EP4638602A1 - Polymeric composition comprising a blend of poly(aryl ether sulfone) polymers suitable for manufacturing articles - Google Patents

Polymeric composition comprising a blend of poly(aryl ether sulfone) polymers suitable for manufacturing articles

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Publication number
EP4638602A1
EP4638602A1 EP23836508.4A EP23836508A EP4638602A1 EP 4638602 A1 EP4638602 A1 EP 4638602A1 EP 23836508 A EP23836508 A EP 23836508A EP 4638602 A1 EP4638602 A1 EP 4638602A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
recurring units
membrane
pes
membranes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23836508.4A
Other languages
German (de)
French (fr)
Inventor
Francesca Rita POMILLA
Emanuele DI NICOLO'
Kamlesh P. NAIR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syensqo Specialty Polymers USA LLC
Original Assignee
Syensqo Specialty Polymers USA LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syensqo Specialty Polymers USA LLC filed Critical Syensqo Specialty Polymers USA LLC
Publication of EP4638602A1 publication Critical patent/EP4638602A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to polymeric compositions suitable for manufacturing articles, particularly membranes, comprising a blend of a poly(aryl ether sulfone) polymer with a more hydrophilic poly(aryl ether sulfone) additive, to articles, particularly films, tubes, fibers or membranes, containing such compositions, and to use of such articles such as porous membranes for medical and/or water filtration applications.
  • PAES poly(aryl ether sulfone)
  • the PAES polymers are made by polycondensation reactions, typically using 4,4’-dichlorodiphenyl sulfone (DCDPS) along with at least one aromatic diol such as bisphenol A, 4,4’-biphenol or 4,4’- dihydroxydiphenylsulfone, also called bisphenol S.
  • DCDPS 4,4’-dichlorodiphenyl sulfone
  • aromatic diol such as bisphenol A, 4,4’-biphenol or 4,4’- dihydroxydiphenylsulfone
  • Their chemical, thermal, and mechanical resistance combined with its excellent hydrolytic stability and relatively inexpensive production costs, make it ideal for widespread use in fabrication of porous membranes, in particular porous hollow-fiber polymeric membranes.
  • Porous membrane is a thin object, the key property of which is its ability to control the permeation rate of chemical species through itself. This feature is exploited in applications like separation applications (water and gas).
  • Porous hollow-fiber polymeric membranes are employed in many applications such as hemodialysis, ultrafiltration, nanofiltration, reverse osmosis, gas separation, microfiltration, desalination via membrane distillation, and pervaporation. For many of these applications, membranes with optimal selectivity as well as chemical, thermal and mechanical stability are desirable.
  • Membranes made from PAES polymers are hydrophobic in nature and therefore endowed of water repellency, low water permeability. These membranes suffer - 2 - SSPU 2022/035 from poor hydrophilicity that affects water permeation performance. Hydrophobicity impedes water to penetrate into the polymeric membrane and therefore water permeability requires higher pressure and consumes more energy. Another relevant issue is the fouling phenomenon.
  • Fouling is frequently the bottleneck of membrane processes, resulting in a sharp decline in permeate flux and decrement in membrane lifetime. Fouling is caused by hydrophobic interactions and electrostatic forces between membrane materials and foulants (e.g., microorganisms, proteins, or organic matter) originating from a fluid to be treated though the membrane. In particular, fouling is initiated by the adsorption of foulants onto the membrane surface and the interior structure, resulting in pore blocking, cake layer formation, or biofilm formation. Fouling reduces temporarily or permanently the flux of permeation of water through the membrane, e.g. in ultrafiltration or microfiltration processes.
  • foulants e.g., microorganisms, proteins, or organic matter
  • Membrane fouling not only decreases membrane permeability and overall lifetime, but also increases maintenance costs due to extensive and frequent cleaning to remove foulants. [0006] For that reason, PAES-based membranes are frequently modified to increase its hydrophilicity and reduce its fouling propensity before its practical use. Enhancing surface hydrophilicity can be achieved by increasing the density of the hydrophilic groups at the membrane surface. By making inner surfaces of the inner pores hydrophilic, the capability of permeating water through porous PAES membrane is generally improved. Besides, it is generally accepted that an increase of the hydrophilicity of PAES membranes offers better fouling resistance because proteins and other foulants are hydrophobic in nature.
  • hydrophilic additives are not permanent and tend to get leached out during prolonged use of the membrane.
  • - 3 - SSPU 2022/035 Another approach is based on hydrophilic species on the surface of membranes, by way of incorporation of hydrophilic comonomers in main polymer chain of PAES polymer, and by way of surface chemical reaction of the polymer such as direct sulfonation by a sulfonation agent are reviewed e.g. in Rana et al (2010) “Surface Modifications for Antifouling Membranes”, Chemical Reviews, Vol.110, No.4, p.2448- 2471.
  • Sulfonated copolymers are described in US2012/083541A1 and US2004101730A1.
  • the preparation of sulfonated polymers can be carried out via direct sulfonation in the monomer or post sulfonation method of an unsulfonated polymer or copolymer as described.
  • US2012/083541A1 describes an aromatic polyether sulfone block copolymer comprising hydrophilic segments which have sulfonic acid groups and hydrophobic segments which have no sulfonic acid groups, wherein the proportion by weight of hydrophilic segments is from 0.02 to 0.35, based on the total block copolymer (corresponding to from 2 to 35% by weight), as well as a process for preparing such aromatic polyether sulfone block copolymers, wherein an aromatic polyether sulfone block copolymer is sulfonated by means of concentrated sulfuric acid at a temperature in the range from 20 to 70° C.
  • sPES sulfonated PES
  • a commercial sPES available in the market produced by Konishi is synthesized by using post-polymerisation sulfonation of PES with a sulfonation agent selected from chlorosulfonic acid, sulfuric anhydride, sulfuric acid, or fuming sulfuric acid - see for example US 2016/9228060.
  • a sulfonation agent selected from chlorosulfonic acid, sulfuric anhydride, sulfuric acid, or fuming sulfuric acid - see for example US 2016/9228060.
  • Hemodialysis is one of the important methods for blood purification. PES has been widely used for this application. However the adsorption of serum proteins onto PES hemodialysis membranes can cause serious or life-threatening complications due to activation of the complement alternative pathway. Anticoagulants are often injected during the process of dialysis to avoid clot formation. To resolve the problem, many studies have aimed to improve the blood compatibility of biomaterials by surface modification, in particular by sulfonation PES. Du et al.
  • sulfonated additives are produced by using harsh chemicals and the post-polymerisation sulfonation can often cause a reduction in molecular weight of the polymer after sulfonation.
  • sulfonated PAES made by sulfonation of the aromatic rings of the PAES polymer has a disadvantage of leaching, that is to say, suffers from weight loss when subjected to water within a given time frame. This effect ia demonstrated with Konishi sPES in the current application.
  • WO2020/187684A1 describes an alternate way to introduce sulfonates on a side- chain functionalized copolymer (P1).
  • the process for preparing such a copolymer comprises reacting a functionalized copolymer (P0) having side-chain allyl/unsaturated carbon-carbon double bonds functional groups which are reacted with a compound R2 - SH, wherein R2 may be - (CH 2 )q – SO 3 Na, with q being selected from 1 to 5.
  • P0 functionalized copolymer
  • R2 may be - (CH 2 )q – SO 3 Na, with q being selected from 1 to 5.
  • Such sulfonated copolymers described therein are taught as notably useful for the manufacture of membranes, although no specific example of the actual manufacture of membranes is provided. No information is provided concerning its hydrophilicity and water permeation.
  • One object of the present invention is to increase the hydrophilicity of aromatic sulfone polymers in order to make porous articles, particularly membranes less susceptible to fouling, with increased hydrophilicity and increased water permeability.
  • Another object is to further reduce the chemical degradation of the aromatic sulfone polymers when subjected to cleaning by an oxidizing agent.
  • a further object is to reduce the loss of membrane weight by leaching when using the sulfonated or carboxylated sulfone polymer additive in a bulk aromatic sulfone polymer.
  • a first aspect of the present invention is directed to a polymeric composition
  • a polymeric composition comprising: - from 1 to 50 parts by weight of a sulfonated and/or carboxylated aromatic sulfone copolymer (P1) and - from 50 to 99 parts by weight of a poly(aryl ether sulfone) (PAES) polymer (P2), said parts by weight being based on the entire weights of copolymer (P1) and polymer (P2).
  • P1 sulfonated and/or carboxylated aromatic sulfone copolymer
  • PAES poly(aryl ether sulfone)
  • the sulfonated and/or carboxylated sulfone copolymer (P1) in the polymeric composition according to the invention comprises collectively at least 80 mol.% of: - recurring units (R P1 ) and - functionalized recurring units (R* P1 ), comprising two carboxylated and/or sulfonated pendant groups which include – COO-M + and/or ⁇ SO 3 -M + , in which M + is a cation, preferably selected from H + , alkali metal cations, alkali earth metal cations, NH4 + or any combination thereof, more preferably selected from H + , K + , Li + , Na + and/or NH4 + , said carboxylated and/or sulfonated pendant groups being covalently attached via a linking group including – S – (CH 2 ) u – or – S – (CH 2 ) q – to different aromatic rings in the recurring units
  • the sulfone recurring units (R P1 ) in the copolymer (P1) are preferably not sulfonated and/or not carboxylated.
  • the PAES copolymer (P2) in the polymeric composition according to the invention - 6 - SSPU 2022/035 comprises at least 80 mol.% of units (R P2 ).
  • the recurring units (R P2 ) may be the same or different than the recurring units (R P1 ) of copolymer (P1).
  • the recurring units (R P2 ) are preferably not sulfonated and/or not carboxylated.
  • the PAES copolymer (P2) in the polymeric composition according to the invention is preferably not sulfonated and/or carboxylated.
  • the polymeric composition preferably comprises: from 1 to 50 parts by weight of a sulfonated and/or carboxylated sulfone copolymer (P1) (hereinafter “copolymer (P1)”) and from 50 to 99 parts by weight of a polyarylethersulfone polymer (P2) (hereinafter “PAES polymer (P2)”), said parts by weight being based on combined weights of the copolymer (P1) and the PAES polymer (P2), said copolymer (P1) comprising collectively at least 80 mol.% of: - sulfone recurring units (R P1 ) of formula (M1): , - , and said units (R P2 ) of formula (M2): , - each R 1 is independently selected from the group consisting of a halogen, al
  • a second aspect of the present invention is directed to a polymeric solution comprising the polymeric composition according to the first aspect of the present invention, which further comprises at least a solvent suitable to dissolve the copolymer (P1) and the PAES polymer (P2), wherein the combined weights of the copolymer (P1) and polymer (P2) is from 5 wt.% to 40 wt.%, preferably from 8 wt.% to 35 wt.%, more preferably from 10 wt.% to 25 wt.%, yet more preferably from 12 wt.% to 20 wt.%, based on the total weight of the polymeric solution.
  • the polymeric solution may further comprise at least one pore forming agent.
  • a third aspect of the present disclosure is directed to the use of the polymeric composition according to the first aspect of the present invention or the polymeric solution according to the second aspect of the present invention to make an article, preferably a film, tube, fiber or membrane, intended for medical applications and/or water filtration applications.
  • a fourth aspect of the present invention is directed to an article, preferably a film, tube, fiber or membrane, intended for medical applications and/or water filtration applications.
  • FIG.1 compares the membrane thickness, water flux and gravimetric porosity for membrane E36 according to the invention containing a blend of a sulfonated PES and PES and for a comparative PES membrane CE35 made without the sPES copolymer additive, wherein these membranes are made using VIPS/NIPS technique and coagulation in water.
  • FIG.2 compares the membrane thickness, water flux and gravimetric porosity for membrane E38 according to the invention containing a blend of a sulfonated PES and PES and for a comparative PES membrane CE37 made without the sPES copolymer additive, wherein these membranes are made using VIPS/NIPS technique and coagulation in a 30w/70w NMP:water bath.
  • FIG.3 compares the membrane thickness, water flux and gravimetric porosity for membrane E41 according to the invention containing a blend of a sulfonated PES and PES and for a comparative PES membrane CE40 made without the sPES - 9 - SSPU 2022/035 copolymer additive, wherein are made using NIPS technique and coagulation in a 30w/70w NMP:water bath.
  • Fig. 4 to 6 represent SEM pictures of membranes E24-E26 according to the invention, respectively.
  • Fig.7 and 8 represent SEM pictures of two comparative membranes CE23 & CE31 made from PES, respectively.
  • FIG.14 compares the membrane thickness, water flux and gravimetric porosity for membrane E46 according to the invention containing a blend of a sulfonated PES and PPSU and for a comparative PPSU membrane CE45 made without the sPES copolymer additive, wherein these membranes are made using NIPS technique and coagulation in a 50w/50w NMP:water bath.
  • the polymeric composition comprises: from 5 to 50 parts by weight of the copolymer (P1), and from 50 to 95 parts by weight of the PAES polymer (P2), said parts by weight (“pbw”) being based on the combined weights of the copolymer (P1) and the PAES polymer (P2).
  • the polymeric composition comprises: - at least 6 pbw, or at least 7 pbw, or at least 8 pbw, or at least 9 pbw, or at least 10 pbw, of the copolymer (P1), and/or - at most 40 pbw, or at most 38 pbw, or at most 35 pbw, or at most 33 pbw, or at most 30 pbw, or at most 28 pbw, or at most 25 pbw, or at most 23 pbw, or at most 20 pbw, of the copolymer (P1), and - at least 60 pbw, or at least 62 pbw, or at least 65 pbw, or at least 67 pbw, or at least 70 pbw, or at least 702 pbw, or at least 75 pbw, or at least 77 pbw, or at least
  • the polymeric composition more preferably comprises from 10 to 40 pbw or from 10 to 30 pbw or from 10 to 20 pbw, of the copolymer (P1), and from 60 to 90 pbw, or from 70 to 90 pbw or from 80 to 90 pbw, of the PAES polymer (P2), said pbw being based on the combined weights of the copolymer (P1) and the PAES polymer (P2).
  • the copolymer (P1) comprises collectively at least 80 mol.% of recurring units (R P1 ) and (R* P1 ), and the PAES polymer (P2) comprises at least 80 mol.% of recurring units (R P2 ).
  • the molar ratio of recurring units (R P1 )/recurring units (R* P1 ) in the copolymer (P1) varies between 100/1 and 1/1, preferably between 50/1 and 2/1, more preferably between 40/1 and 3/1.
  • the recurring units (R P2 ) may be the same or different than the recurring units (R P1 ) of copolymer (P1).
  • the recurring units (R P2 ) are preferably not sulfonated and/or not carboxylated. Additionally, the recurring units (R P1 ) in the copolymer (P1) are preferably not sulfonated and/or not carboxylated. [0029]
  • the PAES copolymer (P2) in the polymeric composition according to the invention is preferably not sulfonated and/or carboxylated.
  • the copolymer (P1) in the polymeric composition according to the invention is sulfonated and/or carboxylated and comprises collectively at least 80 mol.% of: - recurring units (R P1 ) and - sulfonated and/or carboxylated recurring units (R* P1 ), comprising two carboxylated and/or sulfonated pendant groups which include – COO-M + and/or ⁇ SO 3 -M + , in which M + is a cation, preferably selected from H + , alkali metal cations, - 11 - SSPU 2022/035 alkali earth metal cations, NH4 + or any combination thereof, more preferably selected from H + , K + , Li + , Na + and/or NH4 + , said carboxylated and/or sulfonated pendant groups being covalently attached
  • the sulfonated and/or carboxylated groups of copolymer (P1) are derived from internal functionalizations within the copolymer backbone.
  • the internal functionalizations result from a step-growth polymerization in the presence of an allyl-substituted monomer, which advantageously makes the system versatile as the content of functionality can be adjusted by varying the content of allyl- substituted monomer in the reaction mixture.
  • the allyl-substituted monomer comprises two pendant allyl group side chains, each preferably comprising from 3 to 7 carbon atoms.
  • the copolymer (P1) in the polymeric composition of the present invention is in the form of a racemate product.
  • the allyl-substituted monomer Due to the presence of the base and high temperature during polymerization of the copolymer precursor, the allyl-substituted monomer usually racemizes during polymerization in such a way that the position of the double bond may change along the side chains. This leads to the formation of molecules differing from each other by the fact that the double bond may be at the end of the side chain or one carbon before the end of the side chain. The amount of racemization depends on the reaction time and temperature.
  • Sulfonated and/or carboxylated recurring units (R* P1 ) of the copolymer (P1) comprises two sulfonated and/or carboxylated pendant groups in free acid form (— SO 3 H or —COOH) and/or in deprotonated form (— COOM and/or ⁇ SO 3 M, in which M is selected from alkali metals, alkali earth metals, ammonium or any combination thereof), on two side chains which are covalently attached via a linking group including – S – (CH 2 ) q – or – S – (CH 2 ) q – to different aromatic rings in the recurring units (R* P1 ), in which u is an integer selected from 1 to 5, preferably u being 1 or 2; and q is an integer selected from 1 to 5, preferably q being 1, 2 or 3.
  • the sulfonic acid groups may be in form of free acid form or in deprotonated form, depending on the conditions.
  • the sulfonated and/or carboxylated copolymer (P1) comprises two – SO 3 M pendant groups which are covalently attached via a linking group which includes – S – (CH 2 ) 3 – to two different aromatic rings in the recurring units (R* P1 ).
  • the copolymer (P1) of the present invention comprises collectively at least 80 mol.% of recurring units (R P1 ) and (R* P1 ), based on the total number of moles of - 12 - SSPU 2022/035 recurring units in the .
  • the copolymer (P1) may for example comprise collectively at least 85 mol.%, at least 90 mol.%, at least 95 mol.%, at least 98 mol.%, at least 99 mol.%, of recurring units (R P1 ) and (R* P1 ), based on the total number of moles of recurring units in the copolymer (P1). Substantially all of the recurring units in the copolymer (P1) are recurring units (R P1 ) and (R* P1 ). The expression total number of moles of recurring units in the copolymer (P1).
  • Substantin copolymer (P1) is hereby intended to mean that minor amounts, generally below 1 % moles, preferably below 0.5 % moles, of other recurring units may be tolerated, e.g. as a result of lower purity in monomers used.
  • the recurring units (R P1 ) of formula (M1) in the copolymer (P1) are preferably non-sulfonated, or non-carboxylated, or both non-sulfonated and non- carboxylated, meaning that none of the R 1 in formula (M1) comprises –SO3- and/or –COO- groups.
  • i is preferably 0.
  • T 1 is preferably selected from the group consisting of a bond, -SO 2 -, -C(CH 3 ) 2 - and a mixture therefrom.
  • the copolymer (P1) may, for example, comprise some recurring units (R P1 ) in which T 1 is -C(CH 3 ) 2 - and other recurring units (R P1 ) in which T 1 is -SO 2 -.
  • T 1 in recurring units (R P1 ) of formula (M1) is more preferably -C(CH 3 ) 2 - and/or -SO 2 -.
  • each R 4 may be independently selected from the group consisting of a C1-C12 moiety optionally comprising one or more than one heteroatoms; phosphonic acid and phosphonate groups; amine, amide and quaternary ammonium groups.
  • i is zero for each R 1 of recurring units (R P1 ) of formula (M1).
  • the recurring units (R P1 ) in the copolymer (P1) are more preferably according to any of the following formulae (M1a), (M1b) or (M1c): - 13 - SSPU 2022/035 (M1c). [0041] 50 mol.
  • the copolymer (P1) preferably comprises at most 98 mol. %, or at most 97 mol. %, or at most 96 mol. %, or at most 95 mol. %, or at most 94 mol.
  • the copolymer (P1) preferably comprises typically at least 2 mol.%, or at least 3 mol.%, or at least 4 mol.%, or at least 5 mol.%, or at least 6 mol.%, or at least 7 mol.%, of the recurring units (R* P1 ) of the formula (N), based on the total number of moles of recurring units in the copolymer (P1).
  • the copolymer (P1) preferably comprises at most 50 mol. %, or less than 50 mol.%, or at most 45 mol. %, or at most 40 mol. %, or at most 34 mol. %, or at most 30 mol. %, or at most 25 mol. %, or at most 20 mol. %, or at most 18 mol. %, of the recurring units (R P1 ) of the formula (N), based on the total number of moles of recurring units in the copolymer (P1).
  • Each R 2 in the G N groups is more preferably – (CH 2 ) 3 – SO 3 H, – (CH 2 ) 3 – SO 3 Li, – (CH 2 ) 3 – SO 3 K, or – (CH 2 ) 3 – SO 3 Na, and/or – (CH 2 ) 3 – SO 3 NH 4 .
  • W in G N represented by any of the formulae (G N1 ), (G N2 ), (G N3 ), (G N4 ), (G N5 ), (G N6 ) is preferably selected from the group consisting of a bond, -SO 2 -, -C(CH 3 ) 2 - and a mixture therefrom.
  • the copolymer (P1) may be such that W is - C(CH 3 ) 2 - in some recurring units (R* P1 ) and W is -SO 2 - in other recurring units (R*P1).
  • each R 1 is independently selected from the group consisting of a C1-C12 moiety optionally - 14 - SSPU 2022/035 comprising one or more than phosphonic acid and phosphonate groups; amine, amide and quaternary ammonium groups.
  • i is zero for each R 1 of the recurring units (R* P1 ).
  • G N is represented by any of the formulae (G N1 ), (G N2 ), (G N3 ), (G N4 ), (G N5 ), (G N6 ), k is preferably zero and j is preferably 3.
  • the copolymer (P1) may be such that - W is -C(CH 3 ) 2 - in recurring units (R* P1 ) and T 1 is -SO 2 - in recurring units (R P1 ); or - W is -C(CH 3 ) 2 - in recurring units (R* P1 ) and T 1 is -C(CH 3 ) 2 - in recurring units (R P1 ); or - W is -C(CH 3 ) 2 - in recurring units (R* P1 ) and T 1 is a bond in recurring units (R P1 ); or - W is -SO 2 - in recurring units (R* P1 ) and T 1 is -SO 2 - in recurring units (R P1 ); or - W is -SO 2 - in recurring units (R* P1 ) and T 1 is -C(CH 3 ) 2 -in recurring units (R P1 ).
  • the copolymer (P1) is preferably a sulfonated copolymer with a degree of sulfonation from 4 to 50 mol% or a carboxylated copolymer with a degree of carboxylation from 4 to 50 mol%.
  • the copolymer (P1) is more preferably a sulfonated copolymer with a degree of sulfonation from 4 to 30 mol%, or from 4 to 25 mol%, or from 4 to 20 mol%, or a carboxylated copolymer with a degree of carboxylation from 4 to 30 mol%, or from 4 to 25 mol%, or from 4 to 20 mol%.
  • the copolymer (P1) is even more preferably a sulfonated copolymer with a degree of sulfonation from 4 to 18 mol%.
  • the copolymer (P1) in the polymeric composition of the present invention has a Tg ranging from 120 and 250°C, preferably from 170 and 240°C, more preferably from 180 and 230°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.
  • PAES polymer (P2) in the polymeric composition of the present invention is preferably a polymer which does not comprise sulfonated groups in free acid form (—SO 3 H) and/or in deprotonated form, and also does not comprise carboxylated groups in free acid form (—COOH) and/or in deprotonated form, wherein the counterion (M + ) to —SO 3 - or —COO- in the deprotonated form (—SO 3 M or — COOM) may be an alkali metal or alkali earth metal cation or NH 4 + , such as NH 4 + , Na + Li + , and/or K + .
  • T 2 is preferably selected from the group consisting of a bond, -SO 2 - and -C(CH 3 ) 2 -.
  • each R 4 may be independently selected from the group consisting of a halogen, alkyl, alkenyl, - 15 - SSPU 2022/035 alkynyl, aryl, ether, thioether, amide, imide, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium.
  • each m is preferably 0.
  • the recurring units (R P2 ) of the PAES polymer (P2) are preferably represented by at least one of the following formulae (M1a), (M1b), or (M1c): , units (R P2 ) of formula selected from any of formulae (M2), (M1a), (M1b) or (M1c), based on the total number of moles of recurring units in the polymer (P2).
  • substantially all of the recurring units in the polymer (P2) are the recurring units (R P2 ) of formula selected from any of formulae: (M2), (M1a), (M1b) or (M1c).
