Method for producing sulfonated polyarylene sulfone polymer (sP)

Abstract

The present invention relates to a method for producing a sulfonated polyarylenesulfone polymer (sP), to the sulfonated polyarylenesulfone polymer (sP) obtainable by the method of the invention, to a membrane (M) comprising said sulfonated polyarylenesulfone polymer (sP), to a method for producing said membrane and to the use of said membrane (M) for separating gases from a gas mixture.

Description

[Technical field]

[0001] The present invention relates to a method for producing a sulfonated polyarylenesulfone polymer (sP), to the sulfonated polyarylenesulfone polymer (sP) obtainable by the method of the invention, to a membrane (M) comprising said sulfonated polyarylenesulfone polymer (sP), to a method for producing said membrane and to the use of said membrane (M) for separating gases from a gas mixture. [Background technology]

[0002] Politics, society and industry must reduce CO emissions by decarbonizing industry and mobility. 2 The aim is to reduce emissions from renewable energy sources. In this regard, green hydrogen plays a strategic role, since it can replace hydrocarbons for the propulsion of fuel cells in chemical and industrial processes, energy conversion, and mobility applications. Renewable electricity can be used to run electrolysis cells to produce green, 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 be ionically conductive, and at the same time they must separate the gases hydrogen and oxygen. 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.

[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 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 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 large amount of 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] European Patent Application Publication No. 297363 [Patent Document 2] 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 method for producing sulfonated polyarylene sulfone polymers (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 polymers (sP) should be suitable for producing membranes, in particular membranes capable of separating hydrogen from hydrogen-containing gas mixtures. [Means for solving the problem]

[0017] The subject of the present invention is a method for producing a sulfonated polyarylenesulfone polymer (sP), comprising the steps of: 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 % 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 25 to 70, and X 2 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 problem is solved by the method.

[0018] Surprisingly, it has been found that the use of carbonate compound in the amount according to the invention can significantly reduce the condensation time for producing sulfonated polyarylenesulfone polymer (sP).Moreover, the method of the invention can provide sulfonated polyarylenesulfone polymer (sP) with high viscosity number.Moreover, it has been found surprisingly that the sulfonated polyarylenesulfone polymer (sP) can be used to produce membranes with good proton conductivity.

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

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] Another subject of the present invention is therefore a reaction mixture (R G ) further comprises at least one aprotic polar solvent (component (D)).

[0026] 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).

[0027] 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.

[0028] 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.

[0029] The reaction mixture (R GThe 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.

[0030] 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).

[0031] 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.

[0032] 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.

[0033] 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 (B) relative to component (A) as starting compound.

[0034] More preferably, the molar ratio of component (A) to component (B) is from 0.95 to 1.08, particularly from 0.98 to 1.06, and most preferably from 0.985 to 1.05.

[0035] In a preferred embodiment, the ratio of X to Y is between 0.95 and 1.08, in particular between 0.98 and 1.06, most preferably between 0.985 and 1.05.

[0036] More preferably, the molar ratio of component (A) to component (B) is from 0.99 to 1.01, particularly from 0.992 to 1.008, and most preferably from 0.995 to 1.005.

[0037] In a preferred embodiment, the ratio of X to Y is between 0.99 and 1.01, in particular between 0.992 and 1.008, most preferably between 0.995 and 1.005.

[0038] Preferably, the conversion in the polycondensation reaction is at least 0.9.

[0039] 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.

[0040] Product mixture (P G The isolation of the resulting sulfonated polyarylene sulfone polymer (sP) obtained in the above process can be carried out by, for example, separating the product mixture (P) in water or a mixture of water and another solvent. G The sulfonated polyarylenesulfone polymer (P) precipitated can be subsequently extracted with water and then dried. In one embodiment of the present invention, the precipitate can also be taken up in an acidic medium. Suitable acids are, for example, organic or inorganic acids, such as carboxylic acids, for example acetic acid, propionic acid, succinic acid or citric acid, and mineral acids, for example hydrochloric acid, sulfuric acid or phosphoric acid.

[0041] The halide compound is added to the product mixture (P GThe halide compounds may be removed by means routinely known in the art, such as filtration, centrifugation, decantation, and the like.

