Sulfonated poly(arylene ether)s and their metal salts, blends thereof, and uses thereof

Abstract

A polymer blend composition including 99.9 to 0.1 weight percent, preferably 99.9 to 10 weight percent, more preferably 99.9 to 30 weight percent of a sulfonated poly(arylene ether), its metal salt, or a combination thereof, preferably the metal salt of the sulfonated poly(arylene ether), and 0.1 to 95 weight percent, preferably 0.1 to 90 weight percent, more preferably 0.1 to 70 weight percent of a poly etherimide; wherein the polymer blend composition has a single glass transition temperature. The polymer blend composition can be used in selectively permeable separation membranes. Alternatively, a selectively permeable separation membrane can include a first polymer layer wherein the polymer is 100 weight percent of a sulfonated poly(arylene ether), its metal salt, or a combination thereof, and a second layer including a polyetherimide, or the blend of the sulfonated poly( arylene ether), its metal salt, or a combination thereof, and the polyetherimide.

Description

24SHPP0045-WO-PCT (SS290020PCT)SULFONATED POLY(ARYLENE ETHER)S AND THEIR METAL SALTS, BLENDS THEREOF, AND USES THEREOFCROSS REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of European Patent Application No.24223309.6 filed December 26, 2024, the contents of which are hereby incorporated by reference in their entirety.BACKGROUND

[0001] Disclosed herein are compositions including sulfonated poly(arylene ether)s, metal salts of the sulfonated poly(arylene ether)s, blends thereof, and uses thereof, including in separation membranes, and methods for the manufacture and use of such blends, as well as separation membranes.

[0002] Separations of fluids (whether gaseous or liquid) is a critical step in manufacturing and purification processes. Poly(arylene ether)s, particularly polyphenylene ethers, are known to have high fractional free volumes among glassy amorphous polymers. Large fractional free volume elements (holes) allow high penetrant permeability. The premium that is paid for high permeability is moderate selectivity. There remains a need in the art for an improved balance between permeability and selectivity. Moreover, polyphenylene ethers are soluble in a limited number of solvents. Therefore, preparation of separation membranes has challenges using industrial-scale solvents typically used in the membrane industry.

[0003] Accordingly, there remains a continuing need in the art for compositions and methods of manufacture of fluid separation membranes with an improved permeabilityselectivity balance.SUMMARY

[0004] Described herein is a polymer blend composition comprising a sulfonated poly(arylene ether), a metal salt of the sulfonated poly(arylene ether), or a combination thereof, preferably the metal salt of the sulfonated poly(arylene ether), and a polyetherimide. The polymer blend composition can include 99.9 to 0.1 weight percent, preferably 99.9 to 10 weight percent, more preferably 99.9 to 30 weight percent of the sulfonated poly(arylene ether), its metal salt, or combination thereof, and 0.1 to 95 weight percent, preferably 0.1 to 90 weight percent, more preferably 0.1 to 70 weight percent of a polyetherimide, each based on the total weight of the sulfonated poly(arylene ether), its metal salt, or the combination thereof and the24SHPP0045-WO-PCT (SS290020PCT)poly etherimide; wherein the polymer blend composition has a single glass transition temperature as determined using differential scanning calorimetry. In some aspects, the polymer blend composition or a selectively permeable separation membrane including the polymer blend composition has less than 1 weight percent, or less than 0.5 weight percent, or less than 0.1 weight percent of a solvent based on the total weight of the polymer blend composition, as determined using gas chromatography. In some aspects the single glass transition temperature is below 230 °C.

[0005] Another aspect is a selectively permeable separation membrane including the polymer blend composition. The selectively permeable separation membrane can have a porosity of 0.5 cm3tfcO / gram of dry membrane or less, as determined by scanning electron microscopy. Alternatively, a selectively permeable separation membrane includes a first layer wherein only the sulfonated poly (arylene ether), a metal salt of the sulfonated poly (arylene ether), or a combination thereof are present as a polymer component; and a second layer disposed on a surface of the first layer, wherein the second layer includes a polyetherimide.

[0006] Another aspect is a separation system for separating a fluid component from a fluid mixture including the fluid component, the separation system comprising the selectively permeable separation membrane as described herein.

[0007] Another aspect is a method for separating a fluid component from a first fluid mixture including the fluid component, the method including contacting a first side of the selectively permeable separation membrane with the first fluid mixture; and applying a pressure effective to cause the fluid component to selectively permeate to a second side of the selectively permeable separation membrane, to provide a product stream enriched in the fluid component.

[0008] The above described and other features are exemplified by the following figures and detailed description.BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The following figures are exemplary embodiments wherein the like elements are numbered alike.

[0010] FIG. 1 is a schematic diagram of a selectively permeable hollow fiber membrane comprising a blend composition according to an aspect, and having an integral skin.

[0011] FIG. 2 is a schematic illustration of a hollow fiber membrane having an integral skin comprising a blend composition according to an aspect, and further including an additional coating on a surface thereof.

[0012] FIG. 3 is a schematic illustration of a hollow fiber membrane including a first polymer layer having an integral skin wherein the first polymer layer is 100 weight percent of a24SHPP0045-WO-PCT (SS290020PCT)sulfonated poly( arylene ether), a metal salt of a sulfonated poly(arylene ether), or a combination thereof, and a second polymer layer comprising a polyimide, preferably a polyetherimide, or the blend composition according to an aspect.

[0013] FIG. 4 is a schematic illustration of a separation process using a hollow fiber membrane having an integral skin comprising a blend composition according to an aspect.

[0014] FIG. 5 is a schematic illustration of a separation system including a selectively permeable membrane according to an aspect.

[0015] FIG. 6 A is a photograph of the results of an SEM with energy dispersive X-Ray analysis of a film including the blend composition according to an aspect.

[0016] FIG. 6B is a trace showing a particle distribution analysis of a particulate including the blend composition of an aspect.DETAILED DESCRIPTION

[0017] Poly(arylene ether)s, including polyphenylene ethers, have high hydrolytic stability and relatively good acid and alkali resistance, due to the phenylene ether backbone, but unfunctionalized poly(arylene ether)s cannot be used to separate ions, being non-ionic in nature. Poly(arylene ether)s can be functionalized with polar groups such as sulfonic acid groups and carboxylic acid groups to enable cation exchange. The hydrogen bonding in these functionalized poly(arylene ether)s reduces the fractional free volumes and porosity. Thus, compared to unfunctionalized poly(arylene ether)s, sulfonated poly(arylene ether)s offer better balance between permeability and selectivity. Sulfonated poly(arylene ether)s can further be soluble in polar aprotic solvents and can be manipulated to form separation membranes both in dense and porous forms. However, in certain fluid separation applications, particularly in gas separation applications, selectivity of sulfonated poly(arylene ether)s is still less than desired. In other ion separation applications, it is desirable to improve water uptake, swelling, and selectivity of sulfonated poly( arylene ether)s. Development of new stable, high-permeability and high-selectivity membranes is therefore still desired, for certain gas separations.

[0018] The present inventors have discovered that acidic polymers such as sulfonated poly(arylene ether)s can be useful in the formation of polymer blends with basic polymers such as poly etherimides. Blends including the sulfonated poly(arylene ether), a metal salt of the sulfonated poly( arylene ether), or a combination thereof are particularly well suited for formation of robust membranes. The blends can have an improved balance of selectivity and permeability. The blends can further be processed in the same solvents as the fully protonated sulfonated poly( arylene ether)s. The membranes can be used in gas separations, and in particular24SHPP0045-WO-PCT (SS290020PCT)separation of hydrogen sulfide or water vapor from methane in general, and biogas mixtures in particular. A significant improvement is therefore provided by the present disclosure.

[0019] A desired permeability-selectivity balance can be achieved by careful selection of the characteristics of each of the polymers. Without being bound by theory, it is believed that selection of the appropriate type and amount of sulfonated poly(arylene ether) (having, for example, the desired physical properties and degree of sulfonation) provides permeability, while selection of the appropriate polyetherimide provides selectivity, enabling tuning of the properties to achieve the desired balance for a particular application.

[0020] For example, for gas separation applications, selection of the appropriate blend components and their relative amounts provides a combination of the high gas permeability offered by sulfonated poly(arylene ether)s together with the high selectivity offered by polyetherimide (PEI) in the resultant blend compositions, which can be obtained based on the co-solubility of these polymers in common solvents as disclosed herein. The blends can exhibit intermediate fractional free volumes, including intermediate or a distribution of average free volume elements (holes) compared to the parent polymers, thus providing uncompromised gas permeability and higher selectivity.