  • the expression “substantially all” concerning the recurring units selected from any of formulae: (M2), (M1a), (M1b) or (M1c) in the polymer (P2) is hereby intended to mean that minor amounts, generally below 1 % moles, preferably below 0.5 % moles, of other recurring units may be tolerated, e.g. as a result of lower purity in monomers used.
  • the PAES polymer (P2) in the polymeric composition of the present invention is preferably a polysulfone (PSU), a polyethersulfone (PES), or a polyphenylsulfone (PPSU), more preferably a PES or PPSU.
  • a polyethersulfone (PES) denotes any polymer comprising at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 99 mol. % of recurring units (R PES ) of the formula (M1a), the mol. % being based on the total number of moles of recurring units in the PES polymer.
  • PES can be prepared by known methods and is notably available as VERADEL ® PES from Solvay Specialty Polymers USA, L.L.C. - 16 - SSPU 2022/035 [0062]
  • a polysulfone denotes any polymer comprising at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 99 mol. % of recurring units (R PSU ) of the formula (M1b), the mol. % being based on the total number of moles of recurring units in the PSU polymer.
  • PSU can be prepared by known methods and is notably available as Udel® PSU from Solvay Specialty Polymers USA, L.L.C.
  • a polyphenylsulfone denotes any polymer comprising at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 99 mol. % of recurring units (R PPSU ) of the formula (M1c), the mol. % being based on the total number of moles of recurring units in the PPSU polymer.
  • PPSU can be prepared by known methods and is notably available as RADEL ® PPSU from Solvay Specialty Polymers USA, L.L.C.
  • the recurring units (R P1a ) of the copolymer (P1) and the recurring units (R P2 ) of the PAES polymer (P2) preferably are represented by the same formula selected from (M1a), (M1b) or (M1c), more preferably represented by the same formula (M1a).
  • the recurring units (R P1a ) of the copolymer (P1) may be represented by the formula (M1a) and the recurring units (R P2 ) of the PAES polymer (P2) are represented by the formula (M1b) or (M1c).
  • the polymer (P2) in the polymeric composition of the present invention has a Tg ranging from 120 and 250°C, preferably from 170 and 240°C, more preferably from 180 and 230°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.
  • DSC differential scanning calorimetry
  • Process for preparing the copolymer (P1) [0068] The copolymer (P1) can be prepared by various chemical processes, notably by free radical-thermal reaction, by free radical-UV reaction, by base-catalyzed reaction or by nucleophilic-catalysed reaction.
  • the process for preparing copolymer (P1) comprises reacting an allyl/vinylene- functionalized copolymer precursor (P0) with a compound R 2 – SH, wherein R 2 is independently selected from the group consisting of: ⁇ (CH 2 ) u – COOM, ⁇ (CH 2 ) q – SO 3 M, and any combination thereof, with u being an integer selected from 1 to 5, preferably u being 1 or 2, with q being an integer selected from 1 to 5, preferably q being 1, 2 or 3, and with M being selected from H, alkali metals, alkali earth metals, ammonium or any combination thereof, more preferably selected from H, Li, Na and/or NH 4 .
  • the copolymer precursor (P0), used in the process notably comprises recurring units (R* P0 ) with 2 pendant allyl/vinylene side-chains, which are reactive with the compound R 2 – SH.
  • - W is selected from the group consisting of a bond, -SO 2 -, -C(CH 3 ) 2 - and any mixture therefrom, preferably selected from -C(CH 3 ) 2 - and/or –SO 2 -;
  • the copolymer precursor (P0) is such that k is zero in recurring units (R* P0 ).
  • the molar ratio of compound (R 2 –SH)/polymer precursor (P0) varies between varies between 0.01/100 and 100/0.01, preferably between 1/100 and 100/1, more preferably between 1/1 and 10/1.
  • the temperature of the reaction to prepare copolymer (P1) varies between 10°C and 300°C, preferably between room temperature and 200°C, or more preferably between 35°C and 100°C.
  • the process to prepare copolymer (P1) may be carried out by exposing the reaction mixture to UV light at a wavelength ranging from 300 nm to 600 nm, preferably from 350 nm to 450 nm., more preferably at 365 nm.
  • the copolymer precursor (P0) is such that T 1 in recurring units (R P0 ) is selected from the group consisting of a bond, -SO 2 -, -C(CH 3 ) 2 - and - 19 - SSPU 2022/035 any combination thereof.
  • the (P0) may, for example, comprise recurring units (R P0 ) in which T 1 is -C(CH 3 ) 2 - and recurring units (R P1 ) in which T 1 is -SO 2 -.
  • T 1 in recurring units (R P0 ) is preferably -SO 2 - or -C(CH 3 ) 2 -.
  • the copolymer precursor (P0) is such that each R 1 is independently selected from the group consisting of a C1-C12 moiety optionally comprising one or more than one heteroatoms; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.
  • the copolymer precursor (P0) is such that i is zero for each R 1 of recurring units (R P0 ) and recurring units (R* P0 ). [0079] In some embodiments, the copolymer precursor (P0) is such that j is 2 in recurring units (R P0 ).
  • the copolymer precursor (P0) is such that recurring units (R P0 ) are represented by at least one of the following formulae (M1a), (M1b), or (M1c): , at least 90 mol.%, at least 95 mol.%, at least 99 mol.% of recurring units (R P0 ) and (R* P0 ), based on the total number of moles of recurring units in the copolymer precursor (P0). Substantially all of the recurring units in the copolymer precursor (P0) may be recurring units (R P0 ) and (R* P0 ).
  • the copolymer precursor (P0) may have a Tg ranging from 120 and 250°C, preferably from 170 and 240°C, more preferably from 180 and 230°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.
  • DSC differential scanning calorimetry
  • the compound R 2 – SH used to react the copolymer precursor (P0) may be such that R 2 in recurring units (R* P1 ) is independently selected from the group consisting of: - 20 - SSPU 2022/035 – CH 2 – COOM, in which M is H, K or Na, more preferably H, and – (CH 2 ) 3 – SO 3 M , in which M is preferably H, K or Na, more preferably Na.
  • the compound R 2 – SH is preferably 3-mercapto-1-propanesulfonic acid sodium salt (“MPS thiol”) or thioglycolic acid (HS-CH 2 -COOH).
  • the reaction to prepare copolymer (P1) may be carried out in a solvent, sometimes referred to as “reaction solvent”.
  • the reaction solvent preferably comprises, or consists essentially of, for example a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2- pyrrolidone (NEP), N,N-dimethylformamide (DMF), N,N dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole and sulfolane.
  • NMP N-methylpyrrolidone
  • NBP N-butylpyrrolidone
  • NEP N-ethyl-2- pyrrolidone
  • DMF N,N-dimethylformamide
  • DMAc dimethylacet
  • the reaction solvent may also comprise, or consist essentially of, chloroform or dichloromethane (DCM).
  • the reaction solvent preferably comprises, or consists essentially of, DMSO, sulfolane or NMP.
  • the reaction solvent may further comprise up to 10 wt.% water, preferably up to 7.5 wt.% water, more preferably up to 5 wt.% water (based on total weight of reaction solvent).
  • the reaction to prepare copolymer (P1) may be carried out in the presence of a base, for example selected from the group consisting of potassium carbonate (K 2 CO 3 ), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ) and sodium tert- butoxide.
  • a base for example selected from the group consisting of potassium carbonate (K 2 CO 3 ), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ) and sodium tert- butoxide.
  • the base may also be selected from the group consisting of N-Ethyl-N- (propan-2-yl)propan-2-amine (Hunig base), triethylamine (TEA) and pyridine.
  • the reaction to prepare copolymer (P1) may be carried out in the presence of: - at least one free radical initiator, preferably 2,2'-Azobis(2-methylpropionitrile) (AIBN), and/or - at least one catalyst, preferably selected from peroxides.
  • the peroxide catalyst may include a hydroperoxide.
  • the reaction solvent comprises at least 50 wt.% and up to 100 wt.% DMSO.
  • the amount of copolymer (P1) at the end of the reaction is at least 10 wt.% based on the total weight of the copolymer precursor (P0) and the solvent, for example at least 15 wt.%, at least 20 wt.% or at least 30 wt.%.
  • (P1) is separated from the other components (salts, base, ...) to obtain a solution. Filtration can for example be used to separate the copolymer (P1) from the other components. The solution can then be used ’as is’ for reacting the copolymer (P1) with other compounds, or alternatively, the copolymer (P1) can be recovered from the solvent, for example by coagulation or devolatilization of the solvent.
  • the cations of the sulfonated and/or carboxylated groups may be exchanged by other cations.
  • the copolymer (P1) in which the sulfonated groups are in acid form (- SO 3 H) may be dissolved in a suitable solvent, and then the copolymer (P1) may be precipitated in a NH4OH methanol solution to deprotonate the sulfonate to form the - SO 3 NH 4 groups.
  • the copolymer (P1) in solid form may be washed in an aqueous solution containing an appropriate desired cation to be exchanged, such as the cation being in form of salt or acid.
  • the allyl/vinylene-functionalized copolymer (P0) used in the process to make copolymer (P1) has been prepared by condensation of at least one aromatic dihydroxy monomer (a1), with at least one aromatic sulfone monomer (a2) comprising at least two halogen substituents and at least one allyl-substituted aromatic dihydroxy monomer (a3), as well as an additional agent, for example an end-capping agent or a protonating agent.
  • the condensation to prepare copolymer precursor (P0) is preferably carried out in a solvent.
  • the solvent is for example a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N,Ndimethylformamide (DMF), N,N dimethylacetamide (DMAc), 1,3-dimethyl-2- imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene and sulfolane.
  • NMP N-methylpyrrolidone
  • NBP N-butylpyrrolidone
  • DMF N,Ndimethylformamide
  • DMAc N,N dimethylacetamide
  • 1,3-dimethyl-2- imidazolidinone 1,3-dimethyl-2- imidazolidinone
  • THF tetrahydrofuran
  • DMSO dimethyl sulfoxide
  • chlorobenzene and sulfolane is preferably carried out in sulfolane
  • the condensation to prepare the copolymer precursor (P0) may be carried out in the presence of a base, for example selected from the group consisting of potassium carbonate (K 2 CO 3 ), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ) and sodium tert-butoxide.
  • the base acts to deprotonate the components (a1) and (a3) during the condensation reaction.
  • the molar ratio (a1)+(a3)/(a2) may be from 0.9 to 1.1, for example from 0.92 to 1.08 or from 0.95 to 1.05.
  • the monomer (a2) is a 4,4- comprising at least one of a 4,4’- dichlorodiphenyl sulfone (DCDPS) or 4,4’ difluorodiphenyl sulfone (DFDPS), preferably DCDPS.
  • DCDPS dichlorodiphenyl sulfone
  • DDPS difluorodiphenyl sulfone
  • the monomer (a1) comprises, based on the total weight of the monomer (a1), at least 50 wt.% of 4,4’ dihydroxybiphenyl (biphenol), at least 50 wt.% of 2,2-bis(4- hydroxyphenyl)propane (bisphenol A) or at least 50 wt.% of 4, 4’ dihydroxydiphenyl sulfone (bisphenol S).
  • the monomer (a3) comprises, based on the total weight of the monomer (a1), at least 50 wt.% of 2,2’-diallylbisphenol A (DABA).
  • DABA 2,2’-diallylbisphenol A
  • the reaction is preferably conducted in one stage. This means that the deprotonation of monomers (a1) and (a3) and the condensation reaction between the monomers (a1)/(a3) and (a2) takes place in a single reaction stage without isolation of the intermediate products.
  • the condensation is carried out in a mixture of a polar aprotic solvent and a solvent which forms an azeotrope with water.
  • the solvent which forms an azeotrope with water includes aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like. It is preferably toluene or chlorobenzene.
  • the azeotrope-forming solvent and the polar aprotic solvent are used typically in a weight ratio of from about 1:20 to about 1:1, preferably from about 1:10 to about 1:1 or from about 1:5 to about 1:1.
  • Water is continuously removed from the reaction mass as an azeotrope with the azeotrope- forming solvent so that substantially anhydrous conditions are maintained during the polymerization.
  • the azeotrope-forming solvent for example, chlorobenzene, is removed from the reaction mixture, typically by distillation, after the water formed in the reaction is removed leaving the copolymer precursor (P0) dissolved in the polar aprotic solvent.
  • the temperature of the reaction mixture to prepare copolymer precursor (P0) is kept at about 150°C to about 350°C, preferably from about 210°C to about 300°C for about one to 15 hours.
  • the copolymer precursor (P0) possesses end groups derived from the monomers and/or end groups from derived from the end-capping or protonating agents.
  • the copolymer precursor (P0) is generally manufactured by a polycondensation reaction between a dihydroxy component and a dihalo component
  • its end groups usually include hydroxyl groups and halo- - 23 - SSPU 2022/035 groups (such as chlorinated end or fluorinated end groups).
  • halo- - 23 - SSPU 2022/035 groups such as chlorinated end or fluorinated end groups.
  • the remaining halo-groups may be at least partially converted into non- halogenated end groups.
  • the inorganic constituents for example sodium chloride or potassium chloride or excess of base, can be removed, before or after isolation of the copolymer precursor (P0), by suitable methods such as dissolving and filtering, screening or extracting.
  • the amount of copolymer precursor (P0) at the end of the condensation is at least 30 wt.% based on the total weight of the copolymer precursor (P0) and the polar aprotic solvent, for example at least 35 wt.% or at least or at least 37 wt.% or at least 40 wt.%.
  • the copolymer precursor (P0) is separated from the other components (salts, base, ...) to obtain a solution. Filtration can for example be used to separate the copolymer (P0) from the other components. The solution can then be used as such for reacting the copolymer precursor (P0) with the compound R 2 – SH in the process of the present invention, or alternatively, the copolymer precursor (P0) can be recovered from the solvent, for example by coagulation or devolatilization of the solvent.
  • Polymeric Solution [00109] The second aspect of the present invention is directed to a polymeric solution comprising the polymeric composition as described herein according to the first aspect of the present invention.
  • the polymeric solution is preferably used to make an article such as membrane, tube, fiber or film.
  • the polymeric solution further comprises at least a solvent in which the copolymer (P1) and the PAES polymer (P2) are soluble.
  • the term “solubility” or “soluble” is defined herein as the maximum amount of polymer, measured in terms of weight of the polymer per weight of solution, which dissolves at a given temperature affording a transparent homogeneous solution without the presence of any phase separation in the system.
  • the ‘polymer’ in such a definition refers to the copolymer (P1), the PAES polymer (P2), or the blend of copolymer (P1) and PAES polymer (P2).
  • the solvent in the polymeric solution of the present invention may be selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl isosorbide (DMIso), methyl 5-(dimethylamino)-2-methyl-5- - 24 - SSPU 2022/035 oxopentanoate (Rhodiasolv® , cyrene, ⁇ -caprolactam, butyrolactone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, sulfolane and any combination of two or more thereof.
  • NMP N-methylpyrrolidone
  • NBP N-butylpyrroli
  • the concentration of the solvent in the polymeric solution may be at least 20 wt.%, at least 30 wt.%, or at least 40 wt.%, based on the total polymer solution weight and/or is at most 80 wt.%; at most 70 wt.%; or at most 60 wt.%, based on the total polymer solution weight.
  • At least one co-solvent may be also present, in addition to the main solvent described above, in the polymeric solution of the present invention. Examples of co-solvent may be benzyl alcohol, ethanol, isopropyl alcohol and/or sulfolane in instances when sulfolane is not used as the main solvent in the polymeric solution.
  • the concentration of the co-solvent may be from 0.5 wt.% to 15 wt. % based on the total polymer solution weight.
  • the total concentration of the solvent(s) and co-solvent(s) in the polymeric solution may be at least 20 wt.%, at least 30 wt.%, or at least 40 wt.%, based on the total polymer solution weight and/or is at most 80 wt.%; at most 70 wt.%; or at most 60 wt.%, based on the total weight of polymeric solution.
  • the overall concentration of the polymers (copolymer P1 and polymer P2) in the polymeric solution should be at least 8 wt.%, preferably at least 10 wt.%, preferably at least 12 wt.%, based on the total weight of the solution.
  • concentration of the polymers (copolymer P1 and polymer P2) in the polymeric solution does not exceed 40 wt.%, preferably it does not exceed 30 wt.%, more preferably it does not exceed 25 wt.%, yet more preferably it does not exceed 20 wt.%, based on the total weight of the polymeric solution.
  • the combined weights of the copolymer (P1) and polymer (P2) in the polymeric solution may be from 5 wt.% to 40 wt.% or from 8 wt.% to 40 wt.%, preferably from 8 wt.% to 35 wt.% or from 8 wt.% to 30 wt.%, more preferably from 10 wt.% to 25 wt.%, yet more preferably from 10 wt.% to 25 wt.% or from 12 wt.% to 20 wt.%, said wt.% being based on the total weight of the polymeric solution.
  • the total concentration of the copolymer (P1) and the polymer (P2) ranging from 15 to 20 wt.% with respect to the total weight of polymeric solution has been found particularly advantageous.
  • the polymeric solution may further comprise at least one pore forming agent selected from the group consisting of at least one polyvinylpyrrolidone (“PVP”) preferably having a molecular weight of at least 5,000 g/mol to 360,000 g/mol; at least one polyalkylene glycol (e.g., a polyethylene glycol “PEG”) with a formula - 25 - SSPU 2022/035 weight ⁇ 200 g/mol, 200 g/mol to 900 g/mol; at least one (poly)hydroxyl aliphatic alcohol having from 1 to 6 carbon atoms, preferably at least one glycerol compound, at least one carboxylic acid comprising at least 3 carbon atoms, such as propionic acid, and any combination thereof.
  • PVP polyvinylpyrrolidone
  • the (poly)hydroxyl aliphatic alcohols having from 1 to 6 carbon atoms or derivatives thereof may comprise or be at least one ethylene glycol compound and/or at least one glycerol compound.
  • ethylene glycol compound is intended to encompass ethylene glycol, dimers and/or trimers thereof, as well as mono-ether and mono-ester derivatives, to the extent that the ethylene glycol compound comprises at least one free hydroxyl group.
  • ethylene glycol compounds are selected from the group consisting of ethylene glycol, diethylene glycol (DEG), triethylene glycol (TEG), aliphatic mono-ethers and mono-esters, in particular methyl, ethyl or butyl mono-ethers and acetyl monoesters.
  • DEG diethylene glycol
  • TEG triethylene glycol
  • aliphatic mono-ethers and mono-esters in particular methyl, ethyl or butyl mono-ethers and acetyl monoesters.
  • the expression “glycerol compound” is intended to encompass glycerol and dimers thereof, as well as mono-ether, di-ether, mono-ester and di-ester derivatives, to the extent that the glycerol compound comprises at least one free hydroxyl group.
  • Preferred glycerol compounds are selected from the group consisting of glycerol, aliphatic mono- and di-esters thereof, in particular mono-acetyl glycerol, di-acetyl glycerol, aliphatic mono- and di-ethers thereof, in particular methyl, ethyl or butyl mono-ethers or di-ethers, including notably mono-ter-butyl-glycerol, di-ter-butyl- glycerol; glycerol carbonate; glycerol acetals derived from aliphatic aldehydes, including butanal, pentanal, hexanal, octanal and decanal glycerol acetals.
  • the carboxylic acid comprising at least 3 carbon atoms is preferably selected from propionic acid, butyric acid, and/or valeric acid, more preferably propionic acid.
  • the one or more pore forming agent(s), when added to the polymeric solution, is/are present in amounts typically ranging from 0.5 wt.% to 40 wt.%, preferably from 1 wt.% to 40 wt.%, more preferably from 5 wt.% to 35 wt.%, yet more preferably from 10 wt.% to 30 wt.% or from 15 wt.% to 25 wt.%, said wt.% being based on the total weight of the polymeric solution.
  • PEG pore forming agents When one or more PEG pore forming agents are used, their amount is generally of from 10 wt.% to 40 wt.% or from 15 wt.% to 35 wt.%, or from 20 wt.% to 35 wt.% with respect to the total weight of polymeric solution.
  • the PEG preferably has a formula weight from 200 to 900 g/mol.
  • PVP pore forming agents When one or more PVP pore forming agents are employed, their amount is generally from 2 wt.% to 10 wt.% or from 4 wt.% to 8 wt.% with respect to the - 26 - SSPU 2022/035 total weight of polymeric PVP preferably has a molecular weight of from 5,000 g/mol to 360,000 g/mol.
  • PHAs having from 1 to 6 carbon are employed as pore forming agents, their amounts generally should be at least 1% by weight, preferably at least 2% by weight, based on the total weight of the solution.
  • the concentration of the PHAs in the solution does not exceed 20% by weight, preferably it does not exceed 15% by weight, more preferably it does not exceed 14% by weight, based on the total weight of the polymeric solution.
  • propionic acid employed as a pore forming agent in the polymeric solution, its amounts is generally of from 10 to 40 wt.% or from 20 to 35 wt.% with respect to the total weight of polymeric solution.
  • a polymeric solution having from 15 wt.% to 20 wt.% of copolymer (P1) and polymer (P2) may be made with a blend of solvent (e.g., NMP) and propionic acid with a vol/vol ratio of from 50:50 to 95:5, preferably from 60:40 to 80:20, more preferably from 65:35 to 75:25, yet more preferably about 70:30.
  • the polymer solution may exclude a pore forming agent, such as may exclude glycerol, a PVP and/or a PEG having a formula weight of at least 200.
  • the polymeric solution may contain additional components, such as nucleating agents, fillers and the like.
  • the polymer solution may exclude additional components, such as nucleating agents, fillers and the like.
  • additional components such as nucleating agents, fillers and the like.
  • Use of the PAES copolymer (P1) provides the use of the polymeric composition or polymeric solution of the present invention for making an article (or a part thereof) as described herein. This aspect also relates to a method for making an article (or a part thereof) comprising the polymeric composition of the present invention or made from the polymeric solution of the present invention.
  • the polymeric composition or polymeric solution of the present invention may be used to make a non-porous article, such as a dense film. Such a dense film may be a thick or thin film. Such use may include polymer solution casting.
  • the copolymer (P1) and polymer (P2) in the polymeric composition of the present invention may be the sole polymers in the non-porous article; alternatively, the non-porous article may further comprise at least another polymer.
  • the polymeric composition or polymeric solution according to the invention may be used to make a porous article, such as porous film, hollow fiber, hollow tube or porous membrane, using a phase inversion technique selected from nonsolvent induced phase separation or thermally induced phase separation.
  • Such use may - 27 - SSPU 2022/035 include casting or spinning a dope solution comprising the PAES copolymer, a solvent, optionally a co-solvent and optionally at least one pore forming agent, as described previously, into the porous article, which is then cooled or contacted with a non-solvent.
  • the copolymer (P1) and polymer (P2) are the sole aromatic sulfone polymers in the polymeric solution.
  • Article comprising or made from the PAES copolymer (P1) [00138] Another aspect of the present invention provides an article (preferably a shaped article) comprising, or made from, the polymeric solution according to the invention.
  • the article of the present invention comprising or made from the polymeric composition may be porous or non-porous.
  • the article of the present invention comprising or made from the polymeric composition may preferably be a porous article such as porous film, hollow fiber, hollow tube, porous membrane, or a part thereof (such as a (internal) porous layer or porous coating).
  • a “coating” according to the present invention is generally understood to be a layer fixed to the surface of a substrate, especially adhering thereon.
  • a coating may be a thin or thick layer, and/or may be a plurality of layers.
  • a “fiber” according to the present invention is generally understood to be a flexible structure whose width is thin compared to its length. Fibers preferably have a thickness of 0.5 to 100 microns.
  • a “membrane” according to the present invention is a separating article. The membrane may be non-porous, partly porous, selectively permeable, such as a membrane which is pervious in one direction. or may be porous.
  • the article of the present invention preferably excludes polymers other than the copolymer (P1) and the PAES polymer (P2).
  • the polymeric composition may form all, or substantially all, of the article. In other words, the article of the present invention may be essentially made from the polymeric composition.
  • the article of the present invention may comprise the copolymer (P1) as a polymeric hydrophilic additive to at least one bulk PAES polymer (P2), preferably selected from the group consisting of PSU, PPSU, PES, and any combination thereof.