[0042] Thus, the present invention relates to a method further comprising: ii) The product mixture (P G filtering, centrifuging or decanting the mixture. Also provided is a method comprising:

[0043] In one embodiment, the conversion with an aliphatic organohalogen compound is carried out after polycondensation, which end-caps the reactive hydroxyl groups and further stabilizes the polymer. The conversion with an aliphatic organohalogen compound can be carried out before or after filtration.

[0044] Preferred aliphatic organohalogen compounds are alkyl halides, especially alkyl chlorides having linear or branched alkyl groups having 1 to 10 carbon atoms, especially primary alkyl chlorides, particularly preferably methyl halides, especially methyl chloride.

[0045] The reaction with the aliphatic organohalogen compound is preferably carried out at a temperature of 90° C. to 160° C., in particular 100° C. to 150° C. The reaction time can vary widely and is usually at least 5 minutes, in particular at least 15 minutes. The reaction time is preferably 15 minutes to 8 hours, in particular 30 minutes to 4 hours.

[0046] Various methods can be used for adding aliphatic organic halogen compound.Furthermore, the amount of aliphatic organic halogen compound added can be stoichiometric ratio or excess, and the excess can be, for example, up to 5 times excess.In one preferred embodiment, aliphatic organic halogen compound is added continuously, especially through continuous introduction in the form of gas flow.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] "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 "X1 " means the molar amount in mole percent of component (A1), and where "X 2 " means the molar amount in mole % of component (A2).

[0053] X 1 are generally the reaction mixture (R G (A)) is in the range of 25 to 70 mol %, preferably in the range of 27.5 to 65 mol %, more preferably in the range of 30 to 60 mol %, and most preferably in the range of 32.5 to 57.5 mol %, based on the total molar amount of the aromatic dihalogen sulfone component (component (A)) in the copolymer (A).

[0054] X 2 are generally the reaction mixture (R G (A)) is in the range of 30 to 75 mol %, preferably in the range of 35 to 72.5 mol %, more preferably in the range of 40 to 70 mol %, and most preferably in the range of 42.5 to 67.5 mol %, based on the total molar amount of the aromatic dihalogen sulfone component (component (A)) in the copolymer (A).

[0055] X 1 and X 2 The amounts generally total 100 mole %.

[0056] Ingredient (A1) Component (A1), also referred to as sulfonated aromatic dihalogen sulfone, preferably contains at least one -SO 3 X 3 Contains a group.

[0057] Component (A1) preferably contains at least one -SO 3 X 3 In this case, "at least one -SO 3 X 3 The "group" means that the component (A1) has exactly one -SO 3 X 3 Group, and two or more -SO 3 X 3 It is more preferred that component (A1) contains two -SO groups. 3 X 3 Contains a group.

[0058] General formula -SO 3 X 3 Also includes sulfonic acid functional groups and derivatives of sulfonic acid functional groups, such as sulfonates. 3 X 3 In the group, X 3 may be hydrogen and / or one cation equivalent.

[0059] In the context of the present invention, "one cation equivalent" refers to 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, NH 4 , preferably Na, K. Na or K is particularly preferred.

[0060] 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.

[0061] The term "sulfonic acid" and "-SO 3 X 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 "-SO 3 X 3 where X means "group" 3 is hydrogen or a cation equivalent.

[0062] In one embodiment, component (A1) preferably has a cation equivalent of -SO 3 X 3Particularly 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.

[0063] 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.

[0064] 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 X 3 The compound includes at least one aromatic dihalogen sulfone component that includes a group.

[0065] In a further particularly preferred embodiment, component (A1) essentially comprises at least one -SO 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 X 3 The term "essentially consisting of" means that the component (A2) is entirely contained in the reaction mixture (R G %, preferably more than 98% by weight, and more preferably more than 99% by weight, of at least one -SO 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 X 3 It is meant to include at least one aromatic dihalogen sulfone containing group.

[0066] 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).

[0067] 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.

[0068] Ingredients (A2) Component (A2) is also referred to as the non-sulfonated aromatic dihalogen sulfone component and is preferably -SO 3 X 3 Does not contain any group.

[0069] 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.

[0070] 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).

[0071] In a further particularly preferred embodiment, 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, where "consists essentially of" means that component (A2) is entirely present in the reaction mixture (R GIt means that the at least one aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone is contained in an amount of more than 99% by weight, preferably more than 99.5% by weight, and more preferably more than 99.9% by weight, based on the total weight of component (A2) in the composition. In those embodiments, 4,4'-dichlorodiphenyl sulfone is particularly preferred for use as component (A2).

