1) contains 80 mass % or more of 4,4'-dihydroxybiphenyl based on the total mass of the component (B) in the composition (1).

[0134] Here, the mass percentages relating to component (B) further relate to the total sum of 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, bisphenol A (2,2-bis-(4-hydroxyphenyl)propane), 4,4'-dihydroxybenzophenone and hydroquinone used.

[0135] In further particularly preferred embodiments, component (B) consists essentially of at least one aromatic dihydroxy component selected from the group consisting of 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), 4,4'-dihydroxybenzophenone, and hydroquinone. In those embodiments, 4,4'-dihydroxybiphenyl, bisphenol A, and 4,4'-dihydroxydiphenyl sulfone are particularly preferred for use as component (B), while 4,4'-dihydroxybiphenyl is most preferred.

[0136] Ingredients (C) The reaction mixture (R G ) comprises at least one carbonate compound as component (C). In this case, the term "at least one carbonate compound" is understood to mean exactly one carbonate compound, and also a mixture of two or more carbonate compounds. The at least one carbonate compound is preferably at least one metal carbonate. The metal carbonate is preferably anhydrous. In this case, the terms "at least one carbonate compound" and "component (C)" are used synonymously and therefore have the same meaning.

[0137] Alkali metal carbonates and / or alkaline earth metal carbonates are preferred as metal carbonates. At least one metal carbonate selected from the group consisting of sodium carbonate, potassium carbonate and calcium carbonate is particularly preferred as metal carbonate. Potassium carbonate is most preferred.

[0138] For example, component (C) may be added to the reaction mixture (R G ), more preferably 50% by weight or more, more preferably 70% by weight or more, and most preferably 90% by weight or more of potassium carbonate, based on the total weight of the at least one carbonate component in the composition.

[0139] Another object of the present invention is therefore to provide a process for the preparation of a reaction mixture (R G) contains 50 mass% or more of potassium carbonate based on the total mass of component (C) in the composition (C).

[0140] In a preferred embodiment, component (C) consists of potassium carbonate. Potassium carbonate having a volume weighted mean particle size of less than 200 μm, more preferably less than 100 μm, even more preferably less than 70 μm, and most preferably less than 50 μm is preferred as potassium carbonate. The volume weighted mean particle size of potassium carbonate is determined in a suspension of potassium carbonate in a mixture of chlorobenzene / sulfolane (60 / 40 by mass) using a particle size analyzer.

[0141] "Z" preferably refers to the reaction mixture (R G ) in which "Z" preferably refers to the molar amount of component (C) in the reaction mixture (R G (C)) in the aqueous solution.

[0142] Z is in the range of P to Q.

[0143] "P" is of the formula: P = Y × (1.05 + X 1 / 100×1.05) It is calculated according to:

[0144] In this formula, Y is the reaction mixture (R G ) is the molar amount of component (B) in 1 is the reaction mixture (R G ) is the mole percentage of component (A1).

[0145] "Q" is the formula: Q = Y × (1.05 + X 1 / 100×1.4) It is calculated according to:

[0146] In this formula, Y is the reaction mixture (R G ) is the molar amount of component (B) in 1 is the reaction mixture (R G) is the mole percentage of component (A1).

[0147] Ingredients (D) The reaction mixture (R G ) preferably comprises at least one aprotic polar solvent as component (D). According to the present invention, "at least one aprotic polar solvent" is understood to mean exactly one aprotic polar solvent, and also a mixture of two or more aprotic polar solvents. In this case, the terms "at least one aprotic polar solvent" and "component (D)" are used synonymously and therefore have the same meaning.

[0148] Suitable aprotic polar solvents are, for example, selected from the group consisting of anisole, dimethylformamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone, N-ethylpyrrolidone, and N-dimethylacetamide.

[0149] Preferably, component (D) is selected from the group consisting of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide and dimethylformamide. N-methylpyrrolidone is particularly preferred as component (D).