  • the copolymer (P1) is a polymeric additive to a bulk PES or PPSU polymer
  • the weight fraction of the copolymer (P1) in the article may be from 5 to 40 wt.%, or from 10 to 40 wt.%, or - 28 - SSPU 2022/035 from 10 to 30 wt.%, or from 10 said wt.% based on the combined weights of copolymer (P1) and the bulk PAES polymer (P2).
  • the copolymer (P1) in the polymeric composition of the present invention which is used as a polymeric additive in the hydrophobic bulk PAES polymer (P2) improves the wettability, water uptake, water flux rate of such hydrophobic bulk PSU, PPSU or PES polymers that are typically used in forming porous membranes for hemodialysis and for water filtration such as ultrafiltration and microfiltration applications.
  • the polymeric composition of the present invention can be included in at least a portion of a surface of the article, such surface being intended to come in contact with an aqueous solution, water, a biological fluid such as blood, plasma, or serum, or a food product such as fruit juice, milk, beer.
  • the polymeric composition of the present invention may be incorporated into an article having a polymeric layer.
  • a fluid such as an aqueous medium, such as water, an aqueous solution (e.g., alkaline), a biological fluid (e.g., blood, plasma or serum) and/or food product (e.g., fruit juice, milk, beer) based upon the article’s intended application setting.
  • the polymeric layer may be an external or internal layer of the article. At least a portion of that layer may come into direct contact with the fluid in its intended application setting.
  • a medical device may have an external layer intended to come into direct contact with a biological fluid.
  • a thin film composite device like a reverse-osmosis membrane or nanofiltration membrane may have a layer intended to come into direct contact with an aqueous medium or water.
  • the article can comprise a thin selective layer disposed on an underlying layer or porous substrate.
  • the thin selective layer may comprise, or be made from, the polymeric composition of the present invention, while the underlying layer or porous substrate has a composition which excludes at least the more hydrophilic copolymer (P1).
  • the underlying layer or porous substrate may comprise, or be made from, the polymeric composition of the present invention, while the thin selective layer may has a composition which excludes at least the more hydrophilic copolymer (P1).
  • both of the thin selective layer and the underlying layer or porous substrate contain the more hydrophilic copolymer (P1) and the polymer (P2).
  • a film, tube, coating or layer of the present invention comprising or made from the polymeric composition of the present invention may have an average thickness of from about 25 ⁇ m to about 1 mm. - 29 - SSPU 2022/035
  • a porous membrane may be a membrane which can be characterized by its average pore diameter and porosity, i.e., the fraction of the total membrane that is porous.
  • the porous membrane may have a gravimetric porosity (%) of 20 to 90 % and comprises pores, wherein at least 90 % by volume of the said pores has an average pore diameter of less than 5 ⁇ m. Gravimetric porosity of the porous membrane is defined as the volume of the pores divided by the total volume of the membrane.
  • porous membranes comprising the polymeric composition of the present invention may be provided under the form of flat structures (e.g. having a plurality of films or sheets), corrugated structures (such as corrugated sheets), tubular structures (e.g. having a plurality of tubes), or hollow fibers.
  • Tubular porous membranes are classified based on their dimensions in tubular membranes having a diameter greater than 3 mm; capillary membranes, having a diameter comprised between 0.5 mm and 3 mm; and hollow fibers having a diameter of less than 0.5 mm.
  • Capillary membranes are otherwise referred to as hollow fibers. Hollow fibers are particularly advantageous in applications where compact modules with high surface areas are required.
  • full range of membranes non-porous and porous, including for microfiltration, ultrafiltration, nanofiltration, ion-exchange, and reverse osmosis
  • the pore distribution can be isotropic or anisotropic.
  • Membranes having a uniform structure throughout their thickness are generally known as symmetrical membranes; membranes having pores which are not homogeneously distributed throughout their thickness are generally known as asymmetric membranes.
  • Asymmetric membranes are characterized by a thin selective layer (0.1-1 ⁇ m thick) and a highly porous thick layer (100-200 ⁇ m thick) which acts as a support and has little effect on the separation characteristics of the membrane.
  • the asymmetric membrane may comprise a thin selective layer comprising, or made from, the polymeric composition of the present invention, disposed on an underlying layer or substrate having a composition distinct from the polymeric composition of the present invention.
  • the asymmetric membrane may comprise a support layer comprising, or made from, polymeric composition of the present invention, on top of which is disposed a thin selective layer having a composition excluding for example the more hydrophilic copolymer (P1).
  • P1 hydrophilic copolymer
  • Method for making the article - 30 - SSPU 2022/035 An article (e.g., fiber, film, tube, or part thereof such as a layer or coating) according to the present invention can be made using any of the conventionally known preparation methods, such as non-limiting examples, by a polymer solution casting method or solution polymer spinning method. Different shaping techniques can be used depending on the final form of the article to be manufactured.
  • the method for making the article may comprise casting or spinning a polymer solution (sometimes referred to as “polymer dope solution”) into a pre-formed article (such as film, fiber, tube, membrane, coating, layer) which is then cooled and/or contacted with a non-solvent.
  • a polymer solution sometimes referred to as “polymer dope solution”
  • a pre-formed article such as film, fiber, tube, membrane, coating, layer
  • the polymer dope solution comprises the copolymer (P1) and polymer (P2), the solvent in which the copolymer (P1) and the PAES polymer (P2), and optionally at least one pore forming agent.
  • the pore forming agent may be at least one selected from at least one PVP preferably having a molecular weight of at least 5,000 g/mol to 360,000 g/mol; at least one PEG having a formula weight of at least 200, preferably from 200 to 900 g/mol; at least one PHA such as ethylene glycol, glycerol and/or triethylene glycol; at least one carboxylic acid such as propionic acid; or any combination thereof.
  • a porous fiber, film, tube or membrane, or part thereof (such as a layer or coating) according to the present invention may be prepared using a phase inversion technique selected from non-solvent induced phase separation and/or thermally induced phase separation.
  • the polymer solution may be casted as a film over a flat supporting substrate, typically a plate, a belt or a fabric, or a microporous supporting membrane, typically by means of a casting knife, a draw- down bar or a slot die.
  • the polymer solution may be spinned in the form of a tubular film.
  • the tubular film may be manufactured using a spinneret, this technique being otherwise generally referred to as "spinning method". Hollow fibers and capillary membranes may be manufactured according to the spinning method.
  • spinneret is hereby understood to mean an annular nozzle comprising at least two concentric capillaries: a first outer capillary for the passage of the polymer - 31 - SSPU 2022/035 solution and a second inner referred to as “lumen”) for the passage of a supporting fluid, also referred to as “bore fluid”.
  • NIPS non-solvent induced phase separation
  • the pre-shaped article is contacted with a non-solvent medium (medium [NS]) thereby providing a porous article.
  • medium [NS] medium
  • Such step of contacting with a medium [NS] is generally effective for precipitating and coagulating the polymers (P1) and (P2) constituting the pre- shaped article into a porous article.
  • the polymers (P1) and (P2) may be precipitated in said medium [NS] by immersion in a coagulation bath containing a non-solvent medium [NS].
  • the coagulation bath containing at least one non-solvent medium [NS] may also contain a solvent at the beginning of the coagulation, for example from 5 wt.% to 70 wt.% solvent or from 10 wt.% to 70 wt.% solvent, or from 20 wt.% to 60 wt.% solvent, or from 30 wt.% to 50 wt.% solvent, said wt.% being based on the total weight of the coagulation bath.
  • the solvent content provided in the bath corresponds to the initial solvent concentration right before coagulation is started.
  • the coagulation bath preferably comprises a non-solvent selected from water at least one alcohol and/or at least one polyalcohol, such as aliphatic alcohols having a short chain, for example from 1 to 6 carbon atoms, preferably methanol, ethanol, isopropanol, glycerol, ethylene glycol, diethylene glycol and/or triethylene glycol.
  • a non-solvent selected from water at least one alcohol and/or at least one polyalcohol, such as aliphatic alcohols having a short chain, for example from 1 to 6 carbon atoms, preferably methanol, ethanol, isopropanol, glycerol, ethylene glycol, diethylene glycol and/or triethylene glycol.
  • the solvent in which the polymers (P1) and (P2) are soluble, in the coagulation bath may be selected from, but not limited to, NMP, NBP, NEP, sulfolane, DMAc, DMI, dimethyl isosorbide (DMIso), methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv® Polar-clean), cyrene, ⁇ -caprolactam, butyrolactone, DMSO, or any combination of two or more thereof.
  • the solvent present in the coagulation bath at the onset of the coagulation preferably comprises or consists essentially of NMP, sulfolane, DMAc, DMI, dimethyl isosorbide (DMIso), methyl 5- (dimethylamino) -2-methyl-5-oxopentanoate (Rhodiasolv® Polar-clean), cyrene, ⁇ -caprolactam, butyrolactone, DMSO, or any combination of two or more solvents.
  • the coagulation in the NIPS technique typically takes place in the coagulation bath at a temperature generally ranging from 15°C to 60°C, preferably from 20°C to 60°C, more preferably from 25°C to 50°C.
  • contacting the pre-shaped article with medium [NS] may be accomplished by exposing it to a gaseous phase comprising vapors of such medium [NS].
  • This technique is termed “VIPS” for vapor induced phase separation. This typically takes place in a climatic chamber into which the pre-shaped article is introduced in the climatic chamber set at a temperature generally ranging from 20°C to 40°C, preferably at - 32 - SSPU 2022/035 about 35°C and a relative from 50 to 80% RH, preferably at about 60% of humidity.
  • non-solvent is intended to mean a medium consisting of one or more liquid substances incapable of dissolving the polymers (P1) and (P2), and which advantageously promotes the coagulation/precipitation of the polymers (P1) and (P2) from the polymeric solution.
  • the medium (NS) typically comprises water and/or at least one alcohol or polyalcohol, preferably aliphatic alcohols having a short chain, for example from 1 to 6 carbon atoms, more preferably methanol, ethanol, isopropanol, glycerol, triethylene glycol, diethylene glycol, and/or ethylene glycol.
  • coagulation/precipitation of the PAES polymers (P1) and (P2) may be promoted by cooling.
  • the cooling of the pre-shaped article may be typically carried out using any conventional techniques.
  • the solvent in the polymeric solution is advantageously a “latent” solvent (solvent (LT)), i.e. a solvent which behaves as an active solvent towards the polymers (P1) and (P2) only when heated above a certain temperature, and which is not able to solubilize the polymers (P1) and (P2) below such temperature.
  • solvent (LT) solvent which behaves as an active solvent towards the polymers (P1) and (P2) only when heated above a certain temperature, and which is not able to solubilize the polymers (P1) and (P2) below such temperature.
  • the pre- shaping step for the making of the article is generally carried out at a temperature high enough to maintain the polymer solution as a homogeneous solution. Cooling may be achieved by contacting the pre-shaped article with a cooling fluid, which may be a gaseous fluid (i.e. cooled air or cooled modified atmosphere) or may be a liquid fluid. In this latter case, it is usual to make use of non-solvent medium [NS] as above detailed, so that the techniques of non- solvent-induced and thermally-induced precipitation may occur simultaneously.
  • a cooling fluid which may be a gaseous fluid (i.e. cooled air or cooled modified atmosphere) or may be a liquid fluid.
  • solvent and non-solvent are typically selected so as to ensure the solvent having higher volatility than the non-solvent, so that progressive evaporation, generally under controlled conditions, of the - 33 - SSPU 2022/035 solvent leads to the polymers’ and hence actual contact of the pre- shaped article with non-solvent medium.
  • pore forming agents are generally at least partially, if not completely, removed from the porous article in the non- solvent medium [NS], during this step of the method of article manufacture.
  • the method may further include additional treatment steps after shaping and precipitation/coagulation, for instance steps of rinsing and/or stretching the porous article and/or a step of drying the same, especially when the article is a porous membrane.
  • the porous article may be additionally rinsed, preferably with deionized water.
  • the porous article may be advantageously stretched so as to increase its average porosity.
  • the porous article may be advantageously stored in water (storing medium) so as to maintain it in a wet form.
  • the porous article may be advantageously stored in water plus glycerol (storing medium), with preferably from 5 wt.% to 20 wt.% glycerol based on total weight of storing medium (water + glycerol), and then dried at room temperature.
  • the porous article may be dried from its storing medium, either water or water+glycerol, at a temperature of advantageously at least 30°C. Drying can be performed under air or a modified atmosphere, e.g., under an inert gas, typically exempt from moisture (water vapor content of less than 0.001% v/v) after their wetting in isopropyl alcohol or alcohol. Drying can alternatively be performed under vacuum.
  • a suitable example of a method for forming a porous membrane from a polyaryl ether sulfone polymer is described in US2019/054429A1 (Solvay Specialty Polymers USA), incorporated herein by reference.
  • Manufacture of a non-porous article A non-porous (or dense) fiber, film, membrane, or part thereof (such as a layer or coating) according to the present invention may be prepared using polymer solution casting.
  • the PAES polymers (P1) and (P2) may be the sole polymers in the non-porous article; or the non-porous article may further comprise at least one other polymer different than PAES polymers (P1) and (P2).
  • Non-porous articles may be alternatively generated by classical melt processing techniques like film, tube or pipe extrusion, wire coating, injection molding and the like.
  • Non-porous articles can also be generated by solvent medium like in coating or casting. In such instances, the solvent is allowed to evaporate.
  • a polymer solution is fed through a slot die via a gear pump and cast on a moving support (belt). The solvent is let to evaporate in an oven chamber after casting. A polymer film is then detached from the carrier belt.
  • the polymeric composition or polymeric solution according to the present invention which comprises the PAES copolymer (P1) and the PAES polymer (P2) is particularly suitable for manufacturing articles intended for contact with an aqueous medium.
  • the aqueous medium may include or may be a biological fluid such as blood, serum, a food product such as beverages (e.g., fruit juice, milk, beer), water, wastewater, or any aqueous industrial process water stream such as process water, cooling water.
  • the article may be used for medical applications such as hemodialysis membranes, for polymer electrolyte membranes, for aqueous medium filtration, such as reverse osmosis membranes, ultrafiltration membranes, microfiltration membranes, nanofiltration membranes, and/or ion-exchange membranes. Both microfiltration and ultrafiltration membranes can be used in membrane bioreactors, such as wastewater treatment. Membranes may be in flat sheet or hollow fiber configuration.
  • the aqueous medium filtration may include food and beverage filtration, filtration for water purification, filtration for wastewater treatment and filtration for industrial process separations involving aqueous medium.
  • a further aspect of the present invention may be directed to a method for purifying an aqueous medium, said method comprising at least a filtration step through a membrane, fiber(s), tube(s) or film(s) comprising the polymeric composition according to the present invention, or made from the polymeric solution according to the present invention.
  • the inventive polymeric composition or solution can be used in different filter membrane geometries.
  • the polymeric composition or solution can be used in flat membranes and/or in capillary-like hollow fiber membranes.
  • the aqueous medium flow toward these membranes may take in the form of a dead-end flow or of a crossflow.
  • the purification method may be used for purifying a human biological fluid, preferably a blood product, e.g., whole blood, plasma, serum, fractionated blood components or mixtures thereof.
  • the purification is carried out in an extracorporeal circuit which may comprise at least one filtering device (or filter) comprising at least one membrane, fiber or film as described above.
  • a blood purification method through an extracorporeal circuit may comprise hemodialysis (FD) by diffusion, hemofiltration (HF), hemodyafiltration (HDF) and/or hemoconcentration.
  • FD hemodialysis
  • HDF hemodyafiltration
  • Blood purification methods through an extracorporeal circuit are typically carried out by means of a hemodialyzer, i.e., equipment designed to implement any one of FD, HF or HFD. In such methods, blood is filtered from waste solutes and fluids, like urea, potassium, creatinine and uric acid, thereby providing blood free of waste solutes and fluids.
  • a hemodialyzer for carrying out a blood purification method comprises a cylindrical bundle of hollow fibers of membranes, said bundle having two ends, each of them being anchored into a so-called potting compound, which is usually a polymeric material acting as a glue which keeps the bundle ends together. Potting compounds are known in the art and include notably polyurethanes.
  • PES Polyethersulfone
  • Veradel® 3000 MP obtained from Solvay Specialty Polymers – used as a PAES polymer (P2) in some of the examples
  • PPSU polybiphenylsulfone
  • Radel® 5000NT obtained from Solvay Specialty Polymers – used as a PAES polymer (P2) in some of the examples
  • PEG 400 polyethylene glycol 400 obtained from Sigma-Aldrich, U.S.A.
  • PVP k10 polyvinylpyrrolidone K10
  • PVP k90 polyvinylpyrrolidone K90
  • IPA isopropyl alcohol obtained from Sigma-Aldrich, U.S.A.
  • DMSO dimethylsulfoxide obtained from Sigma-Aldrich, U.S.A.
  • Glycerol from Sigma-Aldrich, U.S.A.
  • BSA bovine serum albumin
  • Dextran 4 powder technical grade, from Serva. Before its use, the dextran powder was thermally treated at 100°C for 2 hours to remove eventual humidity.
  • Phosphate buffered saline P4417 from Sigma-Aldrich, U.S.A.
  • s-PES Tetramethylammonium, acid chloride obtained from Sigma-Aldrich, U.S.A.
  • Sodium hypochlorite (NaOCl) obtained from Sigma-Aldrich, U.S.A.
  • GPC Method 1 for measuring molecular weight (Mn, Mw) [00223] Viscotek GPC Max (Autosampler, pump, and degasser) with a TDA302 triple detector array comprised of RALS (Right Angle Light Scattering), RI (Refractive Index) and Viscosity detectors were used. Samples were prepared as ⁇ 2 mg/mL in DMAc/ LiBr.
  • Samples were run in dimethyl acetamide (DMAc) with 0.2 w/w% LiBr at 65°C at 1.0 mL/min through a set of 3 columns: a guard column (CLM1019 - with a 20k Da exclusion limit), a high Mw column (CLM1013 exclusion of 10MM Daltons relative to Poly Styrene) and a low Mw column (CLM1011 - exclusion limit of 20k Daltons relative to PS).
  • Calibration was done with a single, mono-disperse polystyrene standard of ⁇ 100k Da. Light Scattering, RI, and Viscosity detectors were calibrated based on a set of input data supplied with the standards.
  • a copolymer precursor (P0-A) was prepared according to Scheme 1. [00234] The polymerization took place in a 20-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (2030.2 g; 7.07 moles), DHDPS (1673.12 g, 6.68 moles) and daBPA (98.62 g; 0.31 mole) were added to the vessel first, followed by the addition of potassium carbonate (977.14 g; 7.07 moles) and NMP (3996.59 g). The reaction mixture was heated from room temperature to 190 °C using a 10°C/min heating ramp.
  • copolymer P0-A 250 g
  • sodium 3-mercapto-1- propanesulfonate (MPS thiol) 25.75 g
  • DMSO solvent 583.3 g
  • AIBN 3.95 g
  • the reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water.
  • the coagulated sulfonated copolymer was then washed with 2 L of deionized water and then twice with 2 L of methanol.
  • the polymerization took place in a 2-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up.
  • the monomers DCDPS (326.28 g; 1.13 moles), DHDPS (256.21 g, 1.02 moles) and daBPA (31.22 g; 0.1 mole) were added to the vessel first, followed by the addition of potassium carbonate (160.14 g; 1.15 moles) and sulfolane (1465.7 g).
  • the reaction mixture was heated from room temperature to 210°C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around four hours, depending upon the viscosity of the solution.
  • the copolymer P0-A (529.6 g), Sodium 3-mercapto-1- propanesulfonate (MPS thiol) (108.5 g) were first charged and then DMSO solvent (1235 g) was added and the mixture was stirred at 75 °C till a clear solution was obtained. Then nitrogen was purged through the mixture for 45 minutes after which AIBN (16.66 g) was added all at once. The reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water. The coagulated sulfonated copolymer was then washed with 2 L of deionized water and then twice with 2 L of methanol.
  • MPS thiol Sodium 3-mercapto-1- propanesulfonate
  • copolymer precursor (P0-C) was prepared according to Scheme 1 in a similar manner as described for the copolymer precursor (P0-B).
  • Characterization of the copolymer precursor (P0-C) [00259] The Mw, Mn, PDI measured by GPC Method 2 (Sulfones method), the TGA temperature and glass transition temperature Tg by DSC are provided in Table 1. [00260] 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2’-diallyl bisphenol A monomer in the copolymer precursor (P0-C).
  • copolymer (P0-D) was prepared according to Scheme 1.
  • the polymerization took place in a 1-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up.
  • the monomers DCDPS (145.01 g; 0.505 moles), DHDPS (113.87 g, 0.455 moles) and daBPA (13.87 g; 0.045 mole) were added to the vessel first, followed by the addition of potassium carbonate (71.17 g; 0.515 moles) and sulfolane (651.4 g).
  • the reaction mixture was heated from room temperature to 210°C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around six hours, depending upon the viscosity of the solution. The reaction was terminated by adding introducing methyl chloride gas to endcap the polymer for about 30 minutes after which the reaction stopped by ceasing the heating. The reaction mixture was then filtered, coagulated into methanol. The coagulated copolymer precursor was then washed with methanol and water and again with methanol and dried at 110°C.
  • sulfonated copolymer (P1-D) was prepared according to Scheme 2.
  • the reaction took place in a 1-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet.
  • An amount (130.32 g) of the copolymer precursor (P0- D) and sodium 3-mercapto-1-propanesulfonate (MPS thiol) (31.14 g) were first charged to the reactor vessel, and then DMSO solvent (521.2 g) was added. The mixture was stirred at 75 °C till a clear solution was obtained.
  • the monomers DCDPS (2030.2 g; 7.07 moles), DHDPS (1594.28 g, 6.37 moles) and daBPA (197.25 g; 0.63 mole) were added to the vessel first, followed by the addition of potassium carbonate (977.14 g; 7.07 moles) and NMP (4018.9 g).
  • the reaction mixture was heated from room temperature to 190 °C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around eight hours, depending upon the viscosity of the solution.
  • the reaction was terminated by adding DCDPS (140.7 g) and continuing the reaction for another 30 minutes after which fresh NMP (351.77 g) was added and the reaction stopped by ceasing the heating.
  • the mixture was stirred at 75 °C till a clear solution was obtained. Then nitrogen was purged through the mixture for 45 minutes after which AIBN (5.94 g) was added all at once. The reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water. The coagulated sulfonated copolymer was then washed with 2 L of deionized water and then twice with 2 L of methanol. The washed sulfonated copolymer was then dried in a vacuum oven at 110 °C overnight.
  • the polymerization took place in a 20-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up.
  • the monomers DCDPS ( 2010.12 g; 7 moles), DHDPS ( 1576.76 g, 6.3 moles) and daBPA ( 215.8 g; 0.7 mole) were added to the vessel first, followed by the addition of potassium carbonate ( 977.14 g; 7.07 moles) and NMP (4024 g).
  • the reaction mixture was heated from room temperature to 190°C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around 6 hours, depending upon the viscosity of the solution.
  • Table 1 summarizes the properties of the copolymer precursors (P0-A) to (P0-F) and sulfonated copolymers (P1-A) to (P1-F).
  • Table 1 Copolymer p recursors P0-A P0-B P0-C P0-D P0-E P0-F GPC M w 71376 71927 72962 137995 77907 54162 method M n 25407 24453 30606 22636 24645 19873 2 PDI 2.81 2.94 2.38 6.09 3.16 2.72 T GA, °C 486 460 425 462 472 455 T g, °C 228 - 190 208 218 217 Sulfonated c opolymers P1-A P1-B P1-C P1-D P1-E P1-F GPC Mw 109239 94881 77386 306550 252576 81397 method M n 47408 40133 365
  • Example 2 Preparation of films from solutions comprising blends of sPES copolymers (P1) and PES polymer (P2) according to the invention
  • P1 and PES polymer (P2) Preparation of films from solutions comprising blends of sPES copolymers (P1) and PES polymer (P2) according to the invention
  • Example 3 Properties of films comprising blends of sulfonated copolymers (P1) and PES polymer (P2) [00313] Methods [00314] Thickness measurement on dried films [00315] Thickness was measured on dried films by using ABSOLUTE Digimatic Thickness Gauges provided by Mitutoyo. The thickness of each film was referred to the average of at least 5 measures on different positions. [00316] Water uptake measurement on polymeric dense films [00317] The polymeric dense film (20 cm*12.5 cm) prepared in Example 2 were dried at 50° C for 24 hours before testing.