[0072] In a further particularly preferred embodiment, component (A2) consists essentially of 4,4'-dichlorodiphenyl sulfone. Here, "consists essentially of" means that component (A2) comprises more than 99% by weight, preferably more than 99.5% by weight, and more preferably more than 99.9% by weight of 4,4'-dichlorodiphenyl sulfone. In a further particularly preferred embodiment, component (A2) consists essentially of 4,4'-dichlorodiphenyl sulfone.

[0073] Preferably, component (A2) is selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.

[0074] Ingredient (B) Component (B), also known as an aromatic dihydroxy compound, generally contains two hydroxy groups.

[0075] 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.

[0076] "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.

[0077] 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.

[0078] 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.

[0079] 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).

[0080] 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).

[0081] 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.

[0082] In a further particularly preferred embodiment, 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, where "consists essentially of" means that component (B) is entirely present in the reaction mixture (R G It means that the total weight of component (B) in the composition (B) contains more than 98% by weight, preferably more than 99.0% by weight, and more preferably more than 99.5% by weight 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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).

[0087] 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.

[0088] "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.

[0089] Z is in the range of P to Q.

[0090] "P" is of the formula: P = Y × (1.05 + X 1 / 100×1.05) It is calculated according to:

[0091] 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).

[0092] "Q" is the formula: Q = Y × (1.05 + X 1 / 100×1.4) It is calculated according to:

[0093] 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).

[0094] For the composition used in Example 3 of the present invention, P is 2.82 while Q is 3.06. Thus, the range of Z is 2.82 to 3.06, and 2.9 moles are used.

[0095] 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.

[0096] Suitable aprotic polar solvents are, for example, selected from the group consisting of anisole, dimethylformamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone, N-ethylpyrrolidone, and N-dimethylacetamide.

[0097] 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).

[0098] Component (D) is added to the reaction mixture (R GIt 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).

[0099] 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).

[0100] In a preferred embodiment, component (D) consists of N-methylpyrrolidone, also called NMP or N-methyl-2-pyrrolidone.

[0101] Sulfonated polyarylene sulfone polymer (sP) Sulfonated polyarylene sulfone polymers (sP) are a class of polymers known to those skilled in the art. In principle, it is possible to use any sulfonated polyarylene sulfone polymer (sP) known to those skilled in the art and / or which can be produced by known methods. Suitable methods for producing sulfonated polyarylene sulfone polymers (sP) are described in a later stage. Preferred sulfonated polyarylene sulfone polymers (sP) are those of 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-, -SO 2 -, 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 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, 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 equal to or greater than 1; and X 3 is hydrogen or one cation equivalent.

[0102] 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-, -SO 2 -, -S(=O)-, -C(=O)-, -N=N- and -CR a R b - selected from R a and R bare 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, 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 equal to or greater than 1; and X 3 is hydrogen or one cation equivalent, It is a sulfonated polyarylene sulfone polymer (sP).

[0103] 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).

[0104] 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.

[0105] R a and R b are each independently hydrogen or C 1 ~C 12 -alkyl.

[0106] Preferred C 1 ~C 12 -Alkyl groups include linear and branched, saturated alkyl groups of 1 to 12 carbon atoms. The following moieties are particularly suitable: 1 ~C 6 -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.

[0107] Used C 1 ~C 12 The alkyl moiety in the alkoxy group comprises an alkyl group as defined above having 1 to 12 carbon atoms. The cycloalkyl moiety preferably used is in particular 3 ~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.

[0108] Ar and Ar 1 are each independently C 6 ~C 18 Starting 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, and 4,4'-bisphenol. 1 is preferably unsubstituted C 6 or C 12 -arylene group.

[0109] 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, in particular 2,7-dihydroxynaphthalene and 4,4'-bisphenylene.

[0110] The following structural units (Ia)-(Io): [ka]

[0111] [ka]

[0112] [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.

[0113] In the context of the present invention, "one cation equivalent" refers to 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, NH 4 , preferably Na and K.

[0114] 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.

[0115] Copolymers consisting of a combination of various structural units, or sulfonated and non-sulfonated structural units, are also useful.