[0021] In another aspect, in ion separation applications, the extent of sulfonation in the sulfonated poly( arylene ether) blend component can be selected for enhanced ion conductivity, optimum water sorption, and minimum undesired crossovers. For example, the blends are used to manufacture as membrane separators in electrochemical devices. Additionally, blending a sulfonated poly( arylene ether) with a polyetherimide can maintain high membrane conductivity at higher ion exchange capacities, while managing excessive water uptake and swelling, improving chemical inertness, and mechanical properties. These blends allow the design of efficient membrane separator materials. Again, without being bound by theory, it is believed that such ionic acid-based interaction between the sulfonate groups with the imide groups in polyetherimide resins result in compatible acid-base interactions. By adjusting the degree of sulfonation, the extent of such interactions can be manipulated. Acid-base interactions can act as carriers in ion transfer, when used, for example, as membrane separators in applications such as a proton exchange membrane fuel cell (PEMFC), wherein the basic imide groups in the polyetherimide component of the blend acts as proton donor and acceptor in the process of proton conduction. This reduces the dependence of the sulfonated poly( arylene ether) component of the blend on humidity for ion (e.g., proton) conduction.

[0022] Accordingly, in an aspect, the polymer blend compositions described herein include a sulfonated poly(arylene ether), a metal salt of the sulfonated poly(arylene ether), or a24SHPP0045-WO-PCT (SS290020PCT)combination thereof, and a polyetherimide. A metal salt of a sulfonated poly(arylene ether) is especially useful.

[0023] The sulfonated poly(arylene ether) comprises repeating units of formula (I)wherein in the formula (I), Z1is independently at each occurrence a sulfonic acid group, a sulfonyl chloride group, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2is independently at each occurrence a sulfonic acid group, a sulfonyl chloride group, hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and x is 1 or 2. As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it can optionally contain one or more heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. As an example, Z1can be adi-n-butylaminomethyl group formed by reaction of a terminal 3, 5 -dimethyl- 1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0024] In an aspect, x in formula (I) can be 1 , and the sulfonated poly(arylene ether) comprises repeating units of formula (la)24SHPP0045-WO-PCT (SS290020PCT)wherein Z1and Z2are as defined in formula (I).

[0025] In an aspect, x in formula (I) can be 2, and the sulfonated poly(arylene ether) can comprise repeating units of formula (lb)wherein Z1and Z2are as defined in formula 1.

[0026] The sulfonated poly(arylene ether) of the present disclosure is sulfonated and as such, it will be understood that at least a portion of Z1or Z2is replaced with a sulfo group (e.g., a sulfonic acid group, a sulfonic acid metal salt group, or a sulfonyl chloride group).

[0027] In an aspect in formula (1), Z1is independently at each occurrence a sulfonic acid group, a sulfonic acid metal salt group, halogen, unsubstituted or substituted Ci-6 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, Ci-6 hydrocarbylthio, Ci-6 hydrocarbyloxy, or C2-6 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2is independently at each occurrence a sulfonic acid group, hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and x is 1.

[0028] In an aspect, the poly(arylene ether) of formula (I) can comprise2,6-dimethyl-l,4-arylene ether repeating units, 2,3,6-trimethyl-l,4-phenylene ether units, 2,5-dimethyl-l,4-phenylene ether repeating units, 2,2’,5,5’-tetramethyl-4,4’-dihydroxybiphenyl ether repeating units, 2-methyl-6-phenyl-l,4-phenylene ether repeating units, 2,2’-dimethyl-6,6’-diphenyl-4, 4’ -dihydroxybiphenyl ether repeating units, 2,6-diphenyl-l,4-phenylene ether repeating units, 2,2’,6,6’-tetraphenyl-4,4’-dihydroxybiphenyl ether repeating units, 2,6-dimethoxy-l,4-phenylene ether repeating units, 2,2’-6,6’-tetramethoxy-4,4’-dihydroxybiphenyl ether, 3,3’,5,5’-tetramethyl-4,4’-dihydroxybiphenyl ether units, a sulfonated derivative thereof, or a combination thereof. The term “a sulfonated derivative thereof’ or “a sulfonated24SHPP0045-WO-PCT (SS290020PCT)poly(arylene ether)” as used herein refers to the foregoing repeating units having at least one substituent replaced by a sulfo group, e.g., a fully protonated sulfonic acid group, a metal salt thereof, or the corresponding sulfonyl halide. For example, the sulfonated poly(arylene ether) can comprise 2,6-dimethyl-3-sulfo-l,4-phenylene ether repeating units, 2,5-dimethyl-3-sulfo-1 ,4-phenylene ether repeating units, 2,2’,5,5’-tetramethyl-3-sulfo-4,4’-dihydroxybiphenyl ether repeating units, 2-methyl-6-phenyl-3-sulfo-l,4-phenylene ether repeating units, 2,2’-dimethyl-6,6’-3-sulfo-diphenyl-4,4’-dihydroxybiphenyl ether repeating units, 2,6-diphenyl-3-sulfo-l,4-phenylene ether repeating units, 2,2’,6,6’-tetraphenyl-3-sulfo-4,4’-dihydroxybiphenyl ether repeating units, 2,6-dimethoxy-3-sulfo-l,4-phenylene ether repeating units, 2,2’-6,6’-tetramethoxy-3-sulfo-4, 4’ -dihydroxybiphenyl ether, and the like, or a combination thereof.

[0029] In an aspect, the sulfonated poly(arylene ether) can comprise 2,6-dimethyl-l,4-phenylene ether units and 2,6-dimethyl-3-sulfo-l,4-phenylene ether repeating units. Stated another way, the sulfonated poly(arylene ether) can be a sulfonated poly(2,6-dimethyl-l,4-phenylene ether).

[0030] In an aspect, the sulfonated poly(arylene ether) can be a copolymer comprising a first unsulfonated repeating unit of formula (I), or of formula (la) as described above, but including no sulfo groups, for example a first repeating unsulfonated unit of formula (I) or formula (la) wherein each occurrence of Z1is a methyl group, and each occurrence of Z2is hydrogen. The copolymer further includes a second sulfonated repeating unit of formula (I), wherein at least one of Z1, Z2, or a combination thereof is a sulfo group, for example a sulfonic acid or a sulfonic acid metal salt. For example, the second sulfonated repeating unit can be of formula (Ic)wherein Z1and Z2are as defined in formula (I) and formula (la), and X is hydrogen, potassium, sodium, ammonium, or a transition metal such as silver, copper, gold, or a combination thereof. In an aspect, each occurrence of Z1in the copolymer is a methyl group. In an aspect, each occurrence of Z2in the copolymer is hydrogen. In an aspect, the X is sodium or potassium. The unsulfonated first and sulfonated second repeating units of the copolymer can be present in a mole ratio of first:second units of 10:90 to 90:10, or 15:50 to 85:15, each based on the total moles of repeating units in the polymer.

[0031] The sulfonated poly(arylene ether) has a degree of sulfonation of 20 to 50%. Degree of sulfonation can be determined, for example, using proton nuclear magnetic resonance24SHPP0045-WO-PCT (SS290020PCT)(^H NMR) spectroscopy. Accordingly, at least one occurrence of Z1or Z2in the foregoing formulas is a sulfo group, preferably a sulfonate group in at least 20% of the repeating units of the sulfonated poly(arylene ether). Within this range, the sulfonated poly( arylene ether) can have a degree of sulfonation of 20 to 50%, or 20 to 45%, or 20 to 40%, or 20 to 35%.

[0032] The sulfonated poly(arylene ether) can optionally comprise molecules having aminoalkyl-containing end group(s), typically located in a position ortho to the hydroxy group. Also frequently present are tetramethyldiphenoquinone (TMDQ) end groups, typically obtained from 2,6-dimethylphenol-containing reaction mixtures in which tetramethyldiphenoquinone by-product is present.

[0033] The poly (arylene ether) from which the sulfonated poly (arylene ether) can be prepared can be in the form of a homopolymer, a copolymer, a graft copolymer, an ionomer, a block copolymer, or an oligomer as well as combinations thereof. In an aspect, the poly (arylene ether) from which the sulfonated poly(arylene ether) can be a poly(2,6-dimethyl-l,4-arylene ether) having an intrinsic viscosity of 0.03 to 2 deciliter per gram (dl / g). For example, the poly(arylene ether) can have an intrinsic viscosity of 0.25 to 1.7 dl / g, specifically 0.25 to 0.7 dl / g, more specifically 0.35 to 0.55 dl / g, even more specifically 0.35 to 0.50 dl / g, measured at 25°C in chloroform using an Ubbelohde viscometer.

[0034] In an aspect, the sulfonated poly(arylene ether) advantageously has a low sulfonyl chloride content. Specifically, the sulfonated poly(arylene ether) has a sulfonyl chloride (-SO2CI): sulfonic acid (-SO3H) molar ratio of less than or equal to 0.06. For example, the sulfonyl chloride (-SC>2Cl):sulfonic acid (-SO3H) molar ratio can be less than or equal to 0.05, or less than 0.05, or less than or equal to 0.04, or greater than 0 to 0.04, or 0.001 to 0.04, or 0.01 to 0.04, or 0.02 to 0.04, or 0.03 to 0.04.