  • CAB Captive Air Bubble
  • CAB measurements were carried out at room temperature, using an adapted environment controlled chamber filled with deionized water (DI water). Prior to analysis, the films were hydrated in DI water. The wet films samples were wrapped on a 15x15mm glass substrate, fixed on a sample holder with double-sided tape. Film samples were then immersed in DI water, and a air bubble was dropped on the sample surface using a J-shaped syringe.
  • Contact Angle measurements were performed on an optical tensiometer (DSA100 provided by KRUSS) equipped with a high quality monochromatic cold LED (6) and a high resolution (1984x1264) digital camera. Image acquisition parameters were set at 5 Frames Per Second (FPS) and a minimum acquisition time of 60 s.
  • DSA100 optical tensiometer
  • FPS Frames Per Second
  • Each bubble image was stored digitally and an image analysis system (ADVANCE) calculated the contact angle ( ⁇ ) from the shape of the bubble.
  • the CAB contact angle values reported in Tables 2-4 were the average of 5 measurements performed in the air at room temperature on the same sample.
  • Example 4 Leaching test [00341] This test was aimed at comparing the leaching properties and water uptake of the sPES copolymer samples P1-B and P1-D to a commercial sulfonated PES from Konishi having a 32% degree of sulfonation and a Mw of 140,000 g/mol (“Konishi sPES”). - 51 - SSPU 2022/035 [00342] A film CE19 was made from Konishi sPES according to the method provided in Example 2. [00343] The polymeric materials were first dried at 160 o C for 3 hour under vacuum. The drying weight loss calculated in % from the initial weight to the weight after the 3- hour drying was reported in Table 6.
  • Method for powder leaching testing was carried out by subjecting a polymer powder (15 g) for 4 hours at 50 o C in water (0.3 L). The weight loss calculated in % from the initial weight to the weight after 4 hours is reported for PES powder, sPES copolymer (P1-B) and (P1-D) powders and the commercial Konishi sPES powder in Table 6.
  • Method for film leaching testing [00347] A leaching film test was carried out by subjecting a polymer film sample (ca.5 g ) for 48 hours at 35 o C in water (80 mL).
  • the weight loss calculated in % from the initial weight to the final weight after 48 hours is reported in Table 6 for a sample of the PES film CE1, of the film CE7 made from sPES (P1-B), of the film CE12 made from sPES (P1-D) and of the film CE19 made from commercial Konishi sPES.
  • Films CE1, E6, CE7 made in 2 and characterized in Example 3 were used for the chemical resistance testing.
  • 5.2 Method (2) for chemical resistance testing [00360] Films CE1, E9, CE10 made in Example 2 were used for this chemical resistance testing (method 2).
  • a different chemical resistance testing was carried out by submerging three (3) separate polymeric film samples per polymeric material being tested to compare the chemical resistance of films CE1 (PES), E9 (20 wt.% sPES P1- C+80 wt.% PES), and CE10 (sPES P1-C).
  • the tests were carried out on film pieces as described on ASTM D638-14. The dimension/size of the film pieces were cut by a type V specimen in an aqueous sodium hypochlorite solution (containing 5000 ppm NaClO) at 40°C for 3 days, for 1 week and for 2 weeks (3 different time periods).
  • the effect of oxidant NaClO on the samples was evaluated by weight and mechanical test of each sample test before and after the NaClO submersion for each time.
  • the data: weight (%) , modulus (MPa), stress at break (MPa) and strain at break (%) difference between the untreated samples and the samples after a NaClO treatment are the average of the 3 test results are reported in Table 8 (3-day NaClO treatment), Table 9 (1- week NaClO treatment), and Table 10 (2-week NaClO treatment).
  • Table 8 3-day NaClO Film compositions CE1 E9 CE10 sPES (P1-C) wt.% - 20 100 PES wt.% 100 80 - Properties untreated 2210 2330 1880 Tensile Modulus, treated 2320 2120 1790 MPa % change +5 % -9% -5 % untreated 69 82 52 Tensile Stress at Break, MPa treated 76 63 44 % change +10 % -24% -15 % untreated 11 5.3 9.6 Tensile Strain at treated 5.9 8 9.1 break, % % change -46 % +51% -5% Weight % change -2.7% +0.8% +1.0% [00365] Table 9 : 1-week NaClO treatment Film compositions CE1 E9 CE10 sPES (P1-C) wt.% - 20 100 PES wt.% 100 80 - Properties untreated 2210 2330
  • the various amounts of sPES in the polymeric solutions were 5 wt.%, 10 wt.%, or 20 wt.%, said wt.% being relative to the combined weights of sPES and PES in the polymeric solution.
  • the solution 150 grams was made by stirring the polymers, pore forming agents and NMP solvent, so as to obtain 15 wt.% of the blend of PES+sPES, 15 wt.% of PEG400, 5 wt.% of PVP with the remainder of weight being NMP in the polymeric solution. The stirring lasted for several hours at 65°C.
  • the polymeric solution was left at rest under room temperature for 8 hours to remove eventual air bubbles.
  • the solution 150 grams was made by stirring the polymers and NMP solvent, so as to contain 15 wt.% of the blend of PES+sPES in 85 wt.% NMP.
  • reference polymeric solutions were made with only PES (100 wt.% PES with no sPES additive) for making comparative membranes.
  • Porous membrane preparation - 56 - SSPU 2022/035 A4 size flat sheet porous were prepared by filming 20 grams of a polymeric dope solution (polymers + solvent + optional pore formers) as described above, over a suitable smooth glass support by means of an automatized casting knife. [00375] Membrane casting was performed by holding dope solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the polymer. The knife gap was set to 250 ⁇ m. After casting, the polymeric porous films were immediately immersed in a coagulation bath at 25°C in order to induce phase inversion. The coagulation bath consisted of pure de-ionized water.
  • Table 11 provides the compositions of the polymeric solutions used to make membrane samples. Reference polymeric solutions were made with only 15 wt.% PES (100 wt.% PES with no sPES) without or with pore forming agents in NMP for making comparative membranes.
  • a comparative membrane CE23 was made from a polymeric solution containing solely 15 wt.% PES in NMP without pore forming agent. - 57 - SSPU 2022/035 [00379] Three membranes E28-E30 to the invention were made from polymeric solutions containing 15 wt.% of a blend of PES + sPES P1-B with two pore forming agents (15 wt.% PEG 400, 5 wt.% PVP). A comparative membrane CE27 was made from a polymeric solution containing 15 wt.% PES (without sPES) and the same pore forming agents and same respective amounts as in membranes E28- E30.
  • Example 7 Preparation of porous membranes made from polymeric solutions comprising 20 wt.% of blends of sPES copolymer (P1-B) and PES polymer (P2) [00381] Solution preparation for membrane manufacturing [00382] Dope polymeric solutions to make porous membranes were prepared by blending the sPES copolymer (P1-B) with the PES polymer (Veradel® 3000MP) as the PAES polymer (P2) and optionally pore forming agents in NMP and stirring with a mechanical anchor stirrer at 70 o C, similarly as described in Example 6, except that the total content of PES+sPES was maintained at 20 wt.% in the polymeric solution.
  • the selected amount of sPES was 10 wt.% relative to the combined weights of sPES and PES in the polymeric solution to make these membranes.
  • the dope polymeric solution contained 20 wt.% of the blend of PES+sPES, 25 wt.% of PEG400, 5 wt.% of PVP k10 with the remainder of weight being NMP in the polymeric solution.
  • the dope solution contained 20 wt.% of the blend of 90wt.%PES+10wt.%sPES in 80 wt.% NMP.
  • Membrane E34 according to the invention was made from a blend of 90 wt.% PES+10 wt.% sPES with pore forming agents (25 wt.% PEG 400, 5 wt.% PVP), and a comparative membrane CE33 was made from PES (without sPES copolymer) and same kind and amounts of pore forming agents.
  • each flat membrane was referred to the average of at least 5 measures on different positions.
  • Permeability measurements on flat membrane [00398] Water flux (J) through each membrane at given pressure, was defined as the volume which permeates per unit area and per unit time. The flux was calculated with the following equation: - V (L) is the volume of permeate, - A (m 2 ) is the membrane area, and - ⁇ t (h) is the operation time. [00399] Water flux measurements were conducted at room temperature using a dead-end configuration system under a constant nitrogen pressure of 1 bar using pure MilliQ water. Membrane discs with an effective area of 11.3 cm 2 were cut from the membrane sheets (stored in water) and placed on a metal plate.
  • the flux was the average of measurements obtained on at least five different discs. The flux was expressed in LMH (liters/squared meter x hour or L/m 2 h).
  • LMH liters/squared meter x hour or L/m 2 h.
  • Each permeability test was carried out by applying pressure for 30 minutes on wet membranes which were previously stored in water. The reported flux was obtained by collecting data measured from the 27 th to the 30 th minute of each test. - 59 - SSPU 2022/035
  • Gravimetric porosity on flat [00402] Gravimetric porosity of a porous membrane was defined as the volume of the pores divided by the total volume of the membrane. [00403] Membrane porosity ( ⁇ ) was determined according to the gravimetric method detailed below.
  • the contact angles analysis was carried out by depositing a drop of 2 ⁇ L of water Milli Q on the sample surface through a syringe.
  • the drop image was stored by a video camera placed in the instrument OCA 20 (KSV) provided by DATA and an image analysis system (software called SCA20 version 5.0.17) calculated the contact angle ( ⁇ ) from the shape of the water drop.
  • OCA 20 KSV
  • SCA20 version 5.0.17 calculated the contact angle ( ⁇ ) from the shape of the water drop.
  • - 60 - SSPU 2022/035 For each sample, the contact analysis was carried out for dry and wet samples. The wet samples are considered wet after submersion in water Milli Q overnight. Contact angles value were obtained as an average of 7 different static contact angle tests on same membrane surface, all measured in air at room temperature.
  • the sPES copolymer additive presence in the membranes (E24-E26) without pore formers and membranes (E28-30) with pore forming agents increased the gravimetric porosity compared to the PES-based membrane CE23 without pore forming agents and PES-based membrane CE27 with pore forming agents, respectively.
  • the sPES copolymer additive presence in the membrane (E32) without pore formers and membrane (E34) with pore forming agents increased the gravimetric porosity compared to the PES-based membrane CE31 without pore formers and the PES-based membrane CE33 with pore formers, respectively.
  • Example 9 Porous membrane preparation by combined VIPS/NIPS methods and coagulation in water bath at 25°C
  • Flat sheet porous membranes were prepared by filming polymeric solution (polymers + solvent + pore formers), over a suitable smooth glass support by means of an automatized casting knife. Dope solution quantity was 20 grams.
  • Membrane casting was performed by holding dope solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the polymer. The knife gap was set to 250 ⁇ m. After casting, in order to induce a first phase inversion, the polymeric films were immediately introduced in a climatic chamber set at 35°C and 60% of humidity (VIPS- vapor induce phase separation).
  • the membranes formed were immediately immersed in a coagulation bath in order to complete the phase inversion (NIPS- non solvent induce phase separation).
  • the coagulation bath consisted of pure de-ionized water maintained at 25°C. After coagulation the membranes were washed several times in pure water during the following days to remove residual traces of solvent. The membranes were always stored (wet) in water.
  • Table 15 provides the composition of the polymeric solution comprising a total 17 wt.% of polymers (90 wt.% PES + 10 wt.% sPES P1-B), 25 wt.% PEG400 + 5 wt.% PVP k10 in NMP used to make membrane sample E36 by combined VIPS/NIPS methods and coagulation in water.
  • a comparative membrane CE35 was made from solely PES with same amounts and types of pore forming agents using same combined VIPS/NIPS methods and coagulation in water.
  • the wet thickness, liquid flow rate and gravimetric porosity are reported in Table 15 and FIG.1.
  • Example 10 Porous membrane preparation by combined VIPS/NIPS methods and coagulation in a bath containing solvent/non-solvent mixture
  • a flat sheet porous membrane was prepared by filming a polymeric solution (polymers + solvent + pore forming agents), over a suitable smooth glass support by means of an automatized casting knife. Dope solution quantity was 20 grams.
  • Membrane casting was performed by holding dope solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of - 63 - SSPU 2022/035 the polymers.
  • the knife gap to 250 ⁇ m.
  • the polymeric film was immediately introduced in a climatic chamber set at 35°C and 60% of humidity.
  • the membrane formed was immediately immersed in a coagulation bath containing 30 wt.% NMP (solvent) + 70 wt.% deionized water (non-solvent), in order to complete the phase inversion and induce the formation of a sponge structure.
  • Table 15 provides the compositions of the polymeric solutions comprising a total 17 wt.% of polymers (90 wt.% PES + 10 wt.% sPES P1-B), used to make membrane samples E38 and E39 by combined VIPS/NIPS methods and coagulation in the 30w/70w NMP:water bath.
  • the difference between E38 and E39 is that the polymeric solution to make membrane E38 had 25 wt.% PEG400 + 5 wt.% PVP k10 in NMP while the polymeric solution to make membrane E39 had 35 wt.% PEG400 + 5 wt.% PVP k10 in NMP.
  • the water flux, gravimetric porosity and wet thickness for these membranes are reported in Table 15 and illustrated in FIG.2.
  • the membranes E38 and E39 in which the sPES copolymer P1-B additive was added to the PES polymer showed a higher water flux than the comparative PES membrane CE37 made without the sPES copolymer additive.
  • Example 11 Porous membrane preparation by NIPS method (without VIPS) and coagulation bath with solvent/non-solvent mixture
  • a flat sheet porous membrane was prepared by filming a polymeric dope solution (polymers + solvent + pore forming agents), over a suitable smooth glass support.
  • Membrane casting was performed by holding each dope solution, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the sulfone polymer(s). The knife gap was set to 250 ⁇ m.
  • the polymeric films were immediately immersed in a coagulation bath containing 30 wt.% NMP (solvent) + 70 wt.% deionized water (non-solvent) in order to initiate the phase inversion and induce the formation of a sponge structure.
  • a coagulation bath containing 30 wt.% NMP (solvent) + 70 wt.% deionized water (non-solvent) in order to initiate the phase inversion and induce the formation of a sponge structure.
  • NMP solvent + 70 wt.% deionized water (non-solvent)
  • non-solvent deionized water
  • Table 16 provides the composition of the polymeric dope solutions, each comprising a total 17 wt.% of sulfone polymers and two pore forming agents (5 wt.% PVP k10 ; 25 wt.% PEG 400) used to make membrane samples CE40 and E41-E44 by NIPS method (without VIPS) and coagulation in the 30:70 v/v NMP:water bath.
  • the dope solution to make membrane CE40 only contained PES as the sulfone polymer.
  • Each of the dope solutions to make membranes E41-E44 contained a blend of PES + sPES P1-B with a PES:sPES weight ratio of 9:1, 8:2, 7:3 and 1:1, respectively.
  • the membranes E41, E42 and E44 according to the invention also showed a higher thickness than the comparative PES membrane CE40.
  • the membrane E41 which was made by NIPS technique (without VIPS) followed by coagulation in the NMP:water bath (30:70 w/w) at 25 o C had a slightly lower water flux than the membrane E38 made from the same polymeric solution and formed by VIPS/NIPS technique and using same coagulation conditions (30w:70w NMP:water bath).
  • the gravimetric porosity of membrane E41 using only NIPS was higher than the membrane E38 made using combined VIPS/NIPS.
  • BSA bovine serum albumin
  • dextran 4kDa dextran 4kDa
  • COD Analysis The COD was measured using an oven HT 200 S (15 minutes at 170°C) and a spectrophotometer DR 3900 VIS from Hach, using LCK 314 and LCK 514 cuvettes.
  • the retention test was carried out on the membranes CE31 and E32 made from a polymer dope solution in NMP containing 20 wt.% polymers (PES+sPES P1-B with 9:1 weight ratio), 25wt.% PEG 400 and 5 wt.% PVP k10 which was coagulated in a 30:70 w/w NMP/water bath.
  • the retention test was carried out on the membranes CE40 and E41-E44 made from a polymer dope solution in NMP containing 17 wt.% polymers (PES+sPES P1-B with weight ratios being from 9:1 to 1:1), 25wt.% PEG 400 and 5 wt.% PVP k10 which was coagulated (NIPS) in a 30:70 w/w NMP/water bath.
  • PES+sPES P1-B with weight ratios being from 9:1 to 1:1
  • 25wt.% PEG 400 and 5 wt.% PVP k10 which was coagulated (NIPS) in a 30:70 w/w NMP/water bath.
  • the BSA and dextran 4 retentions were reported in Table 17.
  • the pore size diameter of the membrane samples can be considered higher than about 3 nanometers (nm).
  • Example 13 SEM analysis of porous membranes prepared in Examples 6, 7, 9 & 10 [00460] Microscopic observation of the membrane surfaces and cross-section were performed by using a scanning electron microscope (SEM) Hitachi, TM400 Plus II at an accelerating voltage of 10kV. To realize the cross-section samples, the membranes wet in IPA were freeze-fractured in liquid nitrogen instead the surfaces after drying from IPA, were directly placed on the holder. All surfaces and cross- section were coated with Au before use. [00461] The SEM pictures in Fig.4-13 for membrane samples CE23, E24-E26, CE31, E32, E34, CE35, E36, E38 were obtained with a magnification of 2000x. [00462] Fig.
  • Fig.7 and 8 represent SEM pictures of two comparative membranes CE23 & CE31 made from PES.
  • Fig.9 represents a SEM picture of the membrane E32 according to the invention, which was made from a polymeric solution containing 20 wt.% of a blend of 10 wt.% sPES/90 wt.% PES without pore forming agents.
  • Fig.10 represents a SEM picture of the membrane E34 according to the invention, which was made from a polymeric solution containing 20 wt.% of a blend of 10 wt.% sPES/90 wt.% PES with pore forming agents.
  • Fig.11 represents a SEM picture of the comparative membrane CE35 made from a polymeric solution containing 17 wt.% PES with pore forming agents using VIPS/NIPS technique using a climatic chamber followed by coagulation at 25 o C in a water bath.
  • Fig.12 represents a SEM picture of the membrane E36 according to the invention, which was made from a polymeric solution containing 17 wt.% of a blend of 10 wt.% sPES/90 wt.% PES with pore forming agents using combined VIPS/NIPS technique using a climatic chamber followed by coagulation at 25 o C in a water bath.
  • Fig.13 represents a SEM membrane E38 according to the invention, which was made from a polymeric solution containing 17 wt.% of a blend of 10 wt.% sPES/90 wt.% PES with pore forming agents using combined VIPS/NIPS technique using a climatic chamber followed by coagulation at 25 o C in a NMP:water bath (30:70 w/w).
  • the membranes CE23 and CE31 made from solely PES showed a closed layer structure compared to membranes E24-E26, E32 without pore forming agents, and membrane E34 with pore forming agents according to the invention (see Fig.4-6 & 9-10).
  • the SEM picture showed a spongy structure without macrovoid formation.
  • Example 14 Compatibility test of PPSU and sPES (P1-B)
  • Blending of polymers is widely accepted in the industry for the production of a polymeric materials with specific applications through an inexpensive route which otherwise not attainable with a single polymer.
  • One of the important controlling parameter in this case is the degree of compatibility of the polymers blended.
  • a test for polymers compatibly was carried out by preparing a polymeric solution comprising a total 20 wt.% of polymers (PPSU + sPES with a PPSU:sPES weight ratio of 95:5) in NMP as solvent.
  • Example 15 PPSU membranes preparation (15wt.% sulfone polymers in solution with pore forming agents made by NIPS and coagulation in 50w/50w NMP/water at 50°C)
  • Flat sheet porous membranes were prepared by filming polymeric solution (polymers + solvent + pore formers), over a suitable smooth glass support by means of an automatized casting knife. Dope solution quantity was 20 grams.
  • Membrane casting was holding polymeric solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the polymer.
  • the knife gap was set to 250 ⁇ m.
  • the polymeric films were immediately immersed in a coagulation bath in order to complete the phase inversion (NIPS- non solvent induce phase separation).
  • the coagulation bath consisted of 50 wt.% in pure de- ionized water and 50 wt.% of NMP and was maintained at 50°C.

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Abstract

The invention relates to a polymeric composition comprising a blend of a sulfonated and/or carboxylated sulfone copolymer (P1) and a polyarylethersulfone polymer (P2) wherein the copolymer (P1) comprises – (CH2)q – SO3M and/or – (CH2)u – COOM pendant groups on side chains, with q, u being integers independently selected from 1 to 5 and M being selected from H, an alkali or alkali earth metal and/or ammonium. The present invention also relates to a polymeric solution comprising such polymeric composition, to the use of the polymeric composition or solution for making an article, especially a film, tube, fiber or membrane, and to an article, particularly a porous membrane for hemodialysis or water filtration, comprising or made from such polymeric composition and/or made from such polymeric solution.