[0150] Component (D) is added to the reaction mixture (R G It is preferred that the component (D) in the composition contains at least one solvent selected from the group consisting of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide and dimethylformamide in an amount of 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more, based on the total mass of the component (D). N-methylpyrrolidone is particularly preferred as the component (D).

[0151] Another object of the present invention is therefore to provide a method for preparing a reaction mixture (R G The method further comprises the step of: (A) adding at least one solvent selected from the group consisting of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide, and dimethylformamide in an amount of 50 mass% or more based on the total mass of component (D) in the composition (A).

[0152] In a preferred embodiment, component (D) consists of N-methylpyrrolidone, also called NMP or N-methyl-2-pyrrolidone.

[0153] Membrane (M) The sulfonated polyarylene sulfone polymers (sP) according to the invention are suitable for the production of membranes (M). The sulfonated polyarylene sulfone polymers (sP) according to the invention can be used in membranes (M).

[0154] Another subject of the invention is therefore also the use in a membrane (M) of the sulfonated polyarylenesulfone polymer (sP) obtainable by the process according to the invention.

[0155] The membrane (M) may be produced from the sulfonated polyarylenesulfone polymer (sP) according to the invention by any method known to those skilled in the art.

[0156] Preferably, the membrane (M) comprising the sulfonated polyarylenesulfone polymer (sP) according to the invention has i) providing a solution (S) comprising a sulfonated polyarylene sulfone polymer (sP) and at least one solvent; ii) separating said at least one solvent from the solution (S) to obtain a membrane (M). The present invention is produced by a method comprising the steps of:

[0157] Another subject of the invention is therefore a method for the manufacture of a membrane (M) comprising a sulfonated polyarylenesulfone polymer (sP) obtainable by the method of the invention, comprising i) providing a solution (S) comprising the sulfonated polyarylene sulfone polymer (sP) obtainable by the method of the present invention and at least one solvent; ii) separating said at least one solvent from the solution (S) to obtain a membrane (M). The method comprises:

[0158] In a preferred embodiment, a method for producing a membrane (M) comprising a sulfonated polyarylenesulfone polymer (sP) according to any one of claims 1 to 5 is ii-1) preparing a solution (S) comprising the sulfonated polyarylenesulfone polymer (sP) obtained in step ii) of claim 9 and at least one aprotic polar solvent; and iii-1) Separating said at least one aprotic polar solvent from the solution (S) to obtain a membrane (M). Includes.

[0159] A further subject of the present invention is a membrane (M) comprising a sulfonated polyarylenesulfone polymer (sP).

[0160] Another subject of the invention is a membrane (M) comprising a sulfonated polyarylenesulfone polymer (sP) obtainable by the process of the invention.

[0161] The membrane (M) preferably comprises at least 50% by weight of sulfonated polyarylenesulfone polymer (sP), more preferably at least 70% by weight, and most preferably at least 90% by weight of sulfonated polyarylenesulfone polymer (sP), relative to the total weight of the membrane (M).

[0162] The membrane (M) is suitable for separating gases from gas mixtures, in particular for separating hydrogen from hydrogen-containing gas mixtures.

[0163] Another subject of the invention is therefore the use of a membrane (M) obtainable by the process according to the invention for separating a gas from a gas mixture. [Brief description of the drawings]

[0164] [Figure 1] FIG. 2 shows a preferred embodiment of a GPC chart of a sulfonated polyarylene sulfone polymer (sP) having a bimodal molecular weight distribution. EXAMPLES

[0165] The present invention will be further illustrated by the following examples, but is not limited thereto.

[0166] Ingredients used: DCDPS 4,4'-dichlorodiphenyl sulfone sDCDPS 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt BP 4,4'-dihydroxybiphenyl K2CO3 Potassium Carbonate, Anhydrous, Average Particle Size 32.6μm NMP N-Methylpyrrolidone, anhydrous.

[0167] The viscosity number VN of the sulfonated polyarylene sulfone polymers (sP) was determined in 0.5% by weight NMP solution according to DIN ISO 1628-1.