[0035] In an aspect, the sulfonated poly(arylene ether) can have a degree of sulfonation as it pertains to sulfonyl chloride groups of less than 1.25%. Stated another way, the sulfonated poly(arylene ether) comprises less than 1.25 sulfonyl chloride groups per 100 repeating units. Within this range, the sulfonated poly(arylene ether) can have a degree of sulfonation as it pertains to sulfonyl chloride groups of less than or equal to 1.2%, for example 0.1 to 1.2%.

[0036] The sulfonated poly(arylene ether) can have a number average molecular weight (Mn) of 60,000 to 100,000 grams per mole, a weight average molecular weight (Mw) of 130,000 to 200,000 grams per mole, and a dispersity of 1.8 to 2.5. Number average molecular weight, weight average molecular weight, and dispersity are determined using gel permeation chromatography in dimethyl formamide relative to polystyrene standards.

[0037] The sulfonated poly(arylene ether) can comprise reduced levels of oligomers. As used herein, the term “oligomer” refers to arylene ether molecules having a molecular weight of24SHPP0045-WO-PCT (SS290020PCT)less than 1000 atomic mass units (amu; used interchangeably with Daltons (Da) or grams per mole (g / mol)). For example, the sulfonated poly(arylene ether) can comprise less than 1 weight percent, or less than 0.75 weight percent, or less than 0.5 weight percent of an oligomer having a molecular weight of less than 1 ,000 grams per mole, wherein weight percent is based on the total weight of the sulfonated poly(arylene ether). In an aspect, the sulfonated poly(arylene ether) can comprise less than 0.7 weight percent, or less than 0.5 weight percent, or less than 0.4 weight percent of an oligomer having a molecular weight of less than 500 grams per mole, wherein weight percent is based on the total weight of the sulfonated poly( arylene ether).

[0038] As used herein, the term “sulfonated poly(arylene ether)” or “sulfonated repeating unit” refers to any poly(arylene ether) or repeating units thereof having a -SO3X group bound thereto, and includes the sulfonic acid (protonated) form and sulfonate metal salt form. Other sulfonate derivatives (e.g., precursors to the sulfonate metal salt, or sulfonyl halides) can also be present. In an aspect, the polymer or copolymer can have a high degree of monosulfonated repeating units. Stated another way, a majority of sulfonated repeating units of the sulfonated poly(arylene ether) can have a single sulfonate / sulfonic acid group (i.e., a monosubstituted repeating unit). For example, at least 90% of the sulfonated poly(arylene ether) repeating units are monosubstituted. It is noted that the term “monosubstituted” as used herein is not equivalent to “uniformly substituted”. The term “uniform substitution” refers to a sulfonated poly(arylene ether) product having a certain degree of sulfonation that is uniform throughout the mass of the product. In contrast, “monosubstituted” as used herein means that a sulfonated poly(arylene ether) product has a certain (uniform) degree of sulfonation across the mass of the product, and further that at least 90% of the repeat units bearing a sulfonate group have only one sulfonate group. For example, a sulfonated poly(arylene ether) product having a uniform degree of substitution of 20% means that the degree of substitution is 20% across the entire mass of the product. In the present application, a monosulfonated poly(arylene ether) product having a degree of substitution of 20% means that, for example, out of the 20 repeat units which are sulfonated (assuming 100 repeat units total in the polymer for each of calculation), at least 90% of those 20 repeat units have only one sulfonate group (i.e., at least 18 of the 20 repeat units have one sulfonate group). A degree of sulfonation can be determined, for example, by nuclear magnetic resonance spectroscopy as is known in the art.

[0039] The sulfonated poly(arylene ether) can further have a total residual solvent content of less than 1.0 weight percent, or less than 0.5 weight percent, or less than 0.2 weight percent, or less than 0.1 weight percent, each based on the total weight of the polymer. Residual solvent content can be determined using gas chromatography. In an aspect, the sulfonated poly(arylene ether) can have a total residual dimethyl formamide or N-methyl pyrrolidine24SHPP0045-WO-PCT (SS290020PCT)content of less than 1 weight percent, or less than 0.05 weight percent, based on the total weight of the polymer, as determined using gas chromatography.

[0040] In an aspect, the sulfonated poly(arylene ether) can be made by a method known to those of ordinary skill in the art. For example, the sulfonated poly(arylene ether) can be made by a method comprising contacting the poly( arylene ether), e.g., a polyphenylene ether with a sulfonating agent in the presence of a solvent and a cosolvent. In an aspect, the method comprises dissolving the poly(arylene ether), e.g., a polyphenylene ether, in the solvent and the cosolvent to form a poly(arylene ether), e.g., a polyphenylene ether, mixture. Mixing of the components of the mixture can be performed at temperatures of 10 to 60°C, for example 25 to 40°C. The solvent comprises 1 ,2-dichloroethane and is present in a sufficient quantity to dissolve the poly(arylene ether), e.g., a polyphenylene ether. The amount of cosolvent is sufficient to prevent precipitation of the sulfonated poly(arylene ether), e.g., a sulfonated polyarylene ether before the desired degree of sulfonation has been attained.

[0041] The solvent mixture can comprise greater than or equal to 8 weight percent of the poly(arylene ether), e.g., a polyphenylene ether, or greater than 10 weight percent of poly(arylene ether), e.g., a polyphenylene ether, or greater than 12 weight percent of the poly(arylene ether), e.g., a polyphenylene ether. Within this range, the solvent mixture can comprise 8 to 25 weight percent, preferably 8 to 20 weight percent, or 10 to 25 weight percent, or greater than 10 to 25 weight percent, or 10 to 20 weight percent, or 15 to 25 weight percent, or 15 to 20 weight percent of the poly(arylene ether), e.g., a polyphenylene ether, each based on the total weight of the poly(arylene ether), e.g., a polyphenylene ether, the sulfonating agent, the solvent, and the cosolvent.

[0042] The solvent (i.e., the 1 ,2-dichloroethane) can be present in the reaction in an amount of 60 to 99 weight percent, or 70 to 95 weight percent, or 70 to 85 weight percent, each based on the total weight of the poly(arylene ether), e.g., a polyarylene ether, the sulfonating agent, the solvent, and the cosolvent.

[0043] The cosolvent can be present in the reaction in an amount of 7 to 15 weight percent based on the total weight of the solvent and the cosolvent. For example, the cosolvent can be present in an amount of 8 to 12 weight percent. In an aspect, the cosolvent can be present in an amount of at least 10 weight percent, for example 10 to 15 weight percent, or greater than 10 to 15 weight percent, or 11 to 15 weight percent, or 12 to 15 weight percent, each based on the total weight of the solvent and the cosolvent. In an aspect, the sulfonated poly(arylene ether) can be obtained and used in fully protonated form, or converted to a metal salt after isolation or after blending as described below.24SHPP0045-WO-PCT (SS290020PCT)

[0044] Thus, in an aspect, the method further comprises contacting the mixture comprising the sulfonated poly(arylene ether), e.g., a sulfonated polyphenylene ether, with a metal ion precursor, for example a alkali metal or alkaline earth metal or transition metal ion precursor to provide the metal salt of a sulfonated poly(arylene ether). Contacting with the metal ion can be, for example, 5 to 25°C, or 5 to 15°C. The mixture can be stirred e.g., for a period of 60 to 210 minutes, prior to proceeding to isolation of the metal salt product. Suitable metal ion precursors can be selected by a person having skill in the art and guided by the present disclosure. For example, when a sodium salt of a sulfonated poly(arylene ether), is desired, NaCl can be used as the sodium precursor.

[0045] In an aspect, at least 50 mole percent of the sulfonic acid groups can be in the metal salt form. For example, 50 to 100 mole percent, or 50 to 99 mole percent, or 50 to 95 mole percent, or 50 to 90 mole percent, or 50 to 80 mole percent of the sulfonic acid groups are in the metal salt form.

[0046] The method can further comprise isolating the fully protonated sulfonated poly(arylene ether) from the mixture used to prepare it, or the metal salt of the sulfonated poly(arylene ether) from the mixture used to form the metal salt. For example, once the sulfonated poly( arylene ether), e.g., a sulfonated polyphenylene ether has been sulfonated and optionally metalated, the sulfonated poly(arylene ether), e.g., a sulfonated polyphenylene ether can be precipitated from the solvent mixture using an anti-solvent mixture, e.g., containing deionized (DI) water and an organic solvent. As the organic solvent, hexane, heptane, cyclopentane, or cycloheptane can be used (along with de-ionized water) to cause the sulfonated poly(arylene ether), e.g., a sulfonated polyarylene ether, to precipitate out of the reaction solvent mixture. In an aspect, the organic solvent is immiscible with water and does not form an azeotrope with 1 ,2-dichloroethane or ethyl acetate. Preferably, the organic solvent comprises cyclopentane or cycloheptane. In a specific aspect, the organic solvent is cyclopentane.