Description

- 1 - SSPU 2022/035 Description Polymeric composition comprising a blend of poly(aryl ether sulfone) polymers suitable for manufacturing articles Related Applications [0001] This application claims priority to U.S. patent application No.63/476385 filed on December 21, 2022, European patent application No.23172141.6 filed on May 8, 2023, and U.S. patent application No.63/600048 filed on November 17, 2023, the whole content of these applications being incorporated herein by reference for all purposes. Technical Field [0002] The present invention relates to polymeric compositions suitable for manufacturing articles, particularly membranes, comprising a blend of a poly(aryl ether sulfone) polymer with a more hydrophilic poly(aryl ether sulfone) additive, to articles, particularly films, tubes, fibers or membranes, containing such compositions, and to use of such articles such as porous membranes for medical and/or water filtration applications. Background Art [0003] Poly(aryl ether sulfone) (PAES) polymers are high performance polymers with high mechanical strength and thermal stability; they are used in a variety of industrial applications. The PAES polymers are made by polycondensation reactions, typically using 4,4’-dichlorodiphenyl sulfone (DCDPS) along with at least one aromatic diol such as bisphenol A, 4,4’-biphenol or 4,4’- dihydroxydiphenylsulfone, also called bisphenol S. Their chemical, thermal, and mechanical resistance, combined with its excellent hydrolytic stability and relatively inexpensive production costs, make it ideal for widespread use in fabrication of porous membranes, in particular porous hollow-fiber polymeric membranes. [0004] Porous membrane is a thin object, the key property of which is its ability to control the permeation rate of chemical species through itself. This feature is exploited in applications like separation applications (water and gas). Porous hollow-fiber polymeric membranes are employed in many applications such as hemodialysis, ultrafiltration, nanofiltration, reverse osmosis, gas separation, microfiltration, desalination via membrane distillation, and pervaporation. For many of these applications, membranes with optimal selectivity as well as chemical, thermal and mechanical stability are desirable. [0005] Membranes made from PAES polymers are hydrophobic in nature and therefore endowed of water repellency, low water permeability. These membranes suffer - 2 - SSPU 2022/035 from poor hydrophilicity that affects water permeation performance. Hydrophobicity impedes water to penetrate into the polymeric membrane and therefore water permeability requires higher pressure and consumes more energy. Another relevant issue is the fouling phenomenon. The intrinsic hydrophobicity of PAES polymers also makes PAES-based membranes prone to fouling which negatively impacts their performance. Fouling is frequently the bottleneck of membrane processes, resulting in a sharp decline in permeate flux and decrement in membrane lifetime. Fouling is caused by hydrophobic interactions and electrostatic forces between membrane materials and foulants (e.g., microorganisms, proteins, or organic matter) originating from a fluid to be treated though the membrane. In particular, fouling is initiated by the adsorption of foulants onto the membrane surface and the interior structure, resulting in pore blocking, cake layer formation, or biofilm formation. Fouling reduces temporarily or permanently the flux of permeation of water through the membrane, e.g. in ultrafiltration or microfiltration processes. Membrane fouling not only decreases membrane permeability and overall lifetime, but also increases maintenance costs due to extensive and frequent cleaning to remove foulants. [0006] For that reason, PAES-based membranes are frequently modified to increase its hydrophilicity and reduce its fouling propensity before its practical use. Enhancing surface hydrophilicity can be achieved by increasing the density of the hydrophilic groups at the membrane surface. By making inner surfaces of the inner pores hydrophilic, the capability of permeating water through porous PAES membrane is generally improved. Besides, it is generally accepted that an increase of the hydrophilicity of PAES membranes offers better fouling resistance because proteins and other foulants are hydrophobic in nature. [0007] Several strategies have been employed to make the porous PAES membrane more hydrophilic and thus rendering such membrane highly water permeable and highly resistant to fouling. [0008] The blending of PAES with hydrophilic materials attracts much interest due to its ability to improve the permeate flux and rejection. Hydrophilic materials are responsible for enhancing water absorption during a filtration process, which reduces water transport resistance and improves membrane permeability. For example, blending of hydrophilic additives (e.g., polyethylene glycol, polyvinylpyrrolidone, etc.) in a polyethersulfone (PES) matrix membrane is an approach to reduce hydrophobicity and improve flux performances. But usually these hydrophilic additives are not permanent and tend to get leached out during prolonged use of the membrane. - 3 - SSPU 2022/035 [0009] Another approach is based on hydrophilic species on the surface of membranes, by way of incorporation of hydrophilic comonomers in main polymer chain of PAES polymer, and by way of surface chemical reaction of the polymer such as direct sulfonation by a sulfonation agent are reviewed e.g. in Rana et al (2010) “Surface Modifications for Antifouling Membranes”, Chemical Reviews, Vol.110, No.4, p.2448- 2471. [0010] Sulfonated copolymers are described in US2012/083541A1 and US2004101730A1. The preparation of sulfonated polymers can be carried out via direct sulfonation in the monomer or post sulfonation method of an unsulfonated polymer or copolymer as described. US2012/083541A1 describes an aromatic polyether sulfone block copolymer comprising hydrophilic segments which have sulfonic acid groups and hydrophobic segments which have no sulfonic acid groups, wherein the proportion by weight of hydrophilic segments is from 0.02 to 0.35, based on the total block copolymer (corresponding to from 2 to 35% by weight), as well as a process for preparing such aromatic polyether sulfone block copolymers, wherein an aromatic polyether sulfone block copolymer is sulfonated by means of concentrated sulfuric acid at a temperature in the range from 20 to 70° C. [0011] One of the most investigated additive is sulfonated PES (“sPES”) obtained by sulfonation of the aromatic ring of PES. A commercial sPES available in the market produced by Konishi is synthesized by using post-polymerisation sulfonation of PES with a sulfonation agent selected from chlorosulfonic acid, sulfuric anhydride, sulfuric acid, or fuming sulfuric acid - see for example US 2016/9228060. [0012] The use of polyarylethers and sulfonated polyarylethers for the production of membranes is described in the state of art. For example, Matsuyama et al. in “Effect of Molecular Weight of Sulfonated Poly(ether sulfone) (SPES) on the Mechanical Strength and Antifouling Properties of Poly(ether sulfone)/SPES Blend Membranes” Ind. Eng. Chem. Res. 2017, 56, 11302−11311, described that the hydrophilicity and the negative charge density of membranes were increased by the use of Konishi sPES as additive. Matsuyama et al. in “Evaluating the Antifouling Properties of Poly(ether sulfone)/Sulfonated Poly(ether sulfone) Blend Membranes in a Full-Size Membrane Module” Ind. Eng. Chem. Res. 2018, 57, 4430−4441, fabricated a series of full-size membrane modules containing PES/SPES (Konishi sPES) blend hollow fiber and showed that by introducing in the blend a 10% of SPES, an antifouling improvement was achieved. [0013] Nowadays, the wastewater treatment for mariculture industries has attracted many interests whether from academic or practical points of view. In this field, a - 4 - SSPU 2022/035 recent paper demonstrated the PSU/sulfonated PSU membranes, where sPSU was synthesized by direct sulfonation method using chlorosulfuric acid as the sulfonating agent, exhibited good performance including high flux and excellent rejection in the ultrafiltation process – see Di Song et al. (2016) “Polysulfone/ sulfonated polysulfone alloy membranes with an improved performance in processing mariculture wastewater”, Chemical Engineering Journal vol.304, pp.882–889. [0014] Hemodialysis is one of the important methods for blood purification. PES has been widely used for this application. However the adsorption of serum proteins onto PES hemodialysis membranes can cause serious or life-threatening complications due to activation of the complement alternative pathway. Anticoagulants are often injected during the process of dialysis to avoid clot formation. To resolve the problem, many studies have aimed to improve the blood compatibility of biomaterials by surface modification, in particular by sulfonation PES. Du et al. (2009) in “Improvement of Hydrophilicity and Blood Compatibility on Polyethersulfone Membrane by Blending Sulfonated Polyethersulfone”, Chinese Journal of Chemical Engineering, vol.17(2) pp.324-329, reports the sulfonation of PES by using sulfuric acid at 98%. In this research they found a BSA adsorption reduction and a prolonged coagulation time when the PES/sPES blend membrane contacts blood. These indicated that the blood compatibility of PES membrane was improved through blending sPES. [0015] However these sulfonated additives are produced by using harsh chemicals and the post-polymerisation sulfonation can often cause a reduction in molecular weight of the polymer after sulfonation. Moreover, sulfonated PAES made by sulfonation of the aromatic rings of the PAES polymer has a disadvantage of leaching, that is to say, suffers from weight loss when subjected to water within a given time frame. This effect ia demonstrated with Konishi sPES in the current application. [0016] WO2020/187684A1 describes an alternate way to introduce sulfonates on a side- chain functionalized copolymer (P1). The process for preparing such a copolymer comprises reacting a functionalized copolymer (P0) having side-chain allyl/unsaturated carbon-carbon double bonds functional groups which are reacted with a compound R2 - SH, wherein R2 may be - (CH2)q – SO3Na, with q being selected from 1 to 5. Such sulfonated copolymers described therein are taught as notably useful for the manufacture of membranes, although no specific example of the actual manufacture of membranes is provided. No information is provided concerning its hydrophilicity and water permeation. - 5 - SSPU 2022/035 Summary of invention [0001] One object of the present invention is to increase the hydrophilicity of aromatic sulfone polymers in order to make porous articles, particularly membranes less susceptible to fouling, with increased hydrophilicity and increased water permeability. [0002] Another object is to further reduce the chemical degradation of the aromatic sulfone polymers when subjected to cleaning by an oxidizing agent. [0003] A further object is to reduce the loss of membrane weight by leaching when using the sulfonated or carboxylated sulfone polymer additive in a bulk aromatic sulfone polymer. It is expected that these improved properties will result in increasing the lifetime of these membranes during its use in medical applications or water filtration systems and reducing at least the operating costs associated with its use. [0004] A first aspect of the present invention is directed to a polymeric composition comprising: - from 1 to 50 parts by weight of a sulfonated and/or carboxylated aromatic sulfone copolymer (P1) and - from 50 to 99 parts by weight of a poly(aryl ether sulfone) (PAES) polymer (P2), said parts by weight being based on the entire weights of copolymer (P1) and polymer (P2). [0005] The sulfonated and/or carboxylated sulfone copolymer (P1) in the polymeric composition according to the invention comprises collectively at least 80 mol.% of: - recurring units (RP1) and - functionalized recurring units (R*P1), comprising two carboxylated and/or sulfonated pendant groups which include – COO-M+ and/or ─ SO3-M+, in which M+ is a cation, preferably selected from H+, alkali metal cations, alkali earth metal cations, NH4+ or any combination thereof, more preferably selected from H+, K+, Li+, Na+ and/or NH4+, said carboxylated and/or sulfonated pendant groups being covalently attached via a linking group including – S – (CH2)u – or – S – (CH2)q – to different aromatic rings in the recurring units (RP1 *), in which u is an integer selected from 1 to 5, preferably u being 1 or 2; and q is an integer selected from 1 to 5, preferably q being 1, 2 or 3; wherein the molar ratio of recurring units (RP1)/recurring units (R*P1) varies between 100/1 and 1/1, preferably between 50/1 and 2/1, more preferably between 40/1 and 3/1. [0006] The sulfone recurring units (RP1) in the copolymer (P1) are preferably not sulfonated and/or not carboxylated. [0007] The PAES copolymer (P2) in the polymeric composition according to the invention - 6 - SSPU 2022/035 comprises at least 80 mol.% of units (RP2). The recurring units (RP2) may be the same or different than the recurring units (RP1) of copolymer (P1). The recurring units (RP2) are preferably not sulfonated and/or not carboxylated. The PAES copolymer (P2) in the polymeric composition according to the invention is preferably not sulfonated and/or carboxylated. [0008] In particular, the polymeric composition preferably comprises: from 1 to 50 parts by weight of a sulfonated and/or carboxylated sulfone copolymer (P1) (hereinafter “copolymer (P1)”) and from 50 to 99 parts by weight of a polyarylethersulfone polymer (P2) (hereinafter “PAES polymer (P2)”), said parts by weight being based on combined weights of the copolymer (P1) and the PAES polymer (P2), said copolymer (P1) comprising collectively at least 80 mol.% of: - sulfone recurring units (RP1) of formula (M1): , - , and said units (RP2) of formula (M2): , - each R1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4, preferably i=0; - 7 - SSPU 2022/035 - each R4 is independently the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, ester, amide, imide, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each m is independently 0 or an integer from 1 to 4, preferably m=0; - GN is selected from the group consisting of at least one of the following formulae (GN1), (GN2), (GN3), (GN4), (GN5), (GN6): - each j is independently an integer from 3 to 7; - each of T1, T2, and W is independently selected from the group consisting of a bond, -CH2-; -O-; -SO2-; -S-; -C(O)-; -C(CH3)2- ;-C(CF3)2-; -C(=CCl2)-; - C(CH3)(CH2CH2COOH)-; -N=N-; -RaC=CRb-, where each Ra and Rb, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; -(CH2)n- and -(CF2)n- with n being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof, - each ─R2 is independently selected from the group consisting of - 8 - SSPU 2022/035 ─i(CH2)u – COO-M+, ─ (CH2)q – and any combination thereof, in which u is an integer selected from 1 to 5, preferably u being 1 or 2; q is an integer selected from 1 to 5, preferably q being 1, 2 or 3; and M+ is a cation, preferably selected from H+, alkali metal cations, alkali earth metal cations, NH4 + or any combination thereof, more preferably selected from H+, K+, Li+, Na+ and/or NH4 +; wherein the molar ratio of recurring units (RP1)/recurring units (R*P1) varies between 100/1 and 1/1, preferably between 50/1 and 2/1, more preferably between 40/1 and 3/1. [0009] A second aspect of the present invention is directed to a polymeric solution comprising the polymeric composition according to the first aspect of the present invention, which further comprises at least a solvent suitable to dissolve the copolymer (P1) and the PAES polymer (P2), wherein the combined weights of the copolymer (P1) and polymer (P2) is from 5 wt.% to 40 wt.%, preferably from 8 wt.% to 35 wt.%, more preferably from 10 wt.% to 25 wt.%, yet more preferably from 12 wt.% to 20 wt.%, based on the total weight of the polymeric solution. The polymeric solution may further comprise at least one pore forming agent. [0010] A third aspect of the present disclosure is directed to the use of the polymeric composition according to the first aspect of the present invention or the polymeric solution according to the second aspect of the present invention to make an article, preferably a film, tube, fiber or membrane, intended for medical applications and/or water filtration applications. [0011] A fourth aspect of the present invention is directed to an article, preferably a film, tube, fiber or membrane, intended for medical applications and/or water filtration applications. [0012] Brief description of the drawings [0013] FIG.1 compares the membrane thickness, water flux and gravimetric porosity for membrane E36 according to the invention containing a blend of a sulfonated PES and PES and for a comparative PES membrane CE35 made without the sPES copolymer additive, wherein these membranes are made using VIPS/NIPS technique and coagulation in water. [0014] FIG.2 compares the membrane thickness, water flux and gravimetric porosity for membrane E38 according to the invention containing a blend of a sulfonated PES and PES and for a comparative PES membrane CE37 made without the sPES copolymer additive, wherein these membranes are made using VIPS/NIPS technique and coagulation in a 30w/70w NMP:water bath. [0015] FIG.3 compares the membrane thickness, water flux and gravimetric porosity for membrane E41 according to the invention containing a blend of a sulfonated PES and PES and for a comparative PES membrane CE40 made without the sPES - 9 - SSPU 2022/035 copolymer additive, wherein are made using NIPS technique and coagulation in a 30w/70w NMP:water bath. [0016] Fig. 4 to 6 represent SEM pictures of membranes E24-E26 according to the invention, respectively. [0017] Fig.7 and 8 represent SEM pictures of two comparative membranes CE23 & CE31 made from PES, respectively. [0018] Fig.9 and 10 represent SEM pictures of the membranes E32 and E34 according to the invention, respectively. [0019] Fig.11 represents a SEM picture of a comparative membrane CE35 made from PES. [0020] Fig.12 and 13 represent SEM pictures of the membranes E36 and E38 according to the invention, respectively. [0021] FIG.14 compares the membrane thickness, water flux and gravimetric porosity for membrane E46 according to the invention containing a blend of a sulfonated PES and PPSU and for a comparative PPSU membrane CE45 made without the sPES copolymer additive, wherein these membranes are made using NIPS technique and coagulation in a 50w/50w NMP:water bath. Detailed description of preferred embodiments [0022] In the present application: - any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present disclosure; - where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components; any element or component recited in a list of elements or components may be omitted from such list; and - any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents. [0023] Polymeric composition [0024] According to the first aspect of the present invention, the polymeric composition comprises: from 5 to 50 parts by weight of the copolymer (P1), and from 50 to 95 parts by weight of the PAES polymer (P2), said parts by weight (“pbw”) being based on the combined weights of the copolymer (P1) and the PAES polymer (P2). - 10 - SSPU 2022/035 [0025] The polymeric composition comprises: - at least 6 pbw, or at least 7 pbw, or at least 8 pbw, or at least 9 pbw, or at least 10 pbw, of the copolymer (P1), and/or - at most 40 pbw, or at most 38 pbw, or at most 35 pbw, or at most 33 pbw, or at most 30 pbw, or at most 28 pbw, or at most 25 pbw, or at most 23 pbw, or at most 20 pbw, of the copolymer (P1), and - at least 60 pbw, or at least 62 pbw, or at least 65 pbw, or at least 67 pbw, or at least 70 pbw, or at least 702 pbw, or at least 75 pbw, or at least 77 pbw, or at least 80 pbw, of the PAES polymer (P2), and/or - at most 94 pbw, or at most 93 pbw, at most 92 pbw, at most 91 pbw, at most 90 pbw, of the PAES polymer (P2), said pbw being based on the combined weights of the copolymer (P1) and the PAES polymer (P2). [0026] The polymeric composition more preferably comprises from 10 to 40 pbw or from 10 to 30 pbw or from 10 to 20 pbw, of the copolymer (P1), and from 60 to 90 pbw, or from 70 to 90 pbw or from 80 to 90 pbw, of the PAES polymer (P2), said pbw being based on the combined weights of the copolymer (P1) and the PAES polymer (P2). [0027] In the polymeric composition according to the invention, the copolymer (P1) comprises collectively at least 80 mol.% of recurring units (RP1) and (R*P1), and the PAES polymer (P2) comprises at least 80 mol.% of recurring units (RP2). The molar ratio of recurring units (RP1)/recurring units (R*P1) in the copolymer (P1) varies between 100/1 and 1/1, preferably between 50/1 and 2/1, more preferably between 40/1 and 3/1. [0028] The recurring units (RP2) may be the same or different than the recurring units (RP1) of copolymer (P1). The recurring units (RP2) are preferably not sulfonated and/or not carboxylated. Additionally, the recurring units (RP1) in the copolymer (P1) are preferably not sulfonated and/or not carboxylated. [0029] The PAES copolymer (P2) in the polymeric composition according to the invention is preferably not sulfonated and/or carboxylated. [0030] Sulfonated and/or carboxylated copolymer (P1) [0031] The copolymer (P1) in the polymeric composition according to the invention is sulfonated and/or carboxylated and comprises collectively at least 80 mol.% of: - recurring units (RP1) and - sulfonated and/or carboxylated recurring units (R*P1), comprising two carboxylated and/or sulfonated pendant groups which include – COO-M+ and/or ─ SO3-M+, in which M+ is a cation, preferably selected from H+, alkali metal cations, - 11 - SSPU 2022/035 alkali earth metal cations, NH4+ or any combination thereof, more preferably selected from H+, K+, Li+, Na+ and/or NH4+, said carboxylated and/or sulfonated pendant groups being covalently attached via a linking group including – S – (CH2)u – or – S – (CH2)q – to different aromatic rings in the recurring units (RP1 *), in which u is an integer selected from 1 to 5, preferably u being 1 or 2; and q is an integer selected from 1 to 5, preferably q being 1, 2 or 3. [0032] The sulfonated and/or carboxylated groups of copolymer (P1) are derived from internal functionalizations within the copolymer backbone. The internal functionalizations result from a step-growth polymerization in the presence of an allyl-substituted monomer, which advantageously makes the system versatile as the content of functionality can be adjusted by varying the content of allyl- substituted monomer in the reaction mixture. The allyl-substituted monomer comprises two pendant allyl group side chains, each preferably comprising from 3 to 7 carbon atoms. [0033] The copolymer (P1) in the polymeric composition of the present invention is in the form of a racemate product. Due to the presence of the base and high temperature during polymerization of the copolymer precursor, the allyl-substituted monomer usually racemizes during polymerization in such a way that the position of the double bond may change along the side chains. This leads to the formation of molecules differing from each other by the fact that the double bond may be at the end of the side chain or one carbon before the end of the side chain. The amount of racemization depends on the reaction time and temperature. Sulfonated and/or carboxylated recurring units (R*P1) of the copolymer (P1) comprises two sulfonated and/or carboxylated pendant groups in free acid form (— SO3H or —COOH) and/or in deprotonated form (– COOM and/or ─ SO3M, in which M is selected from alkali metals, alkali earth metals, ammonium or any combination thereof), on two side chains which are covalently attached via a linking group including – S – (CH2)q – or – S – (CH2)q – to different aromatic rings in the recurring units (R*P1), in which u is an integer selected from 1 to 5, preferably u being 1 or 2; and q is an integer selected from 1 to 5, preferably q being 1, 2 or 3. A skilled person in the art knows that the sulfonic acid groups may be in form of free acid form or in deprotonated form, depending on the conditions. Preferably, the sulfonated and/or carboxylated copolymer (P1) comprises two – SO3M pendant groups which are covalently attached via a linking group which includes – S – (CH2)3 – to two different aromatic rings in the recurring units (R*P1). [0034] The copolymer (P1) of the present invention comprises collectively at least 80 mol.% of recurring units (RP1) and (R*P1), based on the total number of moles of - 12 - SSPU 2022/035 recurring units in the . The copolymer (P1) may for example comprise collectively at least 85 mol.%, at least 90 mol.%, at least 95 mol.%, at least 98 mol.%, at least 99 mol.%, of recurring units (RP1) and (R*P1), based on the total number of moles of recurring units in the copolymer (P1). Substantially all of the recurring units in the copolymer (P1) are recurring units (RP1) and (R*P1). The expression total number of moles of recurring units in the copolymer (P1). Substantin copolymer (P1) is hereby intended to mean that minor amounts, generally below 1 % moles, preferably below 0.5 % moles, of other recurring units may be tolerated, e.g. as a result of lower purity in monomers used. [0035] The recurring units (RP1) of formula (M1) in the copolymer (P1) are preferably non-sulfonated, or non-carboxylated, or both non-sulfonated and non- carboxylated, meaning that none of the R1 in formula (M1) comprises –SO3- and/or –COO- groups. [0036] In recurring units (RP1) of formula (M1), i is preferably 0. [0037] In recurring units (RP1) of formula (M1), T1 is preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2- and a mixture therefrom. The copolymer (P1) may, for example, comprise some recurring units (RP1) in which T1 is -C(CH3)2- and other recurring units (RP1) in which T1 is -SO2-. T1 in recurring units (RP1) of formula (M1) is more preferably -C(CH3)2- and/or -SO2-. [0038] In recurring units (RP1) of formula (M1), each R4 may be independently selected from the group consisting of a C1-C12 moiety optionally comprising one or more than one heteroatoms; phosphonic acid and phosphonate groups; amine, amide and quaternary ammonium groups. [0039] Preferably, i is zero for each R1 of recurring units (RP1) of formula (M1). [0040] The recurring units (RP1) in the copolymer (P1) are more preferably according to any of the following formulae (M1a), (M1b) or (M1c): - 13 - SSPU 2022/035 (M1c). [0041] 50 mol. %, or at least 55 mol. % or at least 60 mol.%, or at least 66 mol.% or at least 70 mol.% or at least 75 mol.% or at least 80 mol.%, or at least 82 mol.%, of the recurring units (RP1) of formula selected from any of formulae: (M1), (M1a), (M1b) or (M1c), based on the total number of moles of recurring units in the copolymer (P1). [0042] The copolymer (P1) preferably comprises at most 98 mol. %, or at most 97 mol. %, or at most 96 mol. %, or at most 95 mol. %, or at most 94 mol. %, or at most 93 mol. %, of the recurring units (RP1) of formula selected from any of formulae: (M1), (M1a), (M1b) or (M1c), based on the total number of moles of recurring units in the copolymer (P1). [0043] The copolymer (P1) preferably comprises typically at least 2 mol.%, or at least 3 mol.