[0116] The structural units (Ia), (Ib), (Ig) and (Ik) or copolymers thereof are particularly preferably used as repeating units of the general formula (I).

[0117] In one particularly preferred embodiment, Ar is 1,4-phenylene, t is 1, T is a chemical bond, and Y 1 -SO 2 -, 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.

[0118] In a particularly preferred embodiment, Ar is 1,4-phenylene, t is 0, and Y is -SO 2 -, q is 0, n is 0, and k is 0. A polyarylene sulfone composed of repeating units of this listed structure is referred to as sulfonated polyether ether sulfone (sPEES).

[0119] In one advantageous embodiment, the sulfonated polyarylene sulfone polymer (sP) is represented by the formula (1) [ka] and non-sulfonated repeating units of formula (2) [ka] The sulfonated repeat unit comprises:

[0120] In particular, the sulfonated polyarylenesulfone polymer (sP) consists exclusively of non-sulfonated repeat units of formula (1) and sulfonated repeat units of formula (2).

[0121] In a highly advantageous embodiment, the sulfonated polyarylene sulfone polymer (sP) has the formula (1a) [ka] and non-sulfonated repeat units of formula (1b) [ka] The sulfonated repeat unit comprises:

[0122] In particular, the sulfonated polyarylenesulfone polymer (sP) consists exclusively of non-sulfonated repeat units of formula (1a) and sulfonated repeat units of formula (1b).

[0123] The sulfonated polyarylene sulfone polymers (sP) used according to the invention preferably have a viscosity number of 20 ml / g to 250 ml / g, preferably 50 ml / g to 200 ml / g. This viscosity number is quantified in accordance with DIN EN ISO 1628-1 in a 1% solution in N-methylpyrrolidone (NMP) at 25° C. Measurements can also be carried out at lower polymer concentrations, for example 0.5%.

[0124] The weight average molecular weight (M W The mass average molecular weight (M) is generally in the range of 10,000 to 250,000 g / mol, preferably in the range of 15,000 to 200,000 g / mol, and more preferably in the range of 18,000 to 150,000 g / mol. W ) was measured using gel permeation chromatography (GPC). In the measurements, dimethylacetamide (DMAc) was used as the solvent and narrow distribution polymethylmethacrylate was used as the standard.

[0125] The sulfonated polyarylene sulfone polymers (sP) according to the invention preferably have a viscosity number of 80 ml / g or more, preferably 85 ml / g or more and particularly preferably 90 ml / g or more, quantified at 25° C. in a 0.5% solution in N-methylpyrrolidone (NMP) according to DIN EN ISO 1628-1.

[0126] The sulfonated polyarylene sulfone polymers (sP) according to the invention preferably have a viscosity number of 80 ml / g to 150 ml / g, preferably 85 ml / g to 140 ml / g, quantified at 25° C. in a 0.5% solution in N-methylpyrrolidone (NMP) according to DIN EN ISO 1628-1.

[0127] The weight average molecular weight (M W The mass average molecular weight (M) is generally in the range of 40,000 to 250,000 g / mol, preferably in the range of 50,000 to 200,000 g / mol, and more preferably in the range of 60,000 to 150,000 g / mol. W ) was measured using gel permeation chromatography (GPC). In the measurements, dimethylacetamide (DMAc) was used as the solvent and narrow distribution polymethylmethacrylate was used as the standard.

[0128] Another subject of the present invention is therefore the sulfonated polyarylenesulfone polymers (sP) obtainable by the process according to the invention.

[0129] Another subject of the present invention is therefore a sulfonated polyarylenesulfone polymer (sP) comprising recurring units of general formula (I).

[0130] In another embodiment, X 3 isX 3a or X 3b It is.

[0131] Another subject of the invention is a compound having at least one -SO 3 X 3a group and / or at least one -SO 3 X 3b The repeat unit contains a repeat unit containing a group, where X 3a and X 3b are each independently at least one selected from the group consisting of hydrogen and a cation equivalent, and X contained in the sulfonated polyarylene sulfone polymer (sP)3a and X 3b at least 50 mol % of the total amount of the sulfonated polyarylene sulfone polymer (sP) are potassium cations.