[0168] The incorporation rate of sDCDPS is 1 Characterized in CDCl3 by 1 H-NMR.

[0169] The molecular weight distributions of sulfonated polyarylenesulfone polymers having a unimodal molecular weight distribution (Comparative Examples C1, C2, C3, C4, C7, C8, C9 and C10) and sulfonated polyarylenesulfone polymers (sP) having a bimodal molecular weight distribution (Examples 5 and 6) were determined by GPC using DMAc as the solvent and narrowly distributed PMMA as described above.

[0170] In the comparative example, the precipitated sulfonated polyarylene sulfone polymer is dissolved in NMP at the same concentration (20% by weight) as the corresponding solution obtained in the present example. From this solution, an appropriate amount is dissolved in DMAc to a polymer concentration of 4 mg / ml. Then, 100 μl of this solution is injected into the GPC system.

[0171] The isolation of sulfonated polyarylenesulfone polymers with monomodal molecular weight distribution was carried out by precipitation of a NMP solution of the sulfonated polyarylenesulfone polymer (sP) in isopropanol at room temperature. The drop height is 0.5 m. The throughput was about 2.5 l per hour. The resulting precipitate was then extracted with water at 85° C. for 20 hours (water throughput 160 l / h). The material was then heated to a glass transition temperature T g It was dried at a lower temperature to a residual moisture content of less than 2% by weight.

[0172] Filtration of the product mixture was performed in a heated metal pressure filter using a filter with a pore size of 5 μm and 3 bar N2 pressure. The filter was heated to 60° C. to reduce the viscosity of the reaction mixture.

[0173] The yield of sulfonated polyarylene sulfone polymer was determined gravimetrically.

[0174] Comparative Example 1: Sulfonated polyarylene sulfone polymer with a unimodal molecular weight distribution: In a 4 liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 384.81 g (1.34 mol) of DCDPS, 343.84 g (0.70 mol) of sDCDPS, 372.42 g (2.00 mol) of BP and 400.81 g (2.90 mol) of potassium carbonate with a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under a nitrogen atmosphere. The mixture was heated to 190 ° C within 1 h. In the following, the reaction time should be understood as the time during which the reaction mixture was held at 190 ° C. The water formed in the reaction was continuously removed by distillation to replenish the loss of NMP.

[0175] After 8 hours of reaction time, the reaction was stopped by adding 1750 ml of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction was removed by filtration. The resulting polymer solution was precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The precipitate was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0176] Comparative Example 2: Sulfonated polyarylene sulfone polymer with a unimodal molecular weight distribution: In a 4 liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 370.45 g (1.29 mol) of DCDPS, 368.40 g (0.75 mol) of sDCDPS, 372.42 g (2.00 mol) of BP and 407.72 g (2.95 mol) of potassium carbonate with a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under nitrogen atmosphere. The mixture was heated to 190 ° C within 1 h. In the following, the reaction time should be understood as the time during which the reaction mixture was held at 190 ° C. The water formed in the reaction was continuously removed by distillation to replenish the loss of NMP.

[0177] After 8 hours of reaction time, the reaction was stopped by adding 1750 ml of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction was removed by filtration. The resulting polymer solution was precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The precipitate was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0178] Comparative Example 3: Sulfonated polyarylene sulfone polymer with a unimodal molecular weight distribution: In a 4 liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 364.69 g (1.27 mol) of DCDPS, 378.26 g (0.77 mol) of sDCDPS, 372.42 g (2.00 mol) of BP and 414.63 g (3.00 mol) of potassium carbonate with a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under nitrogen atmosphere. The mixture was heated to 190 ° C within 1 h. In the following, the reaction time should be understood as the time during which the reaction mixture was held at 190 ° C. The water formed in the reaction was continuously removed by distillation to replenish the loss of NMP.