%, or at least 4 mol.%, or at least 5 mol.%, or at least 6 mol.%, or at least 7 mol.%, of the recurring units (R*P1) of the formula (N), based on the total number of moles of recurring units in the copolymer (P1). [0044] The copolymer (P1) preferably comprises at most 50 mol. %, or less than 50 mol.%, or at most 45 mol. %, or at most 40 mol. %, or at most 34 mol. %, or at most 30 mol. %, or at most 25 mol. %, or at most 20 mol. %, or at most 18 mol. %, of the recurring units (RP1) of the formula (N), based on the total number of moles of recurring units in the copolymer (P1). [0045] In the recurring units (R*P1) of the formula (N) described earlier, each R2 in the GN groups is preferably – (CH2)q – SO3M, in which q is an integer from 1 to 5, preferably q = 1, 2, 3, and M is preferably H, Li, Na, K, and/or NH4. Each R2 in the GN groups is more preferably – (CH2)3 – SO3H, – (CH2)3 – SO3Li, – (CH2)3 – SO3K, or – (CH2)3 – SO3Na, and/or – (CH2)3 – SO3NH4. [0046] In the recurring units (R*P1) of the formula (N) described earlier, W in GN represented by any of the formulae (GN1), (GN2), (GN3), (GN4), (GN5), (GN6) is preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2- and a mixture therefrom. In some instances, the copolymer (P1) may be such that W is - C(CH3)2- in some recurring units (R*P1) and W is -SO2- in other recurring units (R*P1). [0047] In the recurring units (R*P1) of the formula (N) described earlier, each R1 is independently selected from the group consisting of a C1-C12 moiety optionally - 14 - SSPU 2022/035 comprising one or more than phosphonic acid and phosphonate groups; amine, amide and quaternary ammonium groups. [0048] Preferably, i is zero for each R1 of the recurring units (R*P1). [0049] In the recurring units (R*P1) of the formula (N) described earlier, in which GN is represented by any of the formulae (GN1), (GN2), (GN3), (GN4), (GN5), (GN6), k is preferably zero and j is preferably 3. [0050] In some instances, the copolymer (P1) may be such that - W is -C(CH3)2- in recurring units (R*P1) and T1 is -SO2- in recurring units (RP1); or - W is -C(CH3)2- in recurring units (R*P1) and T1 is -C(CH3)2- in recurring units (RP1); or - W is -C(CH3)2- in recurring units (R*P1) and T1 is a bond in recurring units (RP1); or - W is -SO2- in recurring units (R*P1) and T1 is -SO2- in recurring units (RP1); or - W is -SO2- in recurring units (R*P1) and T1 is -C(CH3)2-in recurring units (RP1). [0051] The copolymer (P1) is preferably a sulfonated copolymer with a degree of sulfonation from 4 to 50 mol% or a carboxylated copolymer with a degree of carboxylation from 4 to 50 mol%. The copolymer (P1) is more preferably a sulfonated copolymer with a degree of sulfonation from 4 to 30 mol%, or from 4 to 25 mol%, or from 4 to 20 mol%, or a carboxylated copolymer with a degree of carboxylation from 4 to 30 mol%, or from 4 to 25 mol%, or from 4 to 20 mol%. The copolymer (P1) is even more preferably a sulfonated copolymer with a degree of sulfonation from 4 to 18 mol%. [0052] The copolymer (P1) in the polymeric composition of the present invention has a Tg ranging from 120 and 250°C, preferably from 170 and 240°C, more preferably from 180 and 230°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418. [0053] PAES polymer (P2) [0054] The PAES polymer (P2) in the polymeric composition of the present invention is preferably a polymer which does not comprise sulfonated groups in free acid form (—SO3H) and/or in deprotonated form, and also does not comprise carboxylated groups in free acid form (—COOH) and/or in deprotonated form, wherein the counterion (M+) to —SO3- or —COO- in the deprotonated form (—SO3M or — COOM) may be an alkali metal or alkali earth metal cation or NH4 +, such as NH4 +, Na+ Li+, and/or K+. [0055] In the recurring units (RP2) of the formula (M2) described previously, T2 is preferably selected from the group consisting of a bond, -SO2- and -C(CH3)2-. [0056] In the recurring units (RP2) of the formula (M2) described previously, each R4 may be independently selected from the group consisting of a halogen, alkyl, alkenyl, - 15 - SSPU 2022/035 alkynyl, aryl, ether, thioether, amide, imide, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium. [0057] In the recurring units (RP2) of the formula (M2) each m is preferably 0. [0058] The recurring units (RP2) of the PAES polymer (P2) are preferably represented by at least one of the following formulae (M1a), (M1b), or (M1c): , units (RP2) of formula selected from any of formulae (M2), (M1a), (M1b) or (M1c), based on the total number of moles of recurring units in the polymer (P2). More preferably substantially all of the recurring units in the polymer (P2) are the recurring units (RP2) of formula selected from any of formulae: (M2), (M1a), (M1b) or (M1c). The expression “substantially all” concerning the recurring units selected from any of formulae: (M2), (M1a), (M1b) or (M1c) in the polymer (P2) is hereby intended to mean that minor amounts, generally below 1 % moles, preferably below 0.5 % moles, of other recurring units may be tolerated, e.g. as a result of lower purity in monomers used. [0060] The PAES polymer (P2) in the polymeric composition of the present invention is preferably a polysulfone (PSU), a polyethersulfone (PES), or a polyphenylsulfone (PPSU), more preferably a PES or PPSU. [0061] As used herein, a polyethersulfone (PES) denotes any polymer comprising at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 99 mol. % of recurring units (RPES) of the formula (M1a), the mol. % being based on the total number of moles of recurring units in the PES polymer. PES can be prepared by known methods and is notably available as VERADEL® PES from Solvay Specialty Polymers USA, L.L.C. - 16 - SSPU 2022/035 [0062] As used herein, a polysulfone denotes any polymer comprising at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 99 mol. % of recurring units (RPSU) of the formula (M1b), the mol. % being based on the total number of moles of recurring units in the PSU polymer. PSU can be prepared by known methods and is notably available as Udel® PSU from Solvay Specialty Polymers USA, L.L.C. [0063] As used herein, a polyphenylsulfone (PPSU) denotes any polymer comprising at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 99 mol. % of recurring units (RPPSU) of the formula (M1c), the mol. % being based on the total number of moles of recurring units in the PPSU polymer. PPSU can be prepared by known methods and is notably available as RADEL® PPSU from Solvay Specialty Polymers USA, L.L.C. [0064] The recurring units (RP1a) of the copolymer (P1) and the recurring units (RP2) of the PAES polymer (P2) preferably are represented by the same formula selected from (M1a), (M1b) or (M1c), more preferably represented by the same formula (M1a). [0065] Alternatively, the recurring units (RP1a) of the copolymer (P1) may be represented by the formula (M1a) and the recurring units (RP2) of the PAES polymer (P2) are represented by the formula (M1b) or (M1c). [0066] The polymer (P2) in the polymeric composition of the present invention has a Tg ranging from 120 and 250°C, preferably from 170 and 240°C, more preferably from 180 and 230°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418. [0067] Process for preparing the copolymer (P1) [0068] The copolymer (P1) can be prepared by various chemical processes, notably by free radical-thermal reaction, by free radical-UV reaction, by base-catalyzed reaction or by nucleophilic-catalysed reaction. [0069] The process for preparing copolymer (P1) comprises reacting an allyl/vinylene- functionalized copolymer precursor (P0) with a compound R2 – SH, wherein R2 is independently selected from the group consisting of: ─ (CH2)u – COOM, ─ (CH2)q – SO3M, and any combination thereof, with u being an integer selected from 1 to 5, preferably u being 1 or 2, with q being an integer selected from 1 to 5, preferably q being 1, 2 or 3, and with M being selected from H, alkali metals, alkali earth metals, ammonium or any combination thereof, more preferably selected from H, Li, Na and/or NH4. [0070] The copolymer precursor (P0), used in the process notably comprises recurring units (R*P0) with 2 pendant allyl/vinylene side-chains, which are reactive with the compound R2 – SH. The copolymer (P0) more precisely comprises: - recurring units (RP0) of formula (M): - 17 - SSPU 2022/035 , - , wherein - a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, ester, amide, imide, alkali or metal alkaline earth phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4, preferably i=0; - T1 is selected from the group consisting of a bond, -CH2-; -O-; -SO2-; -S-; - C(O)-; -C(CH3)2- ;-C(CF3)2-; -C(=CCl2)-; -C(CH3)(CH2CH2COOH)-; -N=N-; - RaC=CRb-, where each Ra and Rb, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; -(CH2)m- and -(CF2)m- with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof, - GP is selected from the group consisting of at least one of the following formulas:
- 18 - SSPU 2022/035 , wherein - W is selected from the group consisting of a bond, -SO2-, -C(CH3)2- and any mixture therefrom, preferably selected from -C(CH3)2- and/or –SO2-; - each k is independently 0 or an integer from 1 to 4, preferably k= 0, 1, 2, or 3, more preferably k=0; and wherein the molar ratio of recurring units (RP0a)/recurring units (R*P0a) varies between 100/1 and 1/1, preferably between 50/1 and 2/1, more preferably between 40/1 and 3/1. [0071] In some embodiments, the copolymer precursor (P0) is such that k is zero in recurring units (R*P0). [0072] The molar ratio of compound (R2–SH)/polymer precursor (P0) varies between varies between 0.01/100 and 100/0.01, preferably between 1/100 and 100/1, more preferably between 1/1 and 10/1. [0073] The temperature of the reaction to prepare copolymer (P1) varies between 10°C and 300°C, preferably between room temperature and 200°C, or more preferably between 35°C and 100°C. [0074] The process to prepare copolymer (P1) may be carried out by exposing the reaction mixture to UV light at a wavelength ranging from 300 nm to 600 nm, preferably from 350 nm to 450 nm., more preferably at 365 nm. [0075] In some embodiments, the copolymer precursor (P0) is such that T1 in recurring units (RP0) is selected from the group consisting of a bond, -SO2-, -C(CH3)2- and - 19 - SSPU 2022/035 any combination thereof. The (P0) may, for example, comprise recurring units (RP0) in which T1 is -C(CH3)2- and recurring units (RP1) in which T1 is -SO2-. [0076] T1 in recurring units (RP0) is preferably -SO2- or -C(CH3)2-. [0077] In some embodiments, the copolymer precursor (P0) is such that each R1 is independently selected from the group consisting of a C1-C12 moiety optionally comprising one or more than one heteroatoms; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups. [0078] In some embodiments, the copolymer precursor (P0) is such that i is zero for each R1 of recurring units (RP0) and recurring units (R*P0). [0079] In some embodiments, the copolymer precursor (P0) is such that j is 2 in recurring units (RP0). [0080] In some embodiments, the copolymer precursor (P0) is such that recurring units (RP0) are represented by at least one of the following formulae (M1a), (M1b), or (M1c): , at least 90 mol.%, at least 95 mol.%, at least 99 mol.% of recurring units (RP0) and (R*P0), based on the total number of moles of recurring units in the copolymer precursor (P0). Substantially all of the recurring units in the copolymer precursor (P0) may be recurring units (RP0) and (R*P0). [0082] The copolymer precursor (P0) may have a Tg ranging from 120 and 250°C, preferably from 170 and 240°C, more preferably from 180 and 230°C, as measured by differential scanning calorimetry (DSC) according to ASTM D3418. [0083] The compound R2 – SH used to react the copolymer precursor (P0) may be such that R2 in recurring units (R*P1) is independently selected from the group consisting of: - 20 - SSPU 2022/035 – CH2 – COOM, in which M is H, K or Na, more preferably H, and – (CH2)3 – SO3M , in which M is preferably H, K or Na, more preferably Na. [0084] The compound R2 – SH is preferably 3-mercapto-1-propanesulfonic acid sodium salt (“MPS thiol”) or thioglycolic acid (HS-CH2-COOH). [0085] The reaction to prepare copolymer (P1) may be carried out in a solvent, sometimes referred to as “reaction solvent”. The reaction solvent preferably comprises, or consists essentially of, for example a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2- pyrrolidone (NEP), N,N-dimethylformamide (DMF), N,N dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole and sulfolane. The reaction solvent may also comprise, or consist essentially of, chloroform or dichloromethane (DCM). The reaction solvent preferably comprises, or consists essentially of, DMSO, sulfolane or NMP. In some embodiments, the reaction solvent may further comprise up to 10 wt.% water, preferably up to 7.5 wt.% water, more preferably up to 5 wt.% water (based on total weight of reaction solvent). [0086] The reaction to prepare copolymer (P1) may be carried out in the presence of a base, for example selected from the group consisting of potassium carbonate (K2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3) and sodium tert- butoxide. The base may also be selected from the group consisting of N-Ethyl-N- (propan-2-yl)propan-2-amine (Hunig base), triethylamine (TEA) and pyridine. [0087] The reaction to prepare copolymer (P1) may be carried out in the presence of: - at least one free radical initiator, preferably 2,2'-Azobis(2-methylpropionitrile) (AIBN), and/or - at least one catalyst, preferably selected from peroxides. [0088] The peroxide catalyst may include a hydroperoxide. [0089] When the free radical initiator and the compound R2 – SH are soluble in the reaction solvent, the compound R2 – SH may be mixed in a solution containing the copolymer (P0) in the reaction solvent, and then the free radical initiator may be added to the resulting solution to initiate the reaction and form the copolymer (P1). If the compound R2 – SH is the MPS thiol, because the MPS thiol has good solubility in DMSO, such an embodiment is particular advantageous when the reaction solvent comprises at least 50 wt.% and up to 100 wt.% DMSO. [0090] The amount of copolymer (P1) at the end of the reaction is at least 10 wt.% based on the total weight of the copolymer precursor (P0) and the solvent, for example at least 15 wt.%, at least 20 wt.% or at least 30 wt.%. - 21 - SSPU 2022/035 [0091] At the end of the reaction, (P1) is separated from the other components (salts, base, …) to obtain a solution. Filtration can for example be used to separate the copolymer (P1) from the other components. The solution can then be used ’as is’ for reacting the copolymer (P1) with other compounds, or alternatively, the copolymer (P1) can be recovered from the solvent, for example by coagulation or devolatilization of the solvent. [0092] The cations of the sulfonated and/or carboxylated groups may be exchanged by other cations. For example the copolymer (P1) in which the sulfonated groups are in acid form (- SO3H) may be dissolved in a suitable solvent, and then the copolymer (P1) may be precipitated in a NH4OH methanol solution to deprotonate the sulfonate to form the - SO3NH4 groups. Alternatively, the copolymer (P1) in solid form may be washed in an aqueous solution containing an appropriate desired cation to be exchanged, such as the cation being in form of salt or acid. [0093] Process for preparing copolymer (P0) [0094] The allyl/vinylene-functionalized copolymer (P0) used in the process to make copolymer (P1) has been prepared by condensation of at least one aromatic dihydroxy monomer (a1), with at least one aromatic sulfone monomer (a2) comprising at least two halogen substituents and at least one allyl-substituted aromatic dihydroxy monomer (a3), as well as an additional agent, for example an end-capping agent or a protonating agent. [0095] The condensation to prepare copolymer precursor (P0) is preferably carried out in a solvent. When the condensation to prepare copolymer (P0) is carried out in a solvent, the solvent is for example a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N,Ndimethylformamide (DMF), N,N dimethylacetamide (DMAc), 1,3-dimethyl-2- imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene and sulfolane. The condensation to prepare the copolymer precursor (P0) is preferably carried out in sulfolane or NMP. [0096] The condensation to prepare the copolymer precursor (P0) may be carried out in the presence of a base, for example selected from the group consisting of potassium carbonate (K2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3) and sodium tert-butoxide. The base acts to deprotonate the components (a1) and (a3) during the condensation reaction. [0097] The molar ratio (a1)+(a3)/(a2) may be from 0.9 to 1.1, for example from 0.92 to 1.08 or from 0.95 to 1.05. - 22 - SSPU 2022/035 [0098] The monomer (a2) is a 4,4- comprising at least one of a 4,4’- dichlorodiphenyl sulfone (DCDPS) or 4,4’ difluorodiphenyl sulfone (DFDPS), preferably DCDPS. [0099] The monomer (a1) comprises, based on the total weight of the monomer (a1), at least 50 wt.% of 4,4’ dihydroxybiphenyl (biphenol), at least 50 wt.% of 2,2-bis(4- hydroxyphenyl)propane (bisphenol A) or at least 50 wt.% of 4, 4’ dihydroxydiphenyl sulfone (bisphenol S). [00100] The monomer (a3) comprises, based on the total weight of the monomer (a1), at least 50 wt.% of 2,2’-diallylbisphenol A (DABA). [00101] According to the condensation to prepare copolymer precursor (P0), the monomers of the reaction mixture are generally reacted concurrently. The reaction is preferably conducted in one stage. This means that the deprotonation of monomers (a1) and (a3) and the condensation reaction between the monomers (a1)/(a3) and (a2) takes place in a single reaction stage without isolation of the intermediate products. [00102] According to an embodiment, the condensation is carried out in a mixture of a polar aprotic solvent and a solvent which forms an azeotrope with water. The solvent which forms an azeotrope with water includes aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like. It is preferably toluene or chlorobenzene. The azeotrope-forming solvent and the polar aprotic solvent are used typically in a weight ratio of from about 1:20 to about 1:1, preferably from about 1:10 to about 1:1 or from about 1:5 to about 1:1. Water is continuously removed from the reaction mass as an azeotrope with the azeotrope- forming solvent so that substantially anhydrous conditions are maintained during the polymerization. The azeotrope-forming solvent, for example, chlorobenzene, is removed from the reaction mixture, typically by distillation, after the water formed in the reaction is removed leaving the copolymer precursor (P0) dissolved in the polar aprotic solvent. [00103] The temperature of the reaction mixture to prepare copolymer precursor (P0) is kept at about 150°C to about 350°C, preferably from about 210°C to about 300°C for about one to 15 hours. [00104] Depending on the method used for making the copolymer (P1), and the possible use of an additional agent during the condensation process, for example an end- capping agent or an protonating agent, the copolymer precursor (P0) possesses end groups derived from the monomers and/or end groups from derived from the end-capping or protonating agents. As the copolymer precursor (P0) is generally manufactured by a polycondensation reaction between a dihydroxy component and a dihalo component, its end groups usually include hydroxyl groups and halo- - 23 - SSPU 2022/035 groups (such as chlorinated end or fluorinated end groups). However, when for example an end-capping agent is used, based on the stoichiometry of the starting monomers (i.e. excess of dihydroxy monomers or excess of dihalo monomers), the remaining halo-groups may be at least partially converted into non- halogenated end groups. [00105] The inorganic constituents, for example sodium chloride or potassium chloride or excess of base, can be removed, before or after isolation of the copolymer precursor (P0), by suitable methods such as dissolving and filtering, screening or extracting. [00106] According to an embodiment, the amount of copolymer precursor (P0) at the end of the condensation is at least 30 wt.% based on the total weight of the copolymer precursor (P0) and the polar aprotic solvent, for example at least 35 wt.% or at least or at least 37 wt.% or at least 40 wt.%. [00107] At the end of the reaction, the copolymer precursor (P0) is separated from the other components (salts, base, …) to obtain a solution. Filtration can for example be used to separate the copolymer (P0) from the other components. The solution can then be used as such for reacting the copolymer precursor (P0) with the compound R2 – SH in the process of the present invention, or alternatively, the copolymer precursor (P0) can be recovered from the solvent, for example by coagulation or devolatilization of the solvent. [00108] Polymeric Solution [00109] The second aspect of the present invention is directed to a polymeric solution comprising the polymeric composition as described herein according to the first aspect of the present invention. [00110] The polymeric solution is preferably used to make an article such as membrane, tube, fiber or film. [00111] The polymeric solution further comprises at least a solvent in which the copolymer (P1) and the PAES polymer (P2) are soluble. [00112] The term “solubility” or “soluble” is defined herein as the maximum amount of polymer, measured in terms of weight of the polymer per weight of solution, which dissolves at a given temperature affording a transparent homogeneous solution without the presence of any phase separation in the system. The ‘polymer’ in such a definition refers to the copolymer (P1), the PAES polymer (P2), or the blend of copolymer (P1) and PAES polymer (P2). [00113] The solvent in the polymeric solution of the present invention may be selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl isosorbide (DMIso), methyl 5-(dimethylamino)-2-methyl-5- - 24 - SSPU 2022/035 oxopentanoate (Rhodiasolv® , cyrene, ε-caprolactam, butyrolactone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, sulfolane and any combination of two or more thereof. [00114] The concentration of the solvent in the polymeric solution may be at least 20 wt.%, at least 30 wt.%, or at least 40 wt.%, based on the total polymer solution weight and/or is at most 80 wt.%; at most 70 wt.%; or at most 60 wt.%, based on the total polymer solution weight. [00115] At least one co-solvent may be also present, in addition to the main solvent described above, in the polymeric solution of the present invention. Examples of co-solvent may be benzyl alcohol, ethanol, isopropyl alcohol and/or sulfolane in instances when sulfolane is not used as the main solvent in the polymeric solution. The concentration of the co-solvent may be from 0.5 wt.% to 15 wt. % based on the total polymer solution weight. [00116] When the solution contains both at least one solvent and at least one co-solvent, the total concentration of the solvent(s) and co-solvent(s) in the polymeric solution may be at least 20 wt.%, at least 30 wt.%, or at least 40 wt.%, based on the total polymer solution weight and/or is at most 80 wt.%; at most 70 wt.%; or at most 60 wt.%, based on the total weight of polymeric solution. [00117] The overall concentration of the polymers (copolymer P1 and polymer P2) in the polymeric solution should be at least 8 wt.%, preferably at least 10 wt.%, preferably at least 12 wt.%, based on the total weight of the solution. Typically the concentration of the polymers (copolymer P1 and polymer P2) in the polymeric solution does not exceed 40 wt.%, preferably it does not exceed 30 wt.%, more preferably it does not exceed 25 wt.%, yet more preferably it does not exceed 20 wt.%, based on the total weight of the polymeric solution. [00118] The combined weights of the copolymer (P1) and polymer (P2) in the polymeric solution may be from 5 wt.% to 40 wt.% or from 8 wt.% to 40 wt.%, preferably from 8 wt.% to 35 wt.% or from 8 wt.% to 30 wt.%, more preferably from 10 wt.% to 25 wt.%, yet more preferably from 10 wt.% to 25 wt.% or from 12 wt.% to 20 wt.%, said wt.% being based on the total weight of the polymeric solution. [00119] The total concentration of the copolymer (P1) and the polymer (P2) ranging from 15 to 20 wt.% with respect to the total weight of polymeric solution has been found particularly advantageous. [00120] The polymeric solution may further comprise at least one pore forming agent selected from the group consisting of at least one polyvinylpyrrolidone (“PVP”) preferably having a molecular weight of at least 5,000 g/mol to 360,000 g/mol; at least one polyalkylene glycol (e.g., a polyethylene glycol “PEG”) with a formula - 25 - SSPU 2022/035 weight ≥ 200 g/mol, 200 g/mol to 900 g/mol; at least one (poly)hydroxyl aliphatic alcohol having from 1 to 6 carbon atoms, preferably at least one glycerol compound, at least one carboxylic acid comprising at least 3 carbon atoms, such as propionic acid, and any combination thereof. [00121] The (poly)hydroxyl aliphatic alcohols having from 1 to 6 carbon atoms or derivatives thereof may comprise or be at least one ethylene glycol compound and/or at least one glycerol compound. [00122] The expression “ethylene glycol compound” is intended to encompass ethylene glycol, dimers and/or trimers thereof, as well as mono-ether and mono-ester derivatives, to the extent that the ethylene glycol compound comprises at least one free hydroxyl group. Preferred ethylene glycol compounds are selected from the group consisting of ethylene glycol, diethylene glycol (DEG), triethylene glycol (TEG), aliphatic mono-ethers and mono-esters, in particular methyl, ethyl or butyl mono-ethers and acetyl monoesters. [00123] The expression “glycerol compound” is intended to encompass glycerol and dimers thereof, as well as mono-ether, di-ether, mono-ester and di-ester derivatives, to the extent that the glycerol compound comprises at least one free hydroxyl group. [00124] Preferred glycerol compounds are selected from the group consisting of glycerol, aliphatic mono- and di-esters thereof, in particular mono-acetyl glycerol, di-acetyl glycerol, aliphatic mono- and di-ethers thereof, in particular methyl, ethyl or butyl mono-ethers or di-ethers, including notably mono-ter-butyl-glycerol, di-ter-butyl- glycerol; glycerol carbonate; glycerol acetals derived from aliphatic aldehydes, including butanal, pentanal, hexanal, octanal and decanal glycerol acetals. [00125] The carboxylic acid comprising at least 3 carbon atoms is preferably selected from propionic acid, butyric acid, and/or valeric acid, more preferably propionic acid. [00126] The one or more pore forming agent(s), when added to the polymeric solution, is/are present in amounts typically ranging from 0.5 wt.% to 40 wt.%, preferably from 1 wt.% to 40 wt.%, more preferably from 5 wt.% to 35 wt.%, yet more preferably from 10 wt.% to 30 wt.% or from 15 wt.% to 25 wt.%, said wt.% being based on the total weight of the polymeric solution. [00127] When one or more PEG pore forming agents are used, their amount is generally of from 10 wt.% to 40 wt.% or from 15 wt.% to 35 wt.%, or from 20 wt.% to 35 wt.% with respect to the total weight of polymeric solution. The PEG preferably has a formula weight from 200 to 900 g/mol. [00128] When one or more PVP pore forming agents are employed, their amount is generally from 2 wt.