[0047] The reaction solvent or salt-forming mixture can be added (e.g., slowly) to the anti-solvent mixture, wherein the anti-solvent mixture can be used in an amount sufficient to induce precipitation. For example, 100 grams (g) reaction mixture can be added to 300 to 700 g, preferably 390 to 595 g, of the anti-solvent mixture. In an aspect, the antisolvent can have an organic solvent to water weight ratio of 1:1 to 1:1, or 1:2 to 1:5, or 1:3 to 1:4.5.

[0048] The precipitated, fully protonated or metal salt of the sulfonated poly(arylene ether), e.g., a polyarylene ether can be filtered, and optionally washed and dried. The filtrate can be diphasic with the 1 ,2-dichloroethane, cosolvent, and optionally organic(s) (e.g., cyclopentane, cyclohexane or cycloheptane) that were part of the anti-solvent mixture, as the organic phase and water as the aqueous phase. Hence, the filtrate can be further processed to recover at least24SHPP0045-WO-PCT (SS290020PCT)one of the 1 ,2-dichloroethane, the cosolvent, or water; preferably to recover 1,2-dichloroethane and the cosolvent, more preferably to recover 1,2-dichloroethane, the cosolvent, and the water. Recovering the materials can comprise decanting the diphasic filtrate to form an aqueous stream and an organic stream. The organic stream can be further processed, e.g., distilled, to recover the 1 ,2-dichloroethane or the cosolvent. The recovered materials can be recycled. Selection of the antisolvent so as not to form an azeotrope with 1 ,2-dichloroethane or ethyl acetate as described herein can advantageously result in increased recovery of solvent or cosolvent for recycling and reuse in subsequent processes.

[0049] In addition to the sulfonated poly(arylene ether) or metal salt thereof (e.g., a sulfonated polyphenylene ether or a metal salt thereof), the polymer blend includes a poly etherimide. Polyetherimides comprise more than 1, for example 2 to 1000, or 5 to 500, or 10 to 100 structural units of formula (1)wherein in formula (1) each R is independently the same or different, and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C6-20 aromatic hydrocarbon group, a substituted or unsubstituted straight or branched chain C4-20 alkylene group, a substituted or unsubstituted C3-8 cycloalkylene group, in particular a halogenated derivative of any of the foregoing. In some embodiments R is divalent group of one or more of the following formulas (2)wherein Q1is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Ra)(=O)- wherein Rais a C1-8 alkyl or C6-12 aryl, - CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups), or -(CeHio)z- wherein z is an integer from 1 to 4. In some24SHPP0045-WO-PCT (SS290020PCT)embodiments R is m-phenylene, p-phenylene, or a diarylene sulfone, in particular bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination comprising at least one of the foregoing. In some embodiments, at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in other embodiments no R groups contain sulfone groups.

[0050] Further in formula (1), T is -O- or a group of the formula -O-Z-O- wherein the divalent bonds of the -O- or the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and Z is an aromatic Ce-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 Ci-s alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula (3)wherein Raand Rbare each independently the same or different, and are a halogen atom or a monovalent Ci-6 alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and Xais a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group. The bridging group Xacan be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a Ci-is organic bridging group. The Ci-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The Ci-is organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-is organic bridging group. A specific example of a group Z is a divalent group of formula (3 a)wherein Q is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Ra)(=O)- wherein Rais a Ci-s alkyl or Ce-12 aryl, or -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group). In a specific embodiment Z is a derived from bisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.

[0051] In an embodiment in formula (1), R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is -O-Z-O- wherein Z is a divalent group of formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a combination24SHPP0045-WO-PCT (SS290020PCT)comprising at least one of the foregoing, and T is -0-Z-0 wherein Z is a divalent group of formula (3a) and Q is 2,2-isopropylidene. Such materials are available under the trade name ULTEM from SABIC. Alternatively, the polyetherimide can be a copolymer comprising additional structural poly etherimide units of formula (1) wherein at least 50 mole percent (mol%) of the R groups are bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination comprising at least one of the foregoing and the remaining R groups are p-phenylene, m-phenylene or a combination comprising at least one of the foregoing; and Z is 2,2-(4-phenylene)isopropylidene, i.e., a bisphenol A moiety, an example of which is commercially available under the trade name EXTEM from SABIC

[0052] In some embodiments, the polyetherimide is a copolymer that optionally comprises additional structural imide units that are not polyetherimide units, for example imide units of formula (4)O OY o Y oN-R(4)wherein R is as described in formula (1) and each V is the same or different, and is a substituted or unsubstituted Ce-20 aromatic hydrocarbon group, for example a tetravalent linker of the formulaswherein W is a single bond, -O-, -S-, -C(O)-, -SO2-, -SO-, a Ci-is hydrocarbylene group, -P(Ra)(=O)- wherein Rais a C1-8 alkyl or C6-12 aryl, or -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups). These additional structural imide units preferably comprise less than 20 mol% of the total number of units, and more preferably can be present in amounts of 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 to 2 mol% of the total number of units. In some embodiments, no additional imide units are present in the polyetherimide.

[0053] The polyetherimide can be prepared by any of the methods known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (5) or a chemical equivalent thereof, with an organic diamine of formula (6)H2N-R-NH2 (6)24SHPP0045-WO-PCT (SS290020PCT)wherein T and R are defined as described above. Copolymers of the polyetherimides can be manufactured using a combination of an aromatic bis(ether anhydride) of formula (5) and an additional bis(anhydride) that is not a bis(ether anhydride), for example pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone dianhydride.

[0054] Illustrative examples of aromatic bis(ether anhydride)s include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (also known as bisphenol A dianhydride or BPADA), 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4’-(hexafluoroisopropylidene)diphthalic anhydride; and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. A combination of different aromatic bis(ether anhydride)s can be used.

[0055] Examples of organic diamines include 1,4-butane diamine, 1 ,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1 ,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-l,3-phenylene-diamine, 5-methyl-4,6-diethyl-l,3-phenylene-diamine, benzidine, 3,3 ’-dimethylbenzidine, 3,3 ’-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl) propane, 2,4-bis(p-amino-t-butyl) toluene, bis(p-amino-t-butylphenyl) ether, bis(p-methyl-o-aminophenyl) benzene, bis(p-methyl-o-aminopentyl) benzene, 1, 3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide, bis-(4-aminophenyl)24SHPP0045-WO-PCT (SS290020PCT)sulfone (also known as 4,4'-diaminodiphenyl sulfone (DDS)), and bis(4-aminophenyl) ether. Any regioisomer of the foregoing compounds can be used. Ci-4 alkylated or poly(Ci-4)alkylated derivatives of any of the foregoing can be used, for example a polymethylated 1,6-hexanediamine. Combinations of these compounds can also be used. In some embodiments the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3, 3 '-diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.

[0056] In an aspect, the polyetherimide can be, or can be formed from an eco-friendly material, which as used herein includes, renewable, sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, post-consumer recycled, or post-industrial recycled materials. The polyetherimide made from any of the foregoing eco-friendly sources can include, for example, an eco-friendly content (e.g., a bio-content, upcycle content, or recycle content) of up to about 99.9%, about 1 to 99%, or 5 to 95%, or 55 to 99%, or 80 to 99%, or 1 to 50%, or 1 to %, or 1 to 15%, or 1 to 10%, or 1-5%, based on the monomer source or the polymer source. Polyetherimides made from eco-friendly sources may include material made by a mass balance approach and certified by regulatory bodies such as, for example, the ISCC Plus.

[0057] Any of the components used in the polymerization reaction or their synthetic precursors, or the solvents used in the process, can be eco-friendly, e.g., bio-sourced, biocircular, or renewable raw materials. Such components and precursors include monomers, reagents, solvents, gases (e.g., oxygen gas), or any combination thereof. In some aspects, reaction components used in the polymerization of poly(arylene ether)s may be from sources as listed in the EU Renewable Energy Directive Annex IX.