[0179] After 8 hours of reaction time, the reaction was stopped by adding 1750 ml of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction was removed by filtration. The resulting polymer solution was precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The precipitate was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0180] Comparative Example 4: Sulfonated polyarylene sulfone polymer with a unimodal molecular weight distribution: In a 4 liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 356.07 g (1.24 mol) of DCDPS, 393.00 g (0.80 mol) of sDCDPS, 372.42 g (2.00 mol) of BP and 421.54 g (3.05 mol) of potassium carbonate with a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under a nitrogen atmosphere. The mixture was heated to 190 ° C within 1 h. In the following, the reaction time should be understood as the time during which the reaction mixture was held at 190 ° C. The water formed in the reaction was continuously removed by distillation to replenish the loss of NMP.

[0181] After 8 hours of reaction time, the reaction was stopped by adding 1750 ml of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction was removed by filtration. The resulting polymer solution was precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The precipitate was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0182] Example 5: Sulfonated polyarylene sulfone polymer (sP) with bimodal molecular weight distribution: In a 4 liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 384.81 g (1.34 mol) of DCDPS, 343.84 g (0.70 mol) of sDCDPS, 372.42 g (2.00 mol) of BP and 400.81 g (2.90 mol) of potassium carbonate with a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under a nitrogen atmosphere. The mixture was heated to 190 ° C within 1 h. In the following, the reaction time should be understood as the time during which the reaction mixture was held at 190 ° C. The water formed in the reaction was continuously removed by distillation to replenish the loss of NMP.

[0183] After 8 hours of reaction time, the reaction was stopped by adding 1750 ml of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction was removed by filtration. The resulting polymer solution was used for the preparation of membranes. The polymer content of this solution was 23.9% by weight.

[0184] Example 6: Sulfonated polyarylene sulfone polymer (sP) with bimodal molecular weight distribution: In a 4 liter glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 370.45 g (1.29 mol) of DCDPS, 368.40 g (0.75 mol) of sDCDPS, 372.42 g (2.00 mol) of BP and 407.72 g (2.95 mol) of potassium carbonate with a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under nitrogen atmosphere. The mixture was heated to 190 ° C within 1 h. In the following, the reaction time should be understood as the time during which the reaction mixture was held at 190 ° C. The water formed in the reaction was continuously removed by distillation to replenish the loss of NMP.

[0185] After 8 hours of reaction time, the reaction was stopped by adding 1750 ml of NMP and cooled to room temperature (within 1 hour). The potassium chloride formed in the reaction was removed by filtration. The resulting polymer solution was used for the preparation of membranes. The polymer content of this solution was 24.0% by weight.

[0186] Comparative Examples 7, 8, 9 and 10: Sulfonated polymers with unimodal molecular weight distribution: Small portions of the polymer solution obtained in Example 5 were precipitated in water (Comparative Example C7), ethanol (Comparative Example C8), methanol (Comparative Example C9), and water / ethanol (1 / 1 by volume) (Comparative Example C10). The resulting polymer was extracted in hot water for 20 hours, then dried at 120° C., and then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0187] To produce the membranes, solutions of the polymers separated from Examples C1, C2, C3, C4, C7, C8, C9 and C10 were prepared using a polymer content of 17.5% by weight. The solutions of Examples 5 and 6 were diluted with NMP to a polymer content of 17.5% by weight. Membranes from those solutions were produced by casting the solutions onto a glass plate with a doctor blade at a speed of 5 mm / s and a temperature of 60° C. The glass plate was transferred into a vacuum oven and the temperature was gradually increased to 100° C. and held there for 12 hours. After cooling to room temperature, the plate was placed in a water bath and the membrane was peeled off from the glass plate. The wet membrane was then clamped and dried in vacuum at 120° C. for 12 hours.

[0188] The membranes prepared as described above were cut to the required size (i.e. 5 × 5 cm). For activation, the membranes were immersed in 0.5 M H2SO4 at 80 °C for 2 h. Subsequently, the membranes were immersed in deionized water (MiliQ 18.2 MΩ) at 80 °C for another 2 h and finally stored at room temperature in a fresh batch of deionized water. For conductivity determination, two rectangular gold electrodes (0.25 cm 2 The membrane was sandwiched in a dedicated Teflon cell equipped with a pressure adjusting mechanism (PFA) and a pressure adjusting mechanism (PFA). A constant pressure was achieved by adjusting the torque of the four screws to 4 Nm.

[0189] [Table 1]

[0190] The membrane with a bimodal molecular weight distribution (M) exhibits higher conductivity.

Claims

1. A sulfonated polyarylene sulfone polymer (sP) having at least a bimodal molecular weight distribution with at least one first peak (P1) and at least one second peak (P2), wherein the maximum of said first peak (P1) is in the relative molecular weight range of 800 to 5000 g / mol and the maximum of said second peak (P2) is in the relative molecular weight range of 8000 to 300000 g / mol, said relative molecular weights being determined by gel permeation chromatography using dimethylacetamide as solvent and narrowly distributed poly(methyl methacrylate) as standard, said sulfonated polyarylene sulfone polymer (sP) being obtained by the reaction mixture (R G i) converting the reaction mixture (R G ) is a component, (A) an aromatic dihalogen sulfone component comprising at least one sulfonated aromatic dihalogen sulfone (component (A1)) and at least one non-sulfonated aromatic dihalogen sulfone (component (A2)); (B) at least one aromatic dihydroxy compound; (C) at least one carbonate compound, and (D) at least one aprotic polar solvent and after step i), a product mixture (P) comprising a sulfonated polyarylene sulfone polymer (sP), at least one aprotic polar solvent, and at least one inorganic halide compound is obtained. G ), and the method further comprises: ii) adding said at least one inorganic halide to the product mixture (P G ) to obtain a solution (S) comprising the sulfonated polyarylene sulfone polymer (sP) and at least one aprotic polar solvent; and iii) separating said at least one aprotic polar solvent from the solution (S) by evaporation to obtain a sulfonated polyarylene sulfone polymer (sP); Including, The sulfonated polyarylene sulfone polymer (sP).

2. 2. The sulfonated polyarylene sulfone polymer (sP) according to claim 1, wherein the maximum point of the first peak (P1) exhibits a first intensity (I1), and the maximum point of the second peak (P2) exhibits a second intensity (I2), and the ratio of the first intensity (I1) to the second intensity (I2) is in the range of 1:10 to 1:1000.

3. The sulfonated polyarylene sulfone polymer (sP) has a weight average molecular weight (M W ), and the mass average molecular weight (M W 2. The sulfonated polyarylene sulfone polymer (sP) of claim 1, characterized by gel permeation chromatography using dimethylacetamide as a solvent and narrowly distributed poly(methyl methacrylate) as a standard.

4. The sulfonated polyarylene sulfone polymer (sP) comprises 15 to 80 mol % of at least one —SO 3 X 3 and sulfonated repeating units containing a group, where X 3 The sulfonated polyarylene sulfone polymer (sP) of claim 1, wherein is hydrogen or one cation equivalent.

5. The sulfonated polyarylene sulfone polymer (sP) has the general formula I: 【Chemistry 1】 wherein: t and q are each independently 0, 1, 2, or 3; Q 1 , T and Y 1 are each independently a chemical bond, or —O—, —S—, or —SO 2 -, -S(=O)-, -C(=O)-, -N=N-, and -CR a R b -, and R a and R b are each independently a hydrogen atom or C 1 ~C 12 -Alkyl, C 1 ~C 12 -alkoxy or C 6 ~C 18 -aryl group, and at least one of Q, T and Y is -SO 2 - and Ar and Ar 1 are each independently C 6 ~C 18 -aryl, and said C 6 ~C 18 - aryl is unsubstituted or C 1 ~C 12 -Alkyl, C 1 ~C 12 -alkoxy, C 6 ~C 18 -aryl, halogen and -SO 3 and is substituted with at least one substituent selected from X; p, m, n, and k are each independently 0, 1, 2, 3, or 4, with the proviso that the total of p, m, n, and k is 1 or greater; and X 3 is hydrogen or one cation equivalent, The sulfonated polyarylene sulfone polymer (sP) according to claim 1.

6. A method for producing the sulfonated polyarylene sulfone polymer (sP) according to claim 1, comprising the steps of: G i) converting said reaction mixture (R G ) is a component, (A) an aromatic dihalogen sulfone component comprising at least one sulfonated aromatic dihalogen sulfone (component (A1)) and at least one non-sulfonated aromatic dihalogen sulfone (component (A2)); (B) at least one aromatic dihydroxy compound, and (C) at least one carbonate compound wherein the reaction mixture (R G ) further comprises at least one aprotic polar solvent (component (D)), and after step i), a product mixture (P) comprising the sulfonated polyarylene sulfone polymer (sP), at least one aprotic polar solvent, and at least one inorganic halide compound is obtained. G ), and the method further comprises: ii) adding said at least one inorganic halide to the product mixture (P G ) to obtain a solution (S) comprising the sulfonated polyarylene sulfone polymer (sP) and at least one aprotic polar solvent; and iii) separating said at least one aprotic polar solvent from the solution (S) by evaporation to obtain a sulfonated polyarylene sulfone polymer (sP); Including, The method.

7. i) Reaction mixture (R G ), wherein the reaction mixture (R G )teeth, The reaction mixture (R G relative to the total molar amount of the aromatic dihalogen sulfone component (component (A)) in X 1 mol % of at least one sulfonated aromatic dihalogen sulfone (component (A1)), and X 2 mol % of at least one non-sulfonated aromatic dihalogen sulfone (component (A2)) where X 1 is in the range of 15 to 80, and X 2 X moles of an aromatic dihalogen sulfone component (component (A)), wherein X moles of the aromatic dihalogen sulfone component (component (A)) is in the range of 20 to 85; Y moles of at least one aromatic dihydroxy compound (component (B)), Z moles of at least one carbonate compound (component (C)) Including, the ratio of X to Y is in the range of 0.95 to 1.05; and Z ranges from P to Q, P has the following formula: P=Y×(1.05+X 1 / 100×1.05) and Q is calculated by the following formula: Q=Y×(1.05+X 1 / 100×1.4) is calculated by The method of claim 6.

8. Component (A1) is a reaction mixture (R G 7. The method of claim 6, wherein the component (A1) contains 80 mass% or more of at least one compound selected from the group consisting of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, based on the total mass of component (A1) in component (A1).

9. Component (A2) is a reaction mixture (R G 7. The method according to claim 6, wherein the component (A2) in the composition (A1) contains at least one aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone in an amount of 80% by mass or more, based on the total mass of the component (A2) in the composition (A1).

10. Component (B) is a reaction mixture (R G The method according to claim 6, wherein the component (B) contains 80% by mass or more of 4,4'-dihydroxybiphenyl based on the total mass of the component (B) in the composition (B).

11. Use of a sulfonated polyarylene sulfone polymer (sP) according to any one of claims 1 to 5 or obtainable by the method according to any one of claims 6 to 10 for the production of a membrane (M).

12. A membrane (M) comprising a sulfonated polyarylene sulfone polymer (sP) according to any one of claims 1 to 5 or obtainable by the method according to any one of claims 6 to 10.

13. A method for producing a membrane (M) comprising a sulfonated polyarylene sulfone polymer (sP) according to any one of claims 1 to 5, comprising: ii-1) preparing a solution (S) comprising the sulfonated polyarylene sulfone polymer (sP) obtained in step ii) of claim 6 and at least one aprotic polar solvent; iii-1) Separating said at least one aprotic polar solvent from the solution (S) to obtain a membrane (M). The method comprising:

14. A membrane (M) obtainable by the method according to claim 13.

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