[0132] Surprisingly, it has been found that the sulfonated polyarylenesulfone polymers (sP) of the present invention can be used to produce membranes with good proton conductivity. The membranes (M) are even more surprising because they exhibit less water swelling and less size change than membranes produced from sulfonated polyarylenesulfone polymers known in the prior art.

[0133] The sulfonated polyarylene sulfone polymer (sP) according to the present invention comprises at least one -SO 3 X 3a group and / or at least one -SO 3 X 3b In this case, the repeat unit contains at least one -SO 3 X 3a group and / or at least one -SO 3 X 3b Repeat units that contain a repeat unit that includes a group are also referred to as sulfonated repeat units.

[0134] The sulfonated polyarylenesulfone polymer (sP) according to the present invention may contain sulfonated and non-sulfonated repeating units. 3 X 3a and -SO 3 X 3b It is understood to mean a repeating unit which does not contain a group.

[0135] In a preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) contains sulfonated repeat units in the range of 25 to 70 mol %, preferably in the range of 27.5 to 65 mol %, more preferably in the range of 30 to 60 mol %, and most preferably in the range of 32.5 to 57.5 mol %, based on the total molar amount of the sulfonated polyarylene sulfone polymer (sP).

[0136] In a preferred embodiment, the sulfonated polyarylene sulfone polymer (sP) contains non-sulfonated repeat units in the range of 30 to 75 mol %, preferably in the range of 35 to 72.5 mol %, more preferably in the range of 40 to 70 mol %, and most preferably in the range of 42.5 to 67.5 mol %, based on the total molar amount of the sulfonated polyarylene sulfone polymer (sP).

[0137] The amount of sulfonated and non-sulfonated repeat units in the sulfonated polyarylene sulfone polymer (sP) generally totals 100 mole %.

[0138] In this case, "at least one -SO 3 X 3a "and "at least one -SO 3 X 3b The term "group" means "at least one -SO 3 X 3 "At least one -SO group" is included in the term "at least one -SO group". 3 X 3 The term "group" means "at least one -SO 3 X 3a "and / or "at least one -SO 3 X 3b It may mean a "group".

[0139] Here, "X 3a " and "X 3b " is "X 3 " At least one -SO 3 X 3 The term "group" means "at least one -SO 3 X 3a "and / or "at least one -SO 3 X 3b It may mean a "group".

[0140] "At least one -SO 3 X 3 All descriptions in view of the "group" include "at least one -SO3 X 3a "and "at least one -SO 3 X 3b This also applies to "groups."

[0141] Furthermore, "X 3 All explanations in light of "X 3a " and "X 3b " also applies.

[0142] In this case, "at least one -SO 3 X 3 The term "group" refers to exactly one -SO 3 X 3 group, and two, three or four -SO 3 X 3 In a preferred embodiment, the sulfonated repeat unit is a repeat unit having one to four -SO 3 X 3 group, more preferably 1 to 3 -SO 3 X 3 groups, and particularly preferably 1 to 2 -SO 3 X 3 In a particularly preferred embodiment, the sulfonated repeat unit contains two -SO groups. 3 X 3 Contains a group.

[0143] X 3a and X 3b are each independently at least one selected from the group consisting of hydrogen and a cation equivalent. The term "cation equivalent" in the context of the present invention 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, NH 4 , preferably Na, K, provided that each of X contained in the sulfonated polyarylene sulfone polymer (sP) 3a and X 3b At least 50 mol %, more preferably at least 55 mol %, even more preferably 60 to 80 mol %, and particularly preferably 62.5 to 77.5 mol % of the total amount are potassium cations.

[0144] In a highly advantageous embodiment, the sulfonated polyarylene sulfone polymer (sP) has the formula (1a) [ka] and non-sulfonated repeat units of formula (1b) [ka] The sulfonated repeat unit comprises:

[0145] In particular, the sulfonated polyarylenesulfone polymer (sP) consists exclusively of non-sulfonated repeat units of formula (1a) and sulfonated repeat units of formula (1b).

[0146] The sulfonated polyarylenesulfone polymer (sP) is suitable for the production of a membrane (M). The sulfonated polyarylenesulfone polymer (sP) obtainable by the process of the invention can be used in a membrane (M).

[0147] 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.

[0148] 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.

[0149] Preferably, the membrane (M) comprising the sulfonated polyarylenesulfone polymer (sP) obtainable by the method of 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:

[0150] 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 the steps of: 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:

[0151] A further subject of the present invention is a membrane (M) comprising a sulfonated polyarylenesulfone polymer (sP), obtainable by the process described above.

[0152] Another subject of the invention is a membrane (M) comprising a sulfonated polyarylenesulfone polymer (sP) obtainable by the process of the invention.

[0153] 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).

[0154] The membrane (M) is suitable for separating gases from gas mixtures, in particular for separating hydrogen from hydrogen-containing gas mixtures.

[0155] 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.

[0156] The present invention will be further illustrated by the following examples, but is not limited thereto. EXAMPLES

[0157] Ingredients used: DCDPS 4,4'-dichlorodiphenyl sulfone sDCDPS 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt BP 4,4'-dihydroxybiphenyl K 2 CO 3 Potassium Carbonate, Anhydrous, Average Particle Size 32.6μm NMP N-Methylpyrrolidone, anhydrous.

[0158] 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.

[0159] The incorporation rate of sDCDPS is 1 H-NMR by CDCl 3 In addition, the polymer content of the polymer solution after filtration was 1 H-NMR by CDCl 3 was quantified in

[0160] The counterion content was determined by atomic spectroscopy.

[0161] The isolation of the sulfonated polyarylenesulfone polymer (sP) was carried out by dropping a solution of the sulfonated polyarylenesulfone polymer (sP) in NMP into isopropanol at room temperature, unless otherwise indicated. 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 subjected to extraction at a glass transition temperature T g It was dried at a lower temperature to a residual moisture content of less than 2% by weight.

[0162] Product mixture (P G ) in a heated metal pressure filter with a 5 μm pore size and 3 bar N 2This was done using pressure. The filter was heated to 60° C. to reduce the viscosity of the reaction mixture.

[0163] The yield of sulfonated polyarylene sulfone polymer (sP) after precipitation was determined gravimetrically.

[0164] Comparative Example 1: In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 384.794 g (1.34 mol) of DCDPS, 343.875 g (0.7 mol) of sDCDPS, 372.42 g (2.00 mol) of BP, and 304.052 g (2.20 mol) of potassium carbonate having a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under a nitrogen atmosphere.

[0165] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to be understood as the time during which the reaction mixture was held at 190° C. Water formed in the reaction was continuously removed by distillation.

[0166] After 16 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 then precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The material was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0167] Comparative Example 2 In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 384.794 g (1.34 mol) of DCDPS, 343.875 g (0.7 mol) of sDCDPS, 372.42 g (2.00 mol) of BP, and 345.525 g (2.50 mol) of potassium carbonate having a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under a nitrogen atmosphere.

[0168] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to be understood as the time during which the reaction mixture was held at 190° C. Water formed in the reaction was continuously removed by distillation.

[0169] After 16 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 then precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The material was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0170] Example 3: In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 384.794 g (1.34 mol) of DCDPS, 343.875 g (0.7 mol) of sDCDPS, 372.42 g (2.00 mol) of BP, and 400.809 g (2.90 mol) of potassium carbonate having a volume average particle size of 32.6 μm were suspended in 1250 ml of NMP under a nitrogen atmosphere.

[0171] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to be understood as the time during which the reaction mixture was held at 190° C. Water formed in the reaction was continuously removed by distillation.

[0172] After 8.5 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 then precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The material was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0173] Example 4: In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 258.444 g (0.900 mol) of DCDPS, 309.487 g (0.63 mol) of sDCDPS, 279.315 g (1.50 mol) of BP, and 321.338 g (2.325 mol) of potassium carbonate having a volume average particle size of 32.6 μm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0174] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to be understood as the time during which the reaction mixture was held at 190° C. Water formed in the reaction was continuously removed by distillation.

[0175] After 8.5 hours of reaction time, the reaction was stopped by adding 2312 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 then precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The material was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0176] Example 5: In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 223.985 g (0.78 mol) of DCDPS, 368.327 g (0.75 mol) of sDCDPS, 279.315 g (1.50 mol) of BP, and 345.525 g (2.5 mol) of potassium carbonate having a volume average particle size of 32.6 μm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0177] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to be understood as the time during which the reaction mixture was held at 190° C. Water formed in the reaction was continuously removed by distillation.

[0178] After 8.5 hours of reaction time, the reaction was stopped by adding 2312 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 then precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The material was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0179] Comparative Example 6 In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 223.985 g (0.78 mol) of DCDPS, 368.327 g (0.75 mol) of sDCDPS, 279.315 g (1.50 mol) of BP, and 414.63 g (3 mol) of potassium carbonate having a volume average particle size of 32.6 μm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0180] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to be understood as the time during which the reaction mixture was held at 190° C. Water formed in the reaction was continuously removed by distillation.

[0181] After 8.5 hours of reaction time, the reaction was stopped by adding 2312 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 then precipitated in isopropanol, and the resulting polymer precipitate was separated and then extracted with hot water (85° C.) for 20 hours. The material was then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0182] [Table 1]

[0183] By using the amount of potassium carbonate of the present invention, it is possible to produce a high molecular weight sulfonated polyarylene sulfone polymer (sP) incorporating a large amount of sDCDPs. Surprisingly, the filtration time of the high molecular weight sulfonated polyarylene sulfone polymer (sP) obtained by the method of the present invention is shorter than that observed for the high molecular weight product obtained with a higher excess of potassium carbonate.

[0184] Comparative Example 7 (C7): In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 288.606 g (1.005 mol) of DCDPS, 257.90 g (0.525 mol) of sDCDPS, 279.315 g (1.5000 mol) of BP, and 248.778 (1.80 mol) of potassium carbonate having a volume average particle size of 32.6 µm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0185] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to 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.

[0186] After 8 hours of reaction time, the reaction was stopped by adding 1312 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 then divided into two equal parts. One part was precipitated in isopropanol, the resulting polymer beads were separated and then extracted with hot water (85° C.) for 20 hours. The beads were then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0187] Comparative Example 8 (C8): In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 288.606 g (1.005 mol) of DCDPS, 257.90 g (0.5250 mol) of sDCDPS, 279.315 g (1.50 mol) of BP, and 310.97 g (2.25 mol) of potassium carbonate having a volume average particle size of 32.6 µm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0188] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to 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.

[0189] After 6.5 hours of reaction time, the torque reached a plateau and the reaction was stopped by adding 1312 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 then divided into two equal parts. One part was precipitated in isopropanol and the resulting polymer beads were separated and then extracted with hot water (85°C) for 20 hours. The beads were then dried under reduced pressure (<100 mbar) at 120°C for 24 hours.

[0190] Comparative example 9 (C9): In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 288.60 g (1.005 mol) of DCDPS, 257.90 g (0.525 mol) of sDCDPS, 279.315 g (1.50 mol) of BP, and 248.778 g (1.80 mol) of potassium carbonate having a volume average particle size of 32.6 µm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0191] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to 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.

[0192] After 8 hours of reaction time, the reaction was stopped by adding 1312 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 then divided into two equal parts. One part was precipitated in isopropanol, the resulting polymer beads were separated and then extracted with hot water (85° C.) for 20 hours. The beads were then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0193] Example 10: In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 281.273 g (0.9795 mol) of DCDPS, 257.90 g (0.525 mol) of sDCDPS, 279.315 g (1.500 mol) of BP, and 310.973 g (2.25 mol) of potassium carbonate having a volume average particle size of 32.6 µm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0194] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to 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.

[0195] After 5.7 hours of reaction time, the reaction was stopped by adding 1312 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 then divided into two equal parts. One part was precipitated in isopropanol, the resulting polymer beads were separated and then extracted with hot water (85° C.) for 20 hours. The beads were then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0196] Example 11: In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 279.981 g (0.975 mol) of DCDPS, 257.90 g (0.525 mol) of sDCDPS, 279.315 g (1.500 mol) of BP, and 310.973 g (2.25 mol) of potassium carbonate having a volume average particle size of 32.6 μm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0197] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to 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.

[0198] After 5.4 hours of reaction time, the reaction was stopped by adding 1312 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 then divided into two equal parts. One part was precipitated in isopropanol, the resulting polymer beads were separated and then extracted with hot water (85° C.) for 20 hours. The beads were then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0199] Comparative Example 12 (C12): In a 4 L glass reactor equipped with a thermometer, a gas inlet tube and a Dean-Stark trap, 255.52 g (1.005 mol) of DFDPS, 257.90 g (0.525 mol) of sDCDPS, 279.315 g (1.5000 mol) of BP, and 248.778 (1.80 mol) of potassium carbonate with a volume average particle size of 32.6 µm were suspended in 938 ml of NMP under a nitrogen atmosphere.

[0200] The mixture was heated to 190° C. within 1 hour. In the following, the reaction time is to 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.

[0201] After 5 hours of reaction time, the reaction was stopped by adding 1312 ml of NMP and cooled to room temperature (within 1 hour). The potassium fluoride formed in the reaction was removed by filtration. The resulting polymer solution was then divided into two equal parts. One part was precipitated in isopropanol, the resulting polymer beads were separated and then extracted with hot water (85° C.) for 20 hours. The beads were then dried under reduced pressure (<100 mbar) at 120° C. for 24 hours.

[0202] [Table 2]

[0203] Film evaluation The sulfonated polyarylenesulfone polymers (sP) from comparative examples C9 and C12 and inventive examples 10 and 11 were dissolved in NMP (20% by weight) and the solution was applied by doctor blade onto a glass support having a thickness of 300 μm. The wet film was first dried in vacuum at room temperature, then the temperature was increased to 140° C. and dried for 12 hours. The obtained films (FC9, F10, F11 and FC12) were subsequently separated from the glass plate, extracted with hot water (85° C.) for 4 hours, and then dried again in a vacuum oven. H-NMR confirmed that the NMP content of the films was less than 0.1% by weight. Two pieces of each film with a mass of 0.1 g were then stored in deionized water until the water absorption no longer changed, and the water content (%) of the films was determined by gravimetric measurement.

[0204] [Table 3]

[0205] Surprisingly, films with higher potassium counterion content exhibited lower water swelling and better three-dimensional stability, which is favorable for technical uses.

Claims

1. 1. A method for producing a sulfonated polyarylene sulfone polymer (sP), comprising the steps of: 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 25 to 70, 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 30 to 75; 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.

2. The reaction mixture (R G 10. The method of claim 1, wherein the solvent (component (D)) further comprises at least one aprotic polar solvent.

3. 3. The method of claim 1, 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.

4. Component (A2) is a reaction mixture (R G 3. The method according to claim 1, 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 mass% or more, based on the total mass of the component (A2) in the composition (A1).

5. Component (B) is a reaction mixture (R G The method according to claim 1 or 2, 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).

6. A sulfonated polyarylene sulfone polymer (sP) obtainable by the process according to claim 1.

7. The sulfonated polyarylene sulfone polymer (sP) has the general formula I: 【Chemistry 1】 wherein the repeating unit is 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 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 6.

8. At least one -SO 3 X 3a group and / or at least one —SO 3 X 3b It contains repeating units containing a group, where X 3a and X 3b are each independently at least one selected from the group consisting of hydrogen and a cation equivalent, and X contained in the sulfonated polyarylene sulfone polymer (sP) 3a and X 3b 7. The sulfonated polyarylene sulfone polymer (sP) of claim 6, wherein at least 50 mol % of the total amount of is potassium cations.

9. At least one -SO 3 X 3a group and / or at least one —SO 3 X 3b It contains repeating units containing a group, where X 3a and X 3b are each independently at least one selected from the group consisting of hydrogen and a cation equivalent, and X contained in the sulfonated polyarylene sulfone polymer (sP) 3a and X 3b at least 50 mol % of the total amount of sulfonated polyarylene sulfone polymer (sP) are potassium cations.

10. 10. Use of the sulfonated polyarylene sulfone polymer (sP) according to any one of claims 6 to 9 for producing a membrane (M).

11. A method for producing a membrane (M) comprising a sulfonated polyarylene sulfone polymer (sP) according to any one of claims 6 to 9, comprising: i) providing a solution (S) comprising the sulfonated polyarylene sulfone polymer (sP) according to any one of claims 6 to 9 and at least one solvent; ii) separating said at least one solvent from the solution (S) to obtain a membrane (M); The method comprising:

12. A membrane (M) obtainable by the method according to claim 11.

13. A membrane (M) comprising a sulfonated polyarylene sulfone polymer (sP) according to any one of claims 6 to 9.

14. 13. Use of a membrane (M) according to claim 12 for separating gases from a gas mixture.

15. 13. Use of the membrane (M) according to claim 12 in electrolysis cells, electrodialysis cells and fuel cells.

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