[0058] Eco-friendly materials can be derived from biomass, consumer, or industrial sources such as waste (e.g., municipal waste). Biomass is a renewable organic material that comes from organic matter. A recycled polyetherimide comprising an open- or closed-loop postconsumer recycled (“PCR”) polyetherimide, an open- or closed-loop post-industrial recycled (“PIR”) polyetherimide, or upcycled polyetherimide or a combination thereof can be used, provided that the desired property or combination of properties can be achieved. As used herein, the term “post-consumer recycle” (PCR) refers to a polyetherimide that has reached the intended user or consumer, and which has been collected or reclaimed after utilization by the end-user or consumer. Thus, for example, it is understood that that the term refers to a polyetherimide material that in whole or in part would have otherwise been disposed of as waste, but has instead been collected and recovered (reclaimed) as a material input, in lieu of a virgin material, for a recycling or manufacturing process. “Post-industrial recycle” (PIR) polyetherimide is inclusive of material that has been reprocessed from collected or reclaimed material by means of a24SHPP0045-WO-PCT (SS290020PCT)manufacturing process, (including e.g., purification, sorting, and pretreating) and made into a product or into a component for incorporation into a product. Such recycled polyetherimide can be further processed, for example, into the form of powders, ground materials, flakes, pellets or other forms. Thus, a PIR polyetherimide refers to a polyetherimide that has never reached the end user and that is production waste arising during polymerization reactions, during further processing, or during manufacturing the resin or an article and includes materials such as, but not limited to, sprues from injection molding, start-up material from injection molding or extrusion, extrusion scrap, molding scrap, edge trims from extruded sheets or films, and the like, including materials diverted from the waste stream during a manufacturing process for an article.

[0059] The polyetherimides can have a melt index of 0.1 to 10 grams per minute (g / min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370°C, using a 6.7 kilogram (kg) weight. In some aspects, the polyetherimide has a weight average molecular weight (Mw) of 1,000 to 150,000 grams / mole (g / mol), as measured by gel permeation chromatography, using polystyrene standards. In some aspects the polyetherimide has an Mwof 10,000 to 80,000 Daltons. Such polyetherimides typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl / g), or, more specifically, 0.35 to 0.7 dl / g as measured in m-cresol at 25 °C.

[0060] A blend of the sulfonated poly(arylene ether) and the polyetherimide can be readily formed by dissolving each separately in a suitable solvent, and combining the two solutions; or by dissolving one polymer to provide one solution, and then dissolving the other polymer in the same solution; or by simultaneously dissolving both polymers in the solvent. In an aspect, the solvent is an aprotic apolar solvent. Suitable solvents depend on the dissolution properties of each polymer, and can be readily selected using the guidance herein. If two different solvents are used for each polymer, the solvents are preferably miscible. Suitable solvents include, for example, dimethyl formamide (DMF), N-methyl pyrrolidone (NMP), or a combination thereof. A miscible cosolvent can optionally be present. In an aspect, the solvent is DMF or NMP.

[0061] The blend can then be isolated by removal of the solvent, co-precipitation (e.g., by addition of an anti-solvent) or like methods, as described above or in further detail below in connection with the formation of a selectively permeable separation membrane and the examples. In an aspect, the blend is isolated by co-precipitation with an anti-solvent, for example an aqueous antisolvent including a salt, for example an inorganic salt, such as sodium chloride, ammonium chloride, sodium nitrate, or ammonium nitrate.

[0062] The polymer blend composition can include 99.9 to 0.1 weight percent of the sulfonated poly( arylene ether), its metal salt, or combination thereof and 0.1 to 95 weight24SHPP0045-WO-PCT (SS290020PCT)percent of the polyetherimide, each based on the total weight of the sulfonated poly(arylene ether), its metal salt, or combination thereof, and the polyetherimide. In aspects, the polymer blend composition can include 99.9 to 10 weight percent, or 99.1 to 30 weight percent, or 99.5 to 30 weight percent, or 99 to 30 weight percent, or 95 to 30 weight percent, or 90 to 40 weight percent, or 85 to 45 weight percent, or 80 to 60 weight percent, or 75 to 50 weight percent of the sulfonated poly( arylene ether), its metal salt, or a combination thereof and correspondingly, 0.1 to 90 weight percent, or 0.1 to 70 weight percent, or 0.5 to 70 weight percent, or 1 to 70 weight percent, or 5 to 70 weight percent, or 10 to 60 weight percent, or 15 to 55 weight percent, or 20 to 40 weight percent, or 25 to 50 weight percent of the polyetherimide. The relative amount of each of the polymers can be selected to provide the desired properties to the polymer blend depending on its intended usage, for example, a desired degree of phase dispersion, porosity, selectivity, mechanical strength, cost, and like considerations. In an aspect, the relative amount of each of the polymers is selected to provide excellent phase dispersion of the polyetherimide in the sulfonated poly(arylene ether), its metal salt, or a combination thereof. Phase dispersion can be determined, for example, by scanning electron microscopy of a sample of the blend, or by Tg, wherein a single Tg indicates good phase dispersion.

[0063] It is to be understood that the “polymer blend composition” as referred to herein can include only the named polymers, or can optionally include a non-polymer component, e.g., residual solvent or additives (e.g., a processing aid, antioxidant, UV stabilizer, thermal stabilizer, colorant, compatibilizer, or the like) as is known in the art. In an aspect, when a non-polymer component is present, the polymer blend composition includes 0.05 to 10 weight percent, or 0.1 to 8 weight percent, or 0.3 to 5 weight percent, or 0.1 to 10 wt%, or to 0.1 to 5 weight percent of the non-polymer component(s), each based on the total weight of the polymers and any non-polymer component, and which totals 100 weight percent.

[0064] The blend comprising the sulfonated poly(arylene ether), its metal salt, or a combination thereof, e.g., the sulfonated polyphenylene ether, its metal salt, or a combination thereof, and the polyetherimide can be particularly well-suited for use as a membrane. A membrane can be formed, for example, by preparing a solution comprising the two polymers and forming a thin layer of the solution using any suitable layer-forming technique. The layer can be dried to provide a free-standing polymer membrane comprising the blend.

[0065] The blend comprising the sulfonated poly(arylene ether,) its metal salt, or a combination thereof, e.g., the sulfonated polyphenylene ether, its metal salt, or a combination thereof, and the polyetherimide can be particularly well-suited for use as a selectively permeable asymmetric separation. Such membranes can be formed from the blend by methods known in the art, for example coagulation using an antisolvent as described below. The selectively24SHPP0045-WO-PCT (SS290020PCT)permeable asymmetric membrane can be of any configuration, e.g., a flat film, a conformal film, a hollow fiber, or the like. The thickness of the selectively permeable asymmetric separation membrane can be adjusted to achieve the desired flow and separation, depending on the mixture being separated. For example, the selectively permeable asymmetric membrane can have a thickness of 100 nanometers to 100 micrometers, for example 200 nanometers to 50 micrometers.

[0066] In an aspect, the blend can be used to provide a selectively permeable separation membrane in the form of a hollow fiber having an integral skin, as shown, for example, in FIG.1. In FIG. 1, the selectively permeable hollow fiber separation membrane 100 includes the blend composition 102. The hollow fiber membrane has a first (inner) surface 104 that defines a lumen and a second outer surface 106. First inner surface 104 and second outer surface 106 have an integral skin that is not formed or deposited separately from the bulk of the hollow fiber membrane. Each further has substantially the same, or the same porosity as the bulk of hollow fiber 100, and substantially the same, or the same composition as the bulk of hollow fiber 100. Methods for forming selectively permeable hollow fiber membranes from polymer solutions include, for example, centrifugal spinning from a solution of the blend using an anti-solvent, and are well-known to those of ordinary skill in the art.

[0067] Optionally, a layer including the selectively permeable membrane including the blend composition and having an integral skin, e.g., a first layer, can be manufactured to further include an additional, e.g., second, non-integral polymer layer (e.g., a coating) disposed on a surface (or on all surfaces) of the selectively permeable membrane. The second layer can be conformal to the surface of the first selectively permeable membrane. In an aspect, the additional layer is also a selectively permeable membrane. More than one additional layer can be present. In an aspect, all of the layers are a selectively permeable membrane. As used herein, “nonintegral” means that the additional layer is formed from a composition separate from the blend composition. For example, a “non-integral” skinned membrane refers to a coating or selective separation layer (which is typically dense) layered on top of a support membrane (which is typically porous) where the materials for the selective separation layer and the support membrane are different. The first membrane layer and the second layer, e.g., a second selectively permeable membrane layer, can be tightly bound, for example by co-casting or sequentially casting, co-extrusion or sequential extrusion, or co-melt-spinning the two (or more) layers. Alternatively, a surface treatment, tie layer, or adhesion layer can be present. In an aspect, the first and additional layer(s) are of different compositions, e.g., two or more different polymer blend compositions, or a polymer blend composition and a polyetherimide composition, or a polymer blend composition and a composition wherein the polymer component includes24SHPP0045-WO-PCT (SS290020PCT)100 weight percent of the sulfonated poly(arylene ether), its metal salt, or a combination thereof, e.g., the sulfonated polyphenylene ether, its metal salt, or any combination thereof. A construction including a first layer including the polymer blend composition and two polyetherimide layers, each disposed, for example, on an opposite side of the first layer can be made. Each of the foregoing layers can be a selectively permeable layer.

[0068] An exemplary aspect of a two-layer construction is shown in FIG. 2. In FIG. 2, the selectively permeable hollow fiber membrane 200 includes a first layer in the form of a selectively permeable hollow fiber separation membrane that includes the polymer blend composition 202. Inner surface 204 forms the lumen of the fiber. A second polymer layer 208 in the form of a selectively permeable membrane is disposed on outer surface 206. Second polymer layer 208 is formed from a composition different than the polymer blend composition 202, for example a polyimide, preferably a polyetherimide; a second blend composition different from the blend composition 202; or a polymer composition wherein the polymer component includes 100 weight percent of the sulfonated poly(arylene ether), its metal salt, or a combination thereof, e.g., the sulfonated polyphenylene ether, its metal salt, or a combination thereof. In an aspect, the first layer is the polymer blend composition, and the second layer is a polyetherimide. It is to be understood that it is also possible for the hollow fiber separation membrane to include the polyetherimide as the first layer and the polymer blend composition to be the polymer blend layer.

[0069] Still another aspect of a multi-layer construction includes the selectively permeable membrane with an integral skin, e.g., a first polymer layer wherein the polymer component is 100 weight percent of the sulfonated poly(arylene ether), its metal salt, or a combination thereof, and a non-integral additional (e.g., second) layer being another polymer composition, e.g., a polyimide, preferably a polyetherimide, or the polymer blend composition described herein. In an aspect, the first layer polymer is 100 weight percent of the sulfonated poly(arylene ether) metal salt, its metal salt, or a combination thereof, e.g., a sulfonated polyphenylene ether, its metal salt, or a combination thereof, and the additional layer(s) is a polyetherimide. As in the polymer blends, optionally a non-polymer component, e.g., residual solvent or an additive (e.g., a processing aid, antioxidant, UV stabilizer, thermal stabilizer, colorant, compatibilizer, or the like) as is known in the art can be present. In an aspect, when a non-polymer component is present, the composition includes 0.05 to 10 weight percent, or 0.1 to 8 weight percent, or 0.3 to 5 weight percent, or 0.1 to 10 wt%, or to 0.1 to 5 weight percent of the non-polymer component(s), and the remainder of the composition (the polymer component) is the sulfonated poly(arylene ether), its metal salt, or a combination thereof, with no additional polymer.24SHPP0045-WO-PCT (SS290020PCT)

[0070] The additional (e.g., second) layer can be disposed on a surface (or on all surfaces) of the selectively permeable membrane of the first layer. The second layer can be conformal to the surface of the first selectively permeable membrane. In an aspect, the additional layer is also a selectively permeable membrane. More than one additional layer(s) can be present. In an aspect, all of the layers are a selectively permeable membrane. The first selectively permeable membrane layer and the second layer, e.g., a second selectively permeable membrane layer, can be tightly bound, for example by co-casting or sequentially casting the two layers. Alternatively, a surface treatment, tie layer, or adhesion layer can be present. An exemplary aspect of this embodiment is shown in FIG. 3. In FIG. 3, a selectively permeable hollow fiber 300 includes a polymer composition wherein the polymer includes 100 weight percent of the sulfonated poly(arylene ether), its metal salt, or a combination thereof, e.g., the sulfonated polyphenylene ether its metal salt, or a combination thereof 302. Inner surface 304 forms the lumen of the fiber. Outer surface 306 includes a non-integral selectively permeable polymer layer having a composition different from the 100 weight percent of the sulfonated poly(arylene ether), its metal salt, or a combination thereof, its metal salt, for example a polyimide, preferably a polyetherimide, or the blend composition described herein. It is to be understood that it is also possible for the hollow fiber separation membrane to include the polyetherimide as the first layer and the outer non-integral layer to include the polymer blend composition or the polymer composition including 100 weight percent of the sulfonated poly(arylene ether), its metal salt, or a combination thereof, e.g., the 100 weight percent of the sulfonated polyphenylene ether, its metal salt, or a combination thereof.

[0071] Methods for the manufacture of the selectively permeable membranes including at least one additional layer can be formed by methods known in the art, for example by first extruding the membrane-forming solution of first layer (e.g., the polymer blend composition or the 100 weight percent sulfonated poly(arylene ether), its metal salt, or a combination thereof composition) through the annulus of a tube-in-orifice spinneret to form a nascent hollow fiber the contacting with an external coagulant. The hollow fiber dipping can be subsequently used to form an additional layer, e.g. a polyetherimide shell can be assembled on the outer wall of the hollow fiber through a combination of spray and spin coating. This is achieved by taking the porous hollow fiber substrate through dipping into or coating with the second composition, e.g., the polyetherimide solution, followed by drying the coated outer surface of the assembled hollow fiber, now with the polyetherimide shell.

[0072] The selectively permeable membranes comprising the polymer blend composition and optional additional layer(s), or the 100 weight percent sulfonated poly(arylene ether), its metal salt, or a combination thereof composition and the additional layer(s) can have,24SHPP0045-WO-PCT (SS290020PCT)for example, a density of 1 to 1.5 grams per cubic centimeter (g / cc), for example 1.1 to 1.3 g / cc, or 1.15 to 1.25 g / cc, or 1.2 g / cc and a porosity of 0.25 to 1 cm3FhO / gm dry membrane, for example 0.35 to 0.65 cm3FhO / gm dry membrane, or 0.4 to 0.6 cm3FhO / gm dry membrane, or 0.45 to 0.55 cm3FhO / gm dry membrane, or 0.48 to 0.52 cm3FhO / gm dry membrane, or 0.5 cm3FFO / gm dry membrane.

[0073] A method of separating a fluid component from a fluid mixture (e.g., a first fluid mixture stream) including the fluid component with the above-described selectively permeable membranes is further disclosed. The method includes contacting a first side of the membrane with the fluid mixture (e.g., the first fluid stream), and applying a pressure to cause the fluid component to selectively permeate to the second, opposite side of the membrane. Thus, a second fluid (product) stream enriched in the fluid component is formed. It can be removed from the second side of the membrane. A third fluid (product) stream depleted in the fluid component is formed, and it can be removed from the first side of the membrane. The second fluid stream enriched in the fluid component has a concentration of the fluid component that is higher than the initial concentration of the fluid component in the mixture and in the third fluid stream.

[0074] An exemplary method for separating a fluid component from a fluid mixture (e.g., a first fluid mixture stream) including the fluid component is shown in FIG. 4. As shown in FIG. 4, the method includes use of selectively permeable hollow fiber membrane 100 formed from the polymer blend composition described herein. Further as shown, inner surface 1 -4 defines a lumen and outer surface 106 includes an integral skin. It is to be understood that a hollow fiber membrane 200 or 300 (including a non-integral skin as in FIG. 2 or FIG. 3) can be used in the method. Referring again to FIG. 4, a first fluid mixture stream 412 including the fluid component is introduced into a first end of the lumen of the hollow fiber 100, and contacts first inner surface 104 of the selectively permeable membrane. The fluid component is selectively filtered through the membrane to exit from second outer surface 106 as a second product stream 414 (a permeate) enriched in the fluid component. A third fluid product stream 416, depleted in the fluid component can exit an opposite end of the lumen of the hollow fiber.

[0075] Contacting the first side of the membrane with the fluid mixture can be, for example, at a temperature of less than 50°C, for example 10 to 40°C, or 20 to 30°C. A pressure differential is maintained between the first and second sides of the membrane. For example, the second side can be maintained at vacuum or at any pressure that is less than the pressure of the first side. In an aspect, the pressure differential can be 1 to 5 bar, for example 2 to 3 bar.

[0076] Advantageously, the second fluid component-enriched product stream resulting from the present method can have a high degree of purity, for example a purity of at least 80 volume percent, or at least 85 volume percent, at least 90 volume percent, or at least 95 volume24SHPP0045-WO-PCT (SS290020PCT)percent, based on the total volume of the second product stream. Stated another way, the second fluid component-enriched product stream can comprise at least 80 volume percent, at least 85 volume percent, at least 90 volume percent 95 volume percent of the fluid component, based on the total volume of the olefin-enriched product stream. Conversely, 20 volume percent, less than 15 volume percent, less than 10 volume percent, or less than 5 volume percent of the total volume of the third product stream can be the other components of the fluid mixture.

[0077] A separation system for separating a fluid component from a first fluid mixture stream is also disclosed, where the separation system includes the selectively permeable membrane including the polymer blend composition as described herein.

[0078] For example, referring to FIG. 5, a separation system 500 can comprise a first fluid chamber 520 adjacent to a first side 104 of the membrane including the polymer blend composition 102, and a second fluid chamber 522 adjacent to a second, opposite side 106 of the membrane. One or a plurality of the hollow fiber membranes can be used in the system. A first fluid port 524 is in fluid communication with the first fluid chamber 520 and is configured to provide the first mixture stream including the fluid component to first fluid chamber 520. A second fluid port 526 is in fluid communication with the second fluid chamber and configured to remove a fluid component-enriched product stream from the second chamber. A third fluid port 528 is in fluid communication with the first fluid chamber 520 and is configured to remove a component-depleted product stream from the first fluid chamber.

[0079] The selectively permeable separation membranes can be useful for the separation of components in a liquid-liquid mixture, the separation of a gas (which includes a vapor) from a liquid-gas mixture, or separation of a gas from a gas-gas mixture. In an aspect, the fluid stream is a fully gaseous fluid stream. In an aspect, the fluid component is water vapor or hydrogen sulfide. A particular application is removal of hydrogen sulfide gas from, for example, a biogas mixture. Other gaseous mixtures can be separated.

[0080] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0081] The following materials were used in the Examples.24SHPP0045-WO-PCT (SS290020PCT)Example 1.

[0082] Various polyetherimides and metal salts of sulfonated polyphenylene ethers were tested for solubility and co-solubility in dimethyl formamide (DMF), dimethyl acetamide (DMAc), N-methyl pyrrolidone (NMP), and 3:1 DMF:l,4-dioxane (1,4-D). Each polymer was first tested in each solvent individually (10 weight percent of polymer in 90 weight percent of solvent) under three conditions, at room temperature (23 °C), after heating at 23°C with sonication, and then upon cooling. Results are shown in Table 1.Table 1Yes - complete dissolution Near - almost complete dissolutionSwelling - significant swelling was observed No - no dissolution was observed

[0083] To test combinations of polymers, a solution including 6 wt% of the PEI and 14 wt% of the sPPE-Na were dissolved simultaneously at room temperature in 80 wt% of DMAc or NMP solvent until visually homogeneous. Results are shown in Table 2.Table 2

[0084] The blends can be precipitated from the solvents using an aqueous medium of high ionic strength. For example, use of a 2-10 wt% aqueous solution of sodium chloride, sodium nitrate, ammonium chloride, or ammonium nitrate resulted in well defined, non-swollen precipitates of the blend composition, using an agitation tip speed of 1.54 meters per second. In particular, for a blend of PEI and sPPE-Na (20%), a 2-5 wt % or 10 wt% of aqueous solution of sodium chloride can be used as the antisolvent for coagulation.24SHPP0045-WO-PCT (SS290020PCT)Example 2.

[0085] Cast films comprising the foregoing blends of polyetherimides and sulfonated polyphenylene ether sodium salts were prepared according to the following general procedure.

[0086] The blend compositions (A to P) in Table 3 were prepared by taking the respective proportions of the sulfonated polyphenylene ethers with polyetherimide in a round bottomed flask and then dissolving in the respective solvents (A to P) and stirring until a visibly homogenous solution was obtained (10 weight percent of solids). The solutions we allowed to stand for an additional hour. The bubble- free solutions were each slowly poured into a clean glass petri dish. The solvent in the cast solutions was allowed to evaporate overnight in nitrogen atmosphere in an oven at 40°C. The cast films were then further dried in nitrogen atmosphere for 5 hours at 60°C, followed by additional 3 days at 80°C in a vacuum oven. This resulted in clear, dense (nonporous) films.

[0087] The Tg of each of the films was measured and is shown in Table 3.Table 3

[0088] None of the cast films of the sPPE metal salts-PEI showed phase segregation. All the blends exhibited only one glass transition temperature (Tg-1), i.e., no second or other glass transition temperature was observed. All blends exhibited a glass transition temperature below24SHPP0045-WO-PCT (SS290020PCT)230 °C. This data reflects the miscibility of the polyetherimides and sulfonated polyphenylene ethers metal salts. Without being bound by theory, it is believed that the miscibility is facilitated by the acid-base ionic interactions between the imide links of the polyetherimides and the sulfonic acid groups of the polyphenylene ethers.Example 3.

[0089] Example O in Table 3 was selected for further analysis. As seen in FIG. 6A, scanning electron microscopy (SEM) with energy dispersive X-Ray analysis (EDX) of Example O from Example 2 showed uniform signals corresponding to sulfur and sodium atoms across the film cross-section as seen in the cross section of the cast film of the 70:30 sPPE-Na (28%):PEI-2. Single phase morphology with no dispersed phase was observed.

[0090] Particles of the composition of Example O in Table 3 were obtained by precipitation using a 10 weight percent NaCl solution in water, followed by filtration and drying at 80°C under 20-30 mm Hg vacuum for 12 hours. Particle size distribution of four samples of the precipitated 70:30 sPPE-Na (28%): high flow PEI composition was analyzed using a Horiba particle size distribution analyzer LA-950V2. Results are shown in FIG. 6B and in Table 4. Table 4Example 4.Asymmetric hollow porous fibers having an integral skin were formed from the blend compositions of Example O. First, a 25% solution of the blend was prepared in NMP solution.24SHPP0045-WO-PCT (SS290020PCT)The resulting solution for preparation of the fiber and a 15 wt % aqueous sodium chloride for the core liquid were extruded against an external counter flow of air through the air gap, respectively from the outer tube of a hollow fiber spinning nozzle with a circular cannula structure, the outer tube of which has an external diameter of 0.4 mm and an internal diameter of 0.26 mm, and from the inner tube of the same nozzle, together into a water coagulation bath, and the resulting solution was dried in air at room temperature, to provide a asymmetric hollow fiber as shown in FIG. 4.Example 5

[0091] Asymmetric hollow porous fibers having a non-integral skin can be formed by depositing a dense polyetherimide onto an sPPE-Na hollow fiber that was prepared from an PEI-sPPE-Na blend using the process described in Example 4.

[0092] This disclosure further encompasses the following aspects.

[0093] Aspect 1: A polymer blend composition comprising 99.9 to 0.1 weight percent, preferably 99.9 to 10 weight percent, more preferably 99.9 to 30 weight percent of a sulfonated poly(arylene ether), its metal salt, or a combination thereof, preferably the metal salt of the sulfonated poly( arylene ether), and 0.1 to 70 weight percent of a polyetherimide, each based on the total weight of the sulfonated poly(arylene ether), its metal salt, or a combination thereof and the poly etherimide; wherein the polymer blend composition has a single glass transition temperature as determined using differential scanning calorimetry. Optionally, the polymer blend composition can further comprise a non-polymer additive other than a solvent. Preferably, a metal salt of the sulfonated poly(arylene ether) is used, for example a sodium, lithium or potassium salt.

[0094] Aspect 2: The blend composition of aspect 1, wherein the of the sulfonated poly(arylene ether), its metal salt, or a combination thereof comprises repeat units of formula (I)wherein in formula (I), Z1is independently at each occurrence a sulfonic acid group, sulfonic acid metal salt group, a sulfonyl chloride group, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-1224SHPP0045-WO-PCT (SS290020PCT)hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2is independently at each occurrence a sulfonic acid group, a sulfonyl chloride group, hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x is 1 or 2; wherein the sulfonated poly (arylene ether), its metal salt, or a combination thereof has a degree of sulfonation of 20 to 50 mole percent wherein at least 50 mole percent of the sulfonic groups are metal salt groups; and the metal is a alkali metal or alkaline earth metal.

[0095] Aspect 3: The blend composition of aspect 2, wherein Z1is independently at each occurrence a sulfonic acid group, a sulfonic acid metal salt group, halogen, haloalkyl, quaternized, unsubstituted or substituted C1-6 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-6 hydrocarbylthio, C1-6 hydrocarbyloxy, or C2-6 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2is independently at each occurrence a sulfonic acid group, hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and x is 1.

[0096] Aspect 4: The polymer blend composition of any aspects 2 or 3, wherein in the sulfonated poly( arylene ether), its metal salt, or a combination thereof, each occurrence of Z2that is not a sulfonate group is hydrogen; and each occurrence of Z1that is not a sulfonate group is a methyl group; x is 1; and the metal is lithium, sodium, or potassium.

[0097] Aspect 5: The polymer blend composition of any of the preceding aspects, wherein the polyetherimide is an upcycled, recycled, or biosourced polyetherimide.

[0098] Aspect 6: The polymer blend composition of any of the preceding aspects, wherein the polyetherimide comprises repeating units derived from meta-phenylene diamine, para-phenylene diamine, 4,4’-(9H-fluoren-9-ylidene)bis-benzenamine, diaminodiphenylether, 4,4'-diaminodiphenyl sulfone, or a combination thereof; and 4,4’ -bisphenol A dianhydride, 4,4'-oxydiphthalic anhydride, or 3,3'-bisphenol A dianhydride, or a combination thereof.

[0099] Aspect 7: The polymer blend composition of any of the preceding aspects, wherein the polyetherimide is a poly(etherimide-siloxane) copolymer.

[0100] Aspect 8: A method of making a selectively permeable separation membrane from the polymer blend composition of any of the preceding aspects, the method comprising forming a solution comprising the sulfonated poly(arylene ether), its metal salt, or a combination24SHPP0045-WO-PCT (SS290020PCT)thereof and the poly ether imide; contacting the solution with an antisolvent in an amount effective to precipitate the blend composition from the solvent to provide the membrane.

[0101] Aspect 9: A selectively permeable separation membrane comprising the polymer blend composition of any one of aspects 1-8, having an integral skin on a surface of the membrane, and optionally further comprising a non-integral additional layer, preferably a polyetherimide layer, disposed on a surface of the membrane.

[0102] Aspect 10: A selectively permeable separation membrane comprising a first selectively permeable polymer layer having an integral skin, wherein the polymer is 100 weight percent of a sulfonated poly(arylene ether), its metal salt, or a combination thereof, preferably a sulfonated polyphenylene ether, its metal salt, or a combination thereof; and a second selectively permeable non-integral polymer layer disposed on a surface of the first layer, wherein the selectively permeable non-integral polymer layer comprises a polyimide, preferably a poly etherimide, or the polymer blend composition of any one of aspects 1 to 8. Optionally, the polymer layer can further comprise a non-polymer additive.

[0103] Aspect 11: The selectively permeable separation membrane of aspect 9 or aspect 10, having a porosity of 0.5 cm3H2O / gram of dry membrane or less, as determined by scanning electron microscopy; or an average pore diameter of 0.1 to 0.7 nanometers, as determined by scanning electron microscopy; or a thickness of 100 nanometers to 100 micrometers, as determined by scanning electron microscopy; less than 1 weight percent, or less than 0.5 weight percent, or less than 0.1 weight percent of a solvent based on the total weight of the polymer blend composition, as determined using gas chromatography or a combination thereof.

[0104] Aspect 12: A separation system for separating a fluid component from a first fluid stream including the fluid component, the separation system comprising the membrane of any one of aspects 9 to 11.

[0105] Aspect 13: A method for separating a fluid component from a first fluid stream including the fluid component, the method comprising: contacting a first side of the selectively permeable membrane of any one of aspects 9 to 11 with the first fluid stream; applying a pressure to cause the fluid component to selectively permeate to a second side of the any membrane to provide a second fluid stream depleted in the fluid component and a third fluid component enriched in the fluid component; and optionally, collecting the second fluid stream, the third fluid stream, or both.

[0106] Aspect 14: The method of aspect 13, wherein the first fluid stream comprises a gas, preferably wherein the first fluid component is hydrogen sulfide or water vapor.

[0107] Aspect 15: The method of aspect 13 or aspect 14, wherein the membrane is in the form of a hollow fiber.24SHPP0045-WO-PCT (SS290020PCT)

[0108] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0109] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “an aspect” means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. The term “combination thereof’ as used herein includes one or more of the listed elements, and is open, allowing the presence of one or more like elements not named. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects.

[0110] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0111] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0112] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dashthat is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0113] As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen.24SHPP0045-WO-PCT (SS290020PCT)The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo atoms (e.g., bromo and fluoro), or only chloro atoms can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.24SHPP0045-WO-PCT (SS290020PCT)

[0114] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

24SHPP0045-WO-PCT (SS290020PCT)CLAIMS1. A polymer blend composition comprising99.9 to 0.1 weight percent, preferably 99.9 to 10 weight percent, more preferably 99.9 to 30 weight percent of a sulfonated poly(arylene ether), its metal salt, or a combination thereof, preferably the metal salt of the sulfonated poly(arylene ether), and0.1 to 95 weight percent, preferably 0.1 to 90 weight percent, more preferably 0.1 to 70 weight percent of a polyetherimide, each based on the total weight of the sulfonated poly(arylene ether), its metal salt, or a combination thereof and the poly etherimide; wherein the polymer blend composition has a single glass transition temperature as determined using differential scanning calorimetry.

2. The blend composition of claim 1, wherein the sulfonated poly (arylene ether), its metal salt, or a combination thereof comprises repeat units of formula (I)wherein in formula (I),Z1is independently at each occurrence a sulfonic acid group, sulfonic acid metal salt group, a sulfonyl chloride group, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;Z2is independently at each occurrence a sulfonic acid group, a sulfonyl chloride group, hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;x is 1 or 2;whereinthe sulfonated poly(arylene ether), its metal salt, or a combination thereof has a degree of sulfonation of 20 to 50 mole percent wherein at least 50 mole percent of the sulfonic groups are sulfonic acid, sulfonic acid metal salts, or a combination thereof; and24SHPP0045-WO-PCT (SS290020PCT)the metal is an alkali metal or alkaline earth metal.

3. The blend composition of claim 2, whereinZ1is independently at each occurrence a sulfonic acid group, a sulfonic acid metal salt group, halogen, haloalkyl, quaternized, unsubstituted or substituted Ci-6 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, Ci-6 hydrocarbylthio, Ci-6 hydrocarbyloxy, or C2-6 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;Z2is independently at each occurrence a sulfonic acid group, hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; andx is 1.

4. The polymer blend composition of any claims 2 or 3, wherein in the sulfonated poly(arylene ether), its metal salt, or a combination thereof,each occurrence of Z2that is not a sulfonate group is hydrogen; and each occurrence of Z1that is not a sulfonate group is a methyl group;x is 1 ; andthe metal is lithium, sodium, or potassium.

5. The polymer blend composition of any of the preceding claims, wherein the polyetherimide is an upcycled, recycled, or biosourced polyetherimide.

6. The polymer blend composition of any of the preceding claims, wherein the polyetherimide comprises repeating units derived from meta-phenylene diamine, para-phenylene diamine, 4,4’-(9H-fluoren-9-ylidene)bis-benzenamine, diaminodiphenylether, 4,4'-diaminodiphenyl sulfone, or a combination thereof; and 4,4’ -bisphenol A dianhydride, 4,4'-oxydiphthalic anhydride, or 3,3'-bisphenol A dianhydride, or a combination thereof.

7. The polymer blend composition of any of the preceding claims, wherein the polyetherimide is a poly(etherimide-siloxane) copolymer.

8. A method of making a selectively permeable separation membrane from the polymer blend composition of any of the preceding claims, the method comprising24SHPP0045-WO-PCT (SS290020PCT)forming a solution comprising the sulfonated poly (arylene ether), its metal salt, or a combination thereof and the poly etherimide;contacting the solution with an antisolvent in an amount effective to precipitate the blend composition from the solvent to provide the membrane.

9. A selectively permeable separation membrane comprising the polymer blend composition of any one of claims 1-8, comprising an integral skin on a surface of the membrane, and optionally further comprising a non-integral additional layer, preferably a polyetherimide layer, disposed on a surface of the membrane.

10. A selectively permeable separation membrane comprisinga first selectively permeable polymer layer having an integral skin wherein the polymer is 100 weight percent of a sulfonated poly(arylene ether), its metal salt, or a combination thereof, preferably a sulfonated polyphenylene ether, its, or a combination thereof, its metal salt, or a combination thereof; anda non-integral second selectively permeable polymer layer disposed on a surface of the first polymer layer, wherein the non-integral selectively permeable polymer layer comprises a polyimide, preferably a polyetherimide, or the polymer blend composition of any one of claims 1 to 8.

11. The selectively permeable separation membrane of claim 9 or claim 10, havinga porosity of 0.5 cm3H2O / gram of dry membrane or less, as determined by scanning electron microscopy; oran average pore diameter of 0.1 to 0.7 nanometers, as determined by scanning electron microscopy; ora layer thickness of 100 nanometers to 100 micrometers, as determined by scanning electron microscopy;less than 1 weight percent, or less than 0.5 weight percent, or less than 0.1 weight percent of a solvent based on the total weight of the polymer blend composition, as determined using gas chromatography; ora combination thereof.

12. A separation system for separating a fluid component from a first fluid stream including the fluid component, the separation system comprising the selectively permeable membrane of any one of claims 9 to 11.24SHPP0045-WO-PCT (SS290020PCT)13. A method for separating a fluid component from a first fluid stream including the fluid component, the method comprising:contacting a first side of the selectively permeable membrane of any one of claims 9 to 11 with the first fluid stream;applying a pressure to cause the fluid component to selectively permeate to a second side of the membrane to provide a second fluid stream depleted in the fluid component and a third fluid component enriched in the fluid component; andoptionally, collecting the second fluid stream, the third fluid stream, or both.

14. The method of claim 13, wherein the first fluid stream comprises a gas, preferably wherein the first fluid component is hydrogen sulfide or water vapor.

15. The method of claim 13 or claim 14, wherein the membrane is in the form of a hollow fiber.

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