% to 10 wt.% or from 4 wt.% to 8 wt.% with respect to the - 26 - SSPU 2022/035 total weight of polymeric PVP preferably has a molecular weight of from 5,000 g/mol to 360,000 g/mol. [00129] When one or more PHAs having from 1 to 6 carbon are employed as pore forming agents, their amounts generally should be at least 1% by weight, preferably at least 2% by weight, based on the total weight of the solution. Typically, the concentration of the PHAs in the solution does not exceed 20% by weight, preferably it does not exceed 15% by weight, more preferably it does not exceed 14% by weight, based on the total weight of the polymeric solution. [00130] When propionic acid is employed as a pore forming agent in the polymeric solution, its amounts is generally of from 10 to 40 wt.% or from 20 to 35 wt.% with respect to the total weight of polymeric solution. In example, a polymeric solution having from 15 wt.% to 20 wt.% of copolymer (P1) and polymer (P2) may be made with a blend of solvent (e.g., NMP) and propionic acid with a vol/vol ratio of from 50:50 to 95:5, preferably from 60:40 to 80:20, more preferably from 65:35 to 75:25, yet more preferably about 70:30. [00131] Alternatively, the polymer solution may exclude a pore forming agent, such as may exclude glycerol, a PVP and/or a PEG having a formula weight of at least 200. [00132] The polymeric solution may contain additional components, such as nucleating agents, fillers and the like. Alternatively, the polymer solution may exclude additional components, such as nucleating agents, fillers and the like. [00133] Use of the PAES copolymer (P1) [00134] Another aspect of the present invention provides the use of the polymeric composition or polymeric solution of the present invention for making an article (or a part thereof) as described herein. This aspect also relates to a method for making an article (or a part thereof) comprising the polymeric composition of the present invention or made from the polymeric solution of the present invention. [00135] The polymeric composition or polymeric solution of the present invention may be used to make a non-porous article, such as a dense film. Such a dense film may be a thick or thin film. Such use may include polymer solution casting. In such instances, the copolymer (P1) and polymer (P2) in the polymeric composition of the present invention may be the sole polymers in the non-porous article; alternatively, the non-porous article may further comprise at least another polymer. [00136] The polymeric composition or polymeric solution according to the invention may be used to make a porous article, such as porous film, hollow fiber, hollow tube or porous membrane, using a phase inversion technique selected from nonsolvent induced phase separation or thermally induced phase separation. Such use may - 27 - SSPU 2022/035 include casting or spinning a dope solution comprising the PAES copolymer, a solvent, optionally a co-solvent and optionally at least one pore forming agent, as described previously, into the porous article, which is then cooled or contacted with a non-solvent. Preferably, the copolymer (P1) and polymer (P2) are the sole aromatic sulfone polymers in the polymeric solution. [00137] Article comprising or made from the PAES copolymer (P1) [00138] Another aspect of the present invention provides an article (preferably a shaped article) comprising, or made from, the polymeric solution according to the invention. [00139] The article of the present invention comprising or made from the polymeric composition may be porous or non-porous. [00140] The article of the present invention comprising or made from the polymeric composition may preferably be a porous article such as porous film, hollow fiber, hollow tube, porous membrane, or a part thereof (such as a (internal) porous layer or porous coating). [00141] As used herein, a “coating” according to the present invention is generally understood to be a layer fixed to the surface of a substrate, especially adhering thereon. A coating may be a thin or thick layer, and/or may be a plurality of layers. The substrate used may be made from any suitable known materials, such as metals, insulating materials, semiconducting materials, crystalline or amorphous polymeric materials, textile fabrics or films. [00142] As used herein, a “fiber” according to the present invention is generally understood to be a flexible structure whose width is thin compared to its length. Fibers preferably have a thickness of 0.5 to 100 microns. [00143] As used herein, a “membrane” according to the present invention is a separating article. The membrane may be non-porous, partly porous, selectively permeable, such as a membrane which is pervious in one direction. or may be porous. [00144] The article of the present invention preferably excludes polymers other than the copolymer (P1) and the PAES polymer (P2). [00145] The polymeric composition may form all, or substantially all, of the article. In other words, the article of the present invention may be essentially made from the polymeric composition. [00146] When the article of the present invention is porous such as a porous film, hollow fiber, hollow tube, porous membrane, or a part thereof, the article may comprise the copolymer (P1) as a polymeric hydrophilic additive to at least one bulk PAES polymer (P2), preferably selected from the group consisting of PSU, PPSU, PES, and any combination thereof. In preferred instances, the copolymer (P1) is a polymeric additive to a bulk PES or PPSU polymer, and the weight fraction of the copolymer (P1) in the article may be from 5 to 40 wt.%, or from 10 to 40 wt.%, or - 28 - SSPU 2022/035 from 10 to 30 wt.%, or from 10 said wt.% based on the combined weights of copolymer (P1) and the bulk PAES polymer (P2). [00147] The copolymer (P1) in the polymeric composition of the present invention which is used as a polymeric additive in the hydrophobic bulk PAES polymer (P2) improves the wettability, water uptake, water flux rate of such hydrophobic bulk PSU, PPSU or PES polymers that are typically used in forming porous membranes for hemodialysis and for water filtration such as ultrafiltration and microfiltration applications. [00148] The polymeric composition of the present invention can be included in at least a portion of a surface of the article, such surface being intended to come in contact with an aqueous solution, water, a biological fluid such as blood, plasma, or serum, or a food product such as fruit juice, milk, beer. [00149] The polymeric composition of the present invention may be incorporated into an article having a polymeric layer. A person of ordinary skill in the art will know which layer is intended to contact a fluid such as an aqueous medium, such as water, an aqueous solution (e.g., alkaline), a biological fluid (e.g., blood, plasma or serum) and/or food product (e.g., fruit juice, milk, beer) based upon the article’s intended application setting. The polymeric layer may be an external or internal layer of the article. At least a portion of that layer may come into direct contact with the fluid in its intended application setting. For example, a medical device may have an external layer intended to come into direct contact with a biological fluid. A thin film composite device like a reverse-osmosis membrane or nanofiltration membrane may have a layer intended to come into direct contact with an aqueous medium or water. In particular, the article can comprise a thin selective layer disposed on an underlying layer or porous substrate. The thin selective layer may comprise, or be made from, the polymeric composition of the present invention, while the underlying layer or porous substrate has a composition which excludes at least the more hydrophilic copolymer (P1). Or the underlying layer or porous substrate may comprise, or be made from, the polymeric composition of the present invention, while the thin selective layer may has a composition which excludes at least the more hydrophilic copolymer (P1). Alternatively, both of the thin selective layer and the underlying layer or porous substrate contain the more hydrophilic copolymer (P1) and the polymer (P2). [00150] A film, tube, coating or layer of the present invention comprising or made from the polymeric composition of the present invention may have an average thickness of from about 25 μm to about 1 mm. - 29 - SSPU 2022/035 [00151] A porous membrane may be a membrane which can be characterized by its average pore diameter and porosity, i.e., the fraction of the total membrane that is porous. [00152] The porous membrane may have a gravimetric porosity (%) of 20 to 90 % and comprises pores, wherein at least 90 % by volume of the said pores has an average pore diameter of less than 5 μm. Gravimetric porosity of the porous membrane is defined as the volume of the pores divided by the total volume of the membrane. [00153] From an architectural perspective, porous membranes comprising the polymeric composition of the present invention may be provided under the form of flat structures (e.g. having a plurality of films or sheets), corrugated structures (such as corrugated sheets), tubular structures (e.g. having a plurality of tubes), or hollow fibers. Tubular porous membranes are classified based on their dimensions in tubular membranes having a diameter greater than 3 mm; capillary membranes, having a diameter comprised between 0.5 mm and 3 mm; and hollow fibers having a diameter of less than 0.5 mm. Capillary membranes are otherwise referred to as hollow fibers. Hollow fibers are particularly advantageous in applications where compact modules with high surface areas are required. [00154] As per the pore size is concerned, full range of membranes (non-porous and porous, including for microfiltration, ultrafiltration, nanofiltration, ion-exchange, and reverse osmosis) can be advantageously manufactured with the polymeric composition of the present invention; the pore distribution can be isotropic or anisotropic. [00155] Membranes having a uniform structure throughout their thickness are generally known as symmetrical membranes; membranes having pores which are not homogeneously distributed throughout their thickness are generally known as asymmetric membranes. Asymmetric membranes are characterized by a thin selective layer (0.1-1 μm thick) and a highly porous thick layer (100-200 μm thick) which acts as a support and has little effect on the separation characteristics of the membrane. As an example, the asymmetric membrane may comprise a thin selective layer comprising, or made from, the polymeric composition of the present invention, disposed on an underlying layer or substrate having a composition distinct from the polymeric composition of the present invention. Alternatively, the asymmetric membrane may comprise a support layer comprising, or made from, polymeric composition of the present invention, on top of which is disposed a thin selective layer having a composition excluding for example the more hydrophilic copolymer (P1). [00156] Method for making the article - 30 - SSPU 2022/035 [00157] An article (e.g., fiber, film, tube, or part thereof such as a layer or coating) according to the present invention can be made using any of the conventionally known preparation methods, such as non-limiting examples, by a polymer solution casting method or solution polymer spinning method. Different shaping techniques can be used depending on the final form of the article to be manufactured. [00158] Various techniques suitable for making the article according to the invention may be found in the book by Chang Dae Han entitled “Rheology and Processing of Polymeric Materials”, Vol 2 (2007), Oxford press, such as in Chapter 2: Plasticating Single-Screw Extrusion (pages 56-131), Chapter 6: Fiber Spinning (pages 257-302) and Chapter 8: Injection molding (pages 351-378). [00159] The method for making the article may comprise casting or spinning a polymer solution (sometimes referred to as “polymer dope solution”) into a pre-formed article (such as film, fiber, tube, membrane, coating, layer) which is then cooled and/or contacted with a non-solvent. The polymer dope solution comprises the copolymer (P1) and polymer (P2), the solvent in which the copolymer (P1) and the PAES polymer (P2), and optionally at least one pore forming agent. The pore forming agent may be at least one selected from at least one PVP preferably having a molecular weight of at least 5,000 g/mol to 360,000 g/mol; at least one PEG having a formula weight of at least 200, preferably from 200 to 900 g/mol; at least one PHA such as ethylene glycol, glycerol and/or triethylene glycol; at least one carboxylic acid such as propionic acid; or any combination thereof. [00160] Manufacture of porous article [00161] A porous fiber, film, tube or membrane, or part thereof (such as a layer or coating) according to the present invention may be prepared using a phase inversion technique selected from non-solvent induced phase separation and/or thermally induced phase separation. [00162] When the final article is a flat film, the polymer solution may be casted as a film over a flat supporting substrate, typically a plate, a belt or a fabric, or a microporous supporting membrane, typically by means of a casting knife, a draw- down bar or a slot die. [00163] Alternatively, the polymer solution may be spinned in the form of a tubular film. The tubular film may be manufactured using a spinneret, this technique being otherwise generally referred to as "spinning method". Hollow fibers and capillary membranes may be manufactured according to the spinning method. The term “spinneret” is hereby understood to mean an annular nozzle comprising at least two concentric capillaries: a first outer capillary for the passage of the polymer - 31 - SSPU 2022/035 solution and a second inner referred to as “lumen”) for the passage of a supporting fluid, also referred to as “bore fluid”. [00164] For the non-solvent induced phase separation (NIPS), the pre-shaped article is contacted with a non-solvent medium (medium [NS]) thereby providing a porous article. Such step of contacting with a medium [NS] is generally effective for precipitating and coagulating the polymers (P1) and (P2) constituting the pre- shaped article into a porous article. The polymers (P1) and (P2) may be precipitated in said medium [NS] by immersion in a coagulation bath containing a non-solvent medium [NS]. In some instances, the coagulation bath containing at least one non-solvent medium [NS] may also contain a solvent at the beginning of the coagulation, for example from 5 wt.% to 70 wt.% solvent or from 10 wt.% to 70 wt.% solvent, or from 20 wt.% to 60 wt.% solvent, or from 30 wt.% to 50 wt.% solvent, said wt.% being based on the total weight of the coagulation bath. The solvent content provided in the bath corresponds to the initial solvent concentration right before coagulation is started. The coagulation bath preferably comprises a non-solvent selected from water at least one alcohol and/or at least one polyalcohol, such as aliphatic alcohols having a short chain, for example from 1 to 6 carbon atoms, preferably methanol, ethanol, isopropanol, glycerol, ethylene glycol, diethylene glycol and/or triethylene glycol. The solvent in which the polymers (P1) and (P2) are soluble, in the coagulation bath may be selected from, but not limited to, NMP, NBP, NEP, sulfolane, DMAc, DMI, dimethyl isosorbide (DMIso), methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv® Polar-clean), cyrene, ε-caprolactam, butyrolactone, DMSO, or any combination of two or more thereof. The solvent present in the coagulation bath at the onset of the coagulation preferably comprises or consists essentially of NMP, sulfolane, DMAc, DMI, dimethyl isosorbide (DMIso), methyl 5- (dimethylamino) -2-methyl-5-oxopentanoate (Rhodiasolv® Polar-clean), cyrene, ε-caprolactam, butyrolactone, DMSO, or any combination of two or more solvents. [00165] The coagulation in the NIPS technique typically takes place in the coagulation bath at a temperature generally ranging from 15°C to 60°C, preferably from 20°C to 60°C, more preferably from 25°C to 50°C. [00166] Alternatively (or usually before immersing in a coagulation bath), contacting the pre-shaped article with medium [NS] may be accomplished by exposing it to a gaseous phase comprising vapors of such medium [NS]. This technique is termed “VIPS” for vapor induced phase separation. This typically takes place in a climatic chamber into which the pre-shaped article is introduced in the climatic chamber set at a temperature generally ranging from 20°C to 40°C, preferably at - 32 - SSPU 2022/035 about 35°C and a relative from 50 to 80% RH, preferably at about 60% of humidity. [00167] For the purpose of the present invention, the term “non-solvent” [NS] is intended to mean a medium consisting of one or more liquid substances incapable of dissolving the polymers (P1) and (P2), and which advantageously promotes the coagulation/precipitation of the polymers (P1) and (P2) from the polymeric solution. The medium (NS) typically comprises water and/or at least one alcohol or polyalcohol, preferably aliphatic alcohols having a short chain, for example from 1 to 6 carbon atoms, more preferably methanol, ethanol, isopropanol, glycerol, triethylene glycol, diethylene glycol, and/or ethylene glycol. [00168] For a thermally induced phase separation (“TIPS”), coagulation/precipitation of the PAES polymers (P1) and (P2) may be promoted by cooling. In this case, the cooling of the pre-shaped article may be typically carried out using any conventional techniques. Generally, when the coagulation/precipitation is thermally induced, the solvent in the polymeric solution is advantageously a “latent” solvent (solvent (LT)), i.e. a solvent which behaves as an active solvent towards the polymers (P1) and (P2) only when heated above a certain temperature, and which is not able to solubilize the polymers (P1) and (P2) below such temperature. When the polymer solution comprises a latent solvent, the pre- shaping step (e.g., casting) for the making of the article is generally carried out at a temperature high enough to maintain the polymer solution as a homogeneous solution. Cooling may be achieved by contacting the pre-shaped article with a cooling fluid, which may be a gaseous fluid (i.e. cooled air or cooled modified atmosphere) or may be a liquid fluid. In this latter case, it is usual to make use of non-solvent medium [NS] as above detailed, so that the techniques of non- solvent-induced and thermally-induced precipitation may occur simultaneously. It is nevertheless generally understood that even in circumstances where the precipitation of the polymers (P1) and (P2) is induced thermally, a further step of non-solvent-induced precipitation, that is to say, contacting with non-solvent medium [NS], is carried out, e.g. for finalizing the polymers’ precipitation and facilitating removal of the solvent(s). [00169] In cases where the polymeric solution comprises both solvent and non-solvent for the PAES polymers (P1) and (P2), at least partially selective evaporation of the solvent may be used for promoting coagulation/precipitation of both PAES polymers (P1) and (P2). In this case, solvent and non-solvent are typically selected so as to ensure the solvent having higher volatility than the non-solvent, so that progressive evaporation, generally under controlled conditions, of the - 33 - SSPU 2022/035 solvent leads to the polymers’ and hence actual contact of the pre- shaped article with non-solvent medium. [00170] When present in the polymeric solution, pore forming agents are generally at least partially, if not completely, removed from the porous article in the non- solvent medium [NS], during this step of the method of article manufacture. [00171] The method may further include additional treatment steps after shaping and precipitation/coagulation, for instance steps of rinsing and/or stretching the porous article and/or a step of drying the same, especially when the article is a porous membrane. [00172] For instance, the porous article may be additionally rinsed, preferably with deionized water. [00173] Further, the porous article may be advantageously stretched so as to increase its average porosity. [00174] The porous article may be advantageously stored in water (storing medium) so as to maintain it in a wet form. [00175] The porous article may be advantageously stored in water plus glycerol (storing medium), with preferably from 5 wt.% to 20 wt.% glycerol based on total weight of storing medium (water + glycerol), and then dried at room temperature. [00176] The porous article may be dried from its storing medium, either water or water+glycerol, at a temperature of advantageously at least 30°C. Drying can be performed under air or a modified atmosphere, e.g., under an inert gas, typically exempt from moisture (water vapor content of less than 0.001% v/v) after their wetting in isopropyl alcohol or alcohol. Drying can alternatively be performed under vacuum. [00177] A suitable example of a method for forming a porous membrane from a polyaryl ether sulfone polymer is described in US2019/054429A1 (Solvay Specialty Polymers USA), incorporated herein by reference. [00178] Manufacture of a non-porous article [00179] A non-porous (or dense) fiber, film, membrane, or part thereof (such as a layer or coating) according to the present invention may be prepared using polymer solution casting. In preferred instances, the PAES polymers (P1) and (P2) may be the sole polymers in the non-porous article; or the non-porous article may further comprise at least one other polymer different than PAES polymers (P1) and (P2). [00180] After the polymeric solution containing the PAES polymers (P1) and (P2) dissolved in a solvent is casted as a film on a substrate, the solvent is generally evaporated to generate the non-porous film. - 34 - SSPU 2022/035 [00181] Generally the production of articles from the polymeric solution comprising both PAES polymers (P1) and (P2) does not involve the use of a non- solvent medium, meaning that, when using polymer solution casting, the polymeric solution comprising both PAES polymers (P1) and (P2) preferably excludes a non-solvent medium. [00182] Non-porous articles may be alternatively generated by classical melt processing techniques like film, tube or pipe extrusion, wire coating, injection molding and the like. In all those processes the common denominator is the use of an equipment (extruder, injection molder), where the polymer is fed (in powder or pellets form), melted and then formed into a desired shape. The shaped article is then left to cool in air or water. [00183] Non-porous articles can also be generated by solvent medium like in coating or casting. In such instances, the solvent is allowed to evaporate. In a typical industrial process to make a self-standing thin cast film, a polymer solution is fed through a slot die via a gear pump and cast on a moving support (belt). The solvent is let to evaporate in an oven chamber after casting. A polymer film is then detached from the carrier belt. See for example, Ulrich Siemann, “Solvent Cast technology – a versatile tool for thin film production”, in Progr Colloid Polym Sci (2005) vol.130: pages 1–14, Springer publisher. [00184] Applications [00185] The polymeric composition or polymeric solution according to the present invention which comprises the PAES copolymer (P1) and the PAES polymer (P2) is particularly suitable for manufacturing articles intended for contact with an aqueous medium. The aqueous medium may include or may be a biological fluid such as blood, serum, a food product such as beverages (e.g., fruit juice, milk, beer), water, wastewater, or any aqueous industrial process water stream such as process water, cooling water. [00186] In particular, the article may be used for medical applications such as hemodialysis membranes, for polymer electrolyte membranes, for aqueous medium filtration, such as reverse osmosis membranes, ultrafiltration membranes, microfiltration membranes, nanofiltration membranes, and/or ion-exchange membranes. Both microfiltration and ultrafiltration membranes can be used in membrane bioreactors, such as wastewater treatment. Membranes may be in flat sheet or hollow fiber configuration. [00187] The aqueous medium filtration may include food and beverage filtration, filtration for water purification, filtration for wastewater treatment and filtration for industrial process separations involving aqueous medium. Among applications of use, mention can be made of healthcare applications, in particular medical applications - 35 - SSPU 2022/035 such as hemodialysis, wherein comprising the PAES polymer (P2) as a bulk polymer and the PAES copolymer (P1) as a hydrophilic polymer additive can advantageously be used in single-use or may be reusable. [00188] Method for purifying an aqueous medium [00189] A further aspect of the present invention may be directed to a method for purifying an aqueous medium, said method comprising at least a filtration step through a membrane, fiber(s), tube(s) or film(s) comprising the polymeric composition according to the present invention, or made from the polymeric solution according to the present invention. [00190] Indeed the inventive polymeric composition or solution can be used in different filter membrane geometries. For instance, the polymeric composition or solution can be used in flat membranes and/or in capillary-like hollow fiber membranes. The aqueous medium flow toward these membranes may take in the form of a dead-end flow or of a crossflow. [00191] In particular, the purification method may be used for purifying a human biological fluid, preferably a blood product, e.g., whole blood, plasma, serum, fractionated blood components or mixtures thereof. The purification is carried out in an extracorporeal circuit which may comprise at least one filtering device (or filter) comprising at least one membrane, fiber or film as described above. [00192] As intended herein, a blood purification method through an extracorporeal circuit may comprise hemodialysis (FD) by diffusion, hemofiltration (HF), hemodyafiltration (HDF) and/or hemoconcentration. In HF, blood is filtered by ultrafiltration, while in HDF blood is filtered by a combination of FD and HF. [00193] Blood purification methods through an extracorporeal circuit are typically carried out by means of a hemodialyzer, i.e., equipment designed to implement any one of FD, HF or HFD. In such methods, blood is filtered from waste solutes and fluids, like urea, potassium, creatinine and uric acid, thereby providing blood free of waste solutes and fluids. [00194] Typically, a hemodialyzer for carrying out a blood purification method comprises a cylindrical bundle of hollow fibers of membranes, said bundle having two ends, each of them being anchored into a so-called potting compound, which is usually a polymeric material acting as a glue which keeps the bundle ends together. Potting compounds are known in the art and include notably polyurethanes. By applying a pressure gradient, blood is pumped through the (lumen side of the) bundle of fibers via the blood ports and the filtration product (the "dialysate") is pumped through the space surrounding the fibers (shell side). [00195] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present - 36 - SSPU 2022/035 application to the extent that it a term unclear, the present description shall take precedence. [00196] EXAMPLES [00197] The invention will now be described with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention. As used in the Examples, “E” denotes an example embodiment of the present invention and “CE” denotes a counter-example. [00198] Raw Materials [00199] K2CO3 (potassium carbonate), obtained from Armand products [00200] daBPA (2,2’-diallyl Bisphenol A), obtained from Sigma-Aldrich, U.S.A. [00201] DCDPS (4,4’-dichlorodiphenyl sulfone), obtained from Solvay Speciality Polymers [00202] DHDPS (4,4’-dihydroxydiphenyl sulfone or Bisphenol S), obtained from Konishi Chemicals, Japan. [00203] Sulfolane, obtained from Chevron Phillips, U.S.A [00204] AIBN (azobisisobutyronitrile), obtained from Sigma-Aldrich, U.S.A. [00205] Sodium 3-mercapto-1-propanesulfonate (MPS thiol), obtained from TCI chemicals, U.S.A. [00206] Methanol, obtained from Sigma-Aldrich, U.S.A. [00207] NMP (N-methyl-2-pyrrolidone) obtained from Sigma-Aldrich, U.S.A. [00208] PES (Polyethersulfone) Veradel® 3000 MP obtained from Solvay Specialty Polymers – used as a PAES polymer (P2) in some of the examples [00209] PPSU (polybiphenylsulfone) Radel® 5000NT obtained from Solvay Specialty Polymers – used as a PAES polymer (P2) in some of the examples [00210] PEG 400 (polyethylene glycol 400) obtained from Sigma-Aldrich, U.S.A. [00211] PVP k10 (polyvinylpyrrolidone K10) and PVP k90 (polyvinylpyrrolidone K90) obtained from Sigma-Aldrich, U.S.A. [00212] IPA (isopropyl alcohol) obtained from Sigma-Aldrich, U.S.A. [00213] DMSO (dimethylsulfoxide) obtained from Sigma-Aldrich, U.S.A. [00214] Glycerol from Sigma-Aldrich, U.S.A. [00215] BSA (bovine serum albumin) from Sigma-Aldrich, U.S.A. [00216] Dextran 4 powder, technical grade, from Serva. Before its use, the dextran powder was thermally treated at 100°C for 2 hours to remove eventual humidity. [00217] Phosphate buffered saline P4417 from Sigma-Aldrich, U.S.A. [00218] Tetramethylammonium, acid chloride obtained from Sigma-Aldrich, U.S.A. [00219] Sodium hypochlorite (NaOCl) obtained from Sigma-Aldrich, U.S.A. [00220] Sulfonated PES (s-PES), obtained from Konishi Chemical Ind. Co., LTD, Japan (lot No EA0628), with Mw= 140,000 g/mol and a degree of sulfonation of 32%; this - 37 - SSPU 2022/035 s-PES is generally following formula and is made by direct sulfonation of a PES with a sulfonation agent. [00222] GPC Method 1 for measuring molecular weight (Mn, Mw) [00223] Viscotek GPC Max (Autosampler, pump, and degasser) with a TDA302 triple detector array comprised of RALS (Right Angle Light Scattering), RI (Refractive Index) and Viscosity detectors were used. Samples were prepared as ~2 mg/mL in DMAc/ LiBr. Samples were run in dimethyl acetamide (DMAc) with 0.2 w/w% LiBr at 65°C at 1.0 mL/min through a set of 3 columns: a guard column (CLM1019 - with a 20k Da exclusion limit), a high Mw column (CLM1013 exclusion of 10MM Daltons relative to Poly Styrene) and a low Mw column (CLM1011 - exclusion limit of 20k Daltons relative to PS). Calibration was done with a single, mono-disperse polystyrene standard of ~100k Da. Light Scattering, RI, and Viscosity detectors were calibrated based on a set of input data supplied with the standards. Samples were prepared as about 2 mg/mL in NMP/LiBr. Viscotek's OMNISec v4.6.1 Software was used for data analysis. [00224] GPC Method 2 for measuring Molecular weight (Mn, Mw) (“sulfone method”) [00225] The molecular weights of polyarylethersulfone polymers were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5µ mixed D columns with guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254nm was used to obtain the chromatogram. A flow rate of 1.5 ml/min and injection volume of 20 µL of a 0.2 w/v% solution in mobile phase was selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (Peak molecular weight range: 371,000 to 580 g/mol). The number average molecular weight Mn, weight average molecular weight Mw, higher average molecular weight Mz, were reported. - 38 - SSPU 2022/035 [00226] Thermal gravimetric analysis [00227] TGA experiments were carried out using a TA Instrument TGA Q500. TGA measurements were obtained by heating the sample at a heating rate of 10°C/min from 20°C to 800°C under nitrogen. [00228] 1H NMR [00229] 1H NMR spectra were measured using a 400 MHz Bruker spectrometer with TCE as the deuterated solvent. All spectra are reference to residual proton in the solvent. [00230] DSC DSC was used to determine glass transition temperatures (Tg) and melting points (Tm)-if present. DSC experiments were carried out using a TA Instrument Q100. DSC curves were recorded by heating, cooling, re-heating, and then re-cooling the sample between 25°C and 320°C at a heating and cooling rate of 20°C/min. All DSC measurements were taken under a nitrogen purge. The reported Tg values (and if any, Tm values) were provided using the second heat curve unless otherwise noted. [00231] Example 1: Preparation of sulfonated PES (‘sPES’) as copolymer (P1) [00232] I. Preparation of copolymer precursor (P0-A) [00233] A copolymer precursor (P0-A) was prepared according to Scheme 1. [00234] The polymerization took place in a 20-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (2030.2 g; 7.07 moles), DHDPS (1673.12 g, 6.68 moles) and daBPA (98.62 g; 0.31 mole) were added to the vessel first, followed by the addition of potassium carbonate (977.14 g; 7.07 moles) and NMP (3996.59 g). The reaction mixture was heated from room temperature to 190 °C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around eight hours, depending upon the viscosity of the solution. The reaction was terminated by adding DCDPS (140.7 g) and continuing the reaction for another 30 minutes after which fresh NMP (351.77 g) was added and the reaction stopped by ceasing the heating. The reaction mixture was filtered, coagulated into methanol. The coagulated copolymer precursor was then washed with methanol and water and again with methanol and dried at 110°C. [00235] Characterization of the copolymer precursor (P0-A) [00236] The Mw, Mn, PDI measured by GPC Method 2 (Sulfones method), the TGA temperature and glass transition temperature Tg by DSC are provided in Table 1. [00237] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2’-diallyl bisphenol A monomer in the copolymer precursor (P0-A). The estimated olefin content measured by 1H NMR was around 4.01 mol%. - 39 - SSPU 2022/035 [00238] II. Preparation of sulfonated (P1-A) [00239] The sulfonated copolymer (P1-A) was prepared according to Scheme 2. [00240] The reaction took place in a 1-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet. The copolymer P0-A (250 g), sodium 3-mercapto-1- propanesulfonate (MPS thiol) (25.75 g) were first charged and then DMSO solvent (583.3 g) was added and the mixture was stirred at 75 °C till a clear solution was obtained. Then nitrogen was purged through the mixture for 45 minutes after which AIBN (3.95 g) was added all at once. The reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water. The coagulated sulfonated copolymer was then washed with 2 L of deionized water and then twice with 2 L of methanol. The washed sulfonated copolymer was then dried in a vacuum oven at 110 °C overnight. [00241] Characterization of the sulfonated copolymer (P1-A) [00242] The Mw, Mn, PDI measured by GPC Method 1, the TGA temperature, glass transition temperature Tg by DSC, and sodium content are provided in Table 1. [00243] 1H NMR: The complete absence of unsaturated groups was confirmed by H NMR analysis indicated the complete conversion of the olefin groups in the reaction. [00244] III. Preparation of copolymer precursor (P0-B) [00245] The copolymer precursor (P0-B) was prepared according to Scheme 1. [00246] The polymerization took place in a 2-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (326.28 g; 1.13 moles), DHDPS (256.21 g, 1.02 moles) and daBPA (31.22 g; 0.1 mole) were added to the vessel first, followed by the addition of potassium carbonate (160.14 g; 1.15 moles) and sulfolane (1465.7 g). The reaction mixture was heated from room temperature to 210°C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around four hours, depending upon the viscosity of the solution. The reaction was terminated by adding fresh sulfolane (~ 150 g) and the reaction stopped by ceasing the heating. The reaction mixture was filtered, coagulated into methanol. The coagulated copolymer precursor was then washed with methanol and water and again with methanol and dried at 110°C. [00247] Characterization of the copolymer precursor (P0-B) [00248] The Mw, Mn, PDI measured by GPC Method 2 (Sulfones method), the TGA temperature and glass transition temperature Tg by DSC are provided in Table 1. [00249] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2’-diallyl - 40 - SSPU 2022/035 bisphenol A monomer in the precursor (P0-B). The estimated olefin content measured by 1H NMR was about 7.91 mol%. [00250] IV. Preparation of sulfonated copolymer (P1-B) [00251] The sulfonated copolymer (P1-B) was prepared according to Scheme 2. [00252] The reaction took place in a 2-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet. The copolymer P0-A (529.6 g), Sodium 3-mercapto-1- propanesulfonate (MPS thiol) (108.5 g) were first charged and then DMSO solvent (1235 g) was added and the mixture was stirred at 75 °C till a clear solution was obtained. Then nitrogen was purged through the mixture for 45 minutes after which AIBN (16.66 g) was added all at once. The reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water. The coagulated sulfonated copolymer was then washed with 2 L of deionized water and then twice with 2 L of methanol. The washed sulfonated copolymer was then dried in a vacuum oven at 110 °C overnight. [00253] Characterization of the sulfonated copolymer (P1-B) [00254] The Mw, Mn, PDI measured by GPC Method 1, the TGA temperature, glass transition temperature Tg by DSC, and sodium content are provided in Table 1. [00255] 1H NMR: The complete absence of unsaturated groups was confirmed by H NMR analysis indicated the complete conversion of the olefin groups in the reaction. [00256] V. Preparation of copolymer precursor (P0-C) [00257] The copolymer precursor (P0-C) was prepared according to Scheme 1 in a similar manner as described for the copolymer precursor (P0-B). [00258] Characterization of the copolymer precursor (P0-C) [00259] The Mw, Mn, PDI measured by GPC Method 2 (Sulfones method), the TGA temperature and glass transition temperature Tg by DSC are provided in Table 1. [00260] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2’-diallyl bisphenol A monomer in the copolymer precursor (P0-C). The estimated olefin content measured by 1H NMR was about 7.78 mol%. [00261] VI. Preparation of sulfonated copolymer (P1-C) [00262] The sulfonated copolymer (P1-C) was prepared according to Scheme 2 in a similar manner as described for sulfonated copolymer (P1-B). [00263] Characterization of the sulfonated copolymer (P1-C) [00264] The Mw, Mn, PDI measured by GPC Method 1, the TGA temperature, glass transition temperature Tg by DSC, and sodium content are provided in Table 1. [00265] 1H NMR: The complete absence of unsaturated groups was confirmed by H NMR analysis indicated the complete conversion of the olefin groups in the reaction. - 41 - SSPU 2022/035 ro s r u c e r p r e my l o p o c S E P d e zi l a n oi t c n u f f o n oi t a 3 e r On a 3 a Cl oC p 0 r OP oC 0 e r K 2 o fl u 1 o C 2 M N9 P S 2 K 1 . 1 e me h c S - 42 - SSPU 2022/035 sf o n oit a r a p e r P. 2 e me h c S
- 43 - SSPU 2022/035 [00266] VII. Preparation of copolymer (P0-D) [00267] The copolymer precursor (P0-D) was prepared according to Scheme 1. [00268] The polymerization took place in a 1-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (145.01 g; 0.505 moles), DHDPS (113.87 g, 0.455 moles) and daBPA (13.87 g; 0.045 mole) were added to the vessel first, followed by the addition of potassium carbonate (71.17 g; 0.515 moles) and sulfolane (651.4 g). The reaction mixture was heated from room temperature to 210°C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around six hours, depending upon the viscosity of the solution. The reaction was terminated by adding introducing methyl chloride gas to endcap the polymer for about 30 minutes after which the reaction stopped by ceasing the heating. The reaction mixture was then filtered, coagulated into methanol. The coagulated copolymer precursor was then washed with methanol and water and again with methanol and dried at 110°C. [00269] Characterization of the copolymer precursor (P0-D) [00270] The Mw, Mn, PDI measured by GPC Method 2 (Sulfones method), the TGA temperature and glass transition temperature Tg by DSC are provided in Table 1. [00271] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2’-diallyl bisphenol A monomer in the copolymer precursor (P0-D). The estimated olefin content measured by 1H NMR was about 6.12 mol%. [00272] VIII. Preparation of sulfonated copolymer (P1-D) [00273] The sulfonated copolymer (P1-D) was prepared according to Scheme 2. [00274] The reaction took place in a 1-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet. An amount (130.32 g) of the copolymer precursor (P0- D) and sodium 3-mercapto-1-propanesulfonate (MPS thiol) (31.14 g) were first charged to the reactor vessel, and then DMSO solvent (521.2 g) was added. The mixture was stirred at 75 °C till a clear solution was obtained. Then nitrogen was purged through the mixture for 45 minutes after which AIBN (4.1 g) was added all at once. The reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water. The coagulated sulfonated copolymer was then washed with 2 L of deionized water and then twice with 2 L of methanol. The washed sulfonated copolymer was then dried in a vacuum oven at 110 °C overnight. [00275] Characterization of the sulfonated copolymer (P1-D) [00276] The Mw, Mn, PDI measured by GPC Method 1, the TGA temperature, glass transition temperature Tg by DSC, and sodium content are provided in Table 1. - 44 - SSPU 2022/035 [00277] 1H NMR: The complete groups was confirmed by H NMR analysis indicated the complete conversion of the olefin groups in the reaction. [00278] IX. Preparation of copolymer precursor (P0-E) [00279] The copolymer precursor (P0-E) was prepared according to Scheme 1. [00280] The polymerization took place in a 20-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (2030.2 g; 7.07 moles), DHDPS (1594.28 g, 6.37 moles) and daBPA (197.25 g; 0.63 mole) were added to the vessel first, followed by the addition of potassium carbonate (977.14 g; 7.07 moles) and NMP (4018.9 g). The reaction mixture was heated from room temperature to 190 °C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around eight hours, depending upon the viscosity of the solution. The reaction was terminated by adding DCDPS (140.7 g) and continuing the reaction for another 30 minutes after which fresh NMP (351.77 g) was added and the reaction stopped by ceasing the heating. The reaction mixture was filtered, coagulated into methanol. The coagulated copolymer precursor was then washed with methanol and water and again with methanol and dried at 110°C. [00281] Characterization of copolymer precursor (P0-E) [00282] The Mw, Mn, PDI measured by GPC Method 2 (Sulfones method), the TGA temperature and glass transition temperature Tg by DSC are provided in Table 1. [00283] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2’-diallyl bisphenol A monomer in the copolymer precursor (P0-E). The estimated olefin content measured by 1H NMR was about 8.5 mol%. [00284] X. Preparation of sulfonated copolymer (P1-E) [00285] The sulfonated copolymer (P1-E) was prepared according to Scheme 2. [00286] The reaction took place in a 1-L glass reactor vessel fitted with an overhead stirrer and nitrogen inlet. A total of 300g of two different batches of the copolymer precursor (P0-E) made according to Section IX and 61.5 g of sodium 3- mercapto-1-propanesulfonate (MPS thiol) were first charged in the reactor vessel, and then DMSO solvent (700 g) was added. The mixture was stirred at 75 °C till a clear solution was obtained. Then nitrogen was purged through the mixture for 45 minutes after which AIBN (5.94 g) was added all at once. The reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water. The coagulated sulfonated copolymer was then washed with 2 L of deionized water and then twice with 2 L of methanol. The washed sulfonated copolymer was then dried in a vacuum oven at 110 °C overnight. - 45 - SSPU 2022/035 [00287] Characterization of the copolymer (P1-E) [00288] The Mw, Mn, PDI measured by GPC Method 1, the TGA temperature, glass transition temperature Tg by DSC, and sodium content are provided in Table 1. [00289] 1H NMR: The complete absence of unsaturated groups was confirmed by H NMR analysis indicated the complete conversion of the olefin groups in the reaction. [00290] XI. Preparation of copolymer precursor (P0-F) [00291] The copolymer precursor (P0-F) was prepared according to Scheme 1. [00292] The polymerization took place in a 20-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS ( 2010.12 g; 7 moles), DHDPS ( 1576.76 g, 6.3 moles) and daBPA ( 215.8 g; 0.7 mole) were added to the vessel first, followed by the addition of potassium carbonate ( 977.14 g; 7.07 moles) and NMP (4024 g). The reaction mixture was heated from room temperature to 190°C using a 10°C/min heating ramp. The temperature of the reaction mixture was maintained for around 6 hours, depending upon the viscosity of the solution. The reaction was terminated by adding fresh NMP (~ 10974 g) and the reaction stopped by ceasing the heating. The reaction mixture was filtered, coagulated into methanol. The coagulated copolymer precursor was then washed with methanol and water and again with methanol and dried at 110°C. [00293] Characterization of the copolymer precursor (P0-F) [00294] The Mw, Mn, PDI measured by GPC Method 2 (Sulfones method), the TGA temperature and glass transition temperature Tg by DSC are provided in Table 1. [00295] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm which indicated the incorporation of the 2,2’-diallyl bisphenol A monomer in the copolymer precursor (P0-F). The estimated olefin content measured by 1H NMR was about 14.4 mol%. [00296] XII. Preparation of sulfonated copolymer (P1-F) [00297] The sulfonated copolymer (P1-F) was prepared according to Scheme 2. [00298] The reaction took place in a 1-L glass reactor vessel fitted with an overhead stirrer and a nitrogen inlet. An amount (130 g) of the copolymer precursor (P0-F) and sodium 3-mercapto-1-propanesulfonate (MPS thiol) (38.65 g) were first charged to the reactor vessel , and then DMSO solvent (303 g) was added. The mixture was stirred at 75 °C till a clear solution was obtained. Then nitrogen was purged through the mixture for 45 minutes after which AIBN (5.94 g) was added all at once. The reaction was allowed to continue for another 12 hours after which the reaction mixture was coagulated in 2 L of distilled water. The coagulated sulfonated copolymer was then washed with 2 L of deionized water and then - 46 - SSPU 2022/035 twice with 2 L of methanol. The sulfonated copolymer was then dried in a vacuum oven at 110 °C overnight. [00299] Characterization of the sulfonated copolymer (P1-F) [00300] The Mw, Mn, PDI measured by GPC Method 1, the TGA temperature, glass transition temperature Tg by DSC, and sodium content are provided in Table 1. [00301] 1H NMR: The complete absence of unsaturated groups was confirmed by H NMR analysis indicated the complete conversion of the olefin groups in the reaction. [00302] Table 1 summarizes the properties of the copolymer precursors (P0-A) to (P0-F) and sulfonated copolymers (P1-A) to (P1-F). [00303] Table 1 Copolymer precursors P0-A P0-B P0-C P0-D P0-E P0-F GPC M w 71376 71927 72962 137995 77907 54162 method M n 25407 24453 30606 22636 24645 19873 2 PDI 2.81 2.94 2.38 6.09 3.16 2.72 TGA, °C 486 460 425 462 472 455 Tg, °C 228 - 190 208 218 217 Sulfonated copolymers P1-A P1-B P1-C P1-D P1-E P1-F GPC Mw 109239 94881 77386 306550 252576 81397 method M n 47408 40133 36521 75528 62615 43397 1 PDI 2.3 2.37 2.12 4.05 4 1.9 TGA, °C 388 374.5 371 372 385 366 Tg, °C 218 224.5 229 229.6 225 227 Na, ppm 3175 7212 2867 6390 6050 5778 % Sulfonation degree based 4.01 7.9 7.78 6.12 8.5 14.4 on % olefins [00304] As used in the Examples 2-16 hereinafter, the sulfonated copolymer (P1) represented by any of the samples P1-A to P1-F described thereabove are identified as “sPES”. [00305] Example 2: Preparation of films from solutions comprising blends of sPES copolymers (P1) and PES polymer (P2) according to the invention [00306] Solution preparation for film manufacturing [00307] Several polymeric solutions for film manufacturing were prepared by adding specific amounts of sPES which was a sulfonated copolymer (P1) selected from samples P1-A to P1-F and of Veradel® 3000MP PES as the PAES polymer (P2) in NMP and stirring at 70°C with a mechanical anchor stirrer. The various amounts - 47 - SSPU 2022/035 of sPES in the polymeric 10 wt.%, 20 wt.%, or 40 wt.% relative to the combined weights of sPES and PES in the solutions. Each casting solution (200 grams) was stirred so as to contain 20 wt.% of the blend of PES+sPES in NMP. Each solution prepare was left overnight rest to remove eventual air bubble and heated at 40°C before use. [00308] Additionally, reference polymeric solutions were made with only PES (100 wt.% PES with no sPES) or only sPES (100 wt.% sPES with no PES) for making comparative films. [00309] Film preparation [00310] A4 size films were prepared by filming any of the polymeric solution (polymers + solvent) described above, over a suitable smooth glass support by means of an automatized casting knife (wet thickness=1000 micrometer). The casting solution for each film was ca.50 grams. The film formation was accomplished by solvent evaporation method by thermal treating the film at 160°C for 4 hours under vacuum. The film formed was then cooled down and detached from glass support by submerging in a box filled with deionized water (obtained with Milli Q). The films were washed several times in pure water and then dried and room temperature. [00311] Tables 2-4 provide the compositions for the films according to the invention and the compositions for the comparative films. [00312] Example 3: Properties of films comprising blends of sulfonated copolymers (P1) and PES polymer (P2) [00313] Methods [00314] Thickness measurement on dried films [00315] Thickness was measured on dried films by using ABSOLUTE Digimatic Thickness Gauges provided by Mitutoyo. The thickness of each film was referred to the average of at least 5 measures on different positions. [00316] Water uptake measurement on polymeric dense films [00317] The polymeric dense film (20 cm*12.5 cm) prepared in Example 2 were dried at 50° C for 24 hours before testing. [00318] The weighted dense film (W0) was then submerged in deionized water at room temperature for T1= 24 hours and T2= 48 hours. At each time (T1 and T2), the samples were weighed, after the removal of liquid water on the surface by using tissue paper, obtaining the weight W1 and W2 respectively. [00319] At the end of the test, the samples were dried at 50°C for 24 h and weighted (W3). [00320] The water uptake (WU) was expressed as weight increasing % and reported as average of a minimum of 3 tests for each sample with a dimension of 20 cm*12.5 cm. [00321] The WU was calculated as reported below: - 48 - SSPU 2022/035 [00322] where W1 (x=1) was in water and W2 (x=2) was obtained after 48 [00323] The weight loss of the sample in water was verified by comparing the W0 and W3 weights. [00324] The water uptake (WU) values were reported in Tables 2-4. [00325] Captive air bubble contact angle measurement on polymeric film [00326] Contact angles were measured by the Captive Air Bubble (CAB) method. This method measures the contact angle of an air bubble at a surface of a sample immersed in a liquid, in this case water and, as the sample is already wet, swelling and absorption are suppressed. [00327] CAB measurements were carried out at room temperature, using an adapted environment controlled chamber filled with deionized water (DI water). Prior to analysis, the films were hydrated in DI water. The wet films samples were wrapped on a 15x15mm glass substrate, fixed on a sample holder with double-sided tape. Film samples were then immersed in DI water, and a air bubble was dropped on the sample surface using a J-shaped syringe. [00328] Contact Angle measurements were performed on an optical tensiometer (DSA100 provided by KRUSS) equipped with a high quality monochromatic cold LED (6) and a high resolution (1984x1264) digital camera. Image acquisition parameters were set at 5 Frames Per Second (FPS) and a minimum acquisition time of 60 s. The instrument was calibrated using a calibration ball (CA = 143.15°) with an accepted error of 0.03°. Each bubble image was stored digitally and an image analysis system (ADVANCE) calculated the contact angle (θ) from the shape of the bubble. [00329] The CAB contact angle values reported in Tables 2-4 were the average of 5 measurements performed in the air at room temperature on the same sample. [00330] Based on the water uptake data in Tables 2-4, it was confirmed that the films CE4, CE7, CE10, CE12, CE15 and CE18 made of 100 wt.% sPES copolymer had a higher water uptake % compared to the film CE1 made from 100 wt.% PES. This confirmed the increased hydrophilicity of the sPES copolymers resulting from the presence of the sulfonic groups. - 49 - SSPU 2022/035 [00331] Table 2 Film compositions CE1 E2 E3 CE4 E5 E6 CE7 PES, wt.%* 100 90 60 - 90 80 - sPES copolymer (P1-A), wt.% * - 10 40 100 - - - sPES copolymer (P1-B), wt.% * - - - - 10 20 100 Film Thickness, mm 0.128 0.124 0.122 0.130 0.117 0.116 0.133 Water update, wt.% 1.6 1.5 1.9 2.6 1.4 1.9 4.6 @ 24 hrs Water update, wt.% 1.7 1.5 1.9 2.4 1.7 1.9 4.6 @ 48 hrs CAB contact angle , o 107.6 111.2 - 113.0 - 117.1 121.1 * wt.% relative to the combined amounts of PES and sPES copolymer [00332] Table 3 Film compositions CE1 E8 E9 CE10 E11 CE12 PES, wt.%* 100 90 80 - 90 - sPES copolymer (P1-C), wt.%* - 10 20 100 - - sPES copolymer (P1-D), wt.%* - - - 10 100 Film Thickness, mm 0.128 0.114 0.122 0.121 0.126 0.113 Water update, wt.% 1.6 1.9 2.3 4.9 1.8 3.8 @ 24 hrs Water update, wt.% 1.7 1.8 2.3 4.6 1.6 3.6 @ 48 hrs CAB contact angle , o 107.6 113.4 117.5 118.3 - - * wt.% relative to the combined amounts of PES and sPES copolymer Table 4 Film compositions CE1 E13 E14 CE15 E16 E17 CE18 PES, wt.%* 100 90 60 - 90 60 - sPES copolymer (P1-E), wt.%* - 10 40 100 - - sPES copolymer (P1-F), wt.%* - - - - 10 40 100 Film Thickness, mm 0.128 0.122 0.121 0.118 0.124 0.119 0.153 Water update, wt.% @ 24 hrs 1.6 2.1 2.6 3.7 1.7 2.5 4.4 Water update, wt.% @ 48 hrs 1.7 2.0 2.4 3.6 2.0 2.6 3.9 CAB contact angle , o 107.6 121 - 123 - - - * wt.% relative to the combined amounts of PES and sPES copolymer - 50 - SSPU 2022/035 [00334] It was also observed that when copolymer additive was blended with PES, the water uptake % showed an increased hydrophilicity, albeit this effect was observed only at higher sPES additive concentrations (20-40 wt.% added sPES copolymer, the wt.% being relative to the combined amounts of PES and sPES copolymer). Without wishing to be bound by theory, it is believed to be due to the dense natural structure of films that renders it more resistant to water permeation. [00335] Moreover, increasing the content of the sPES copolymer additive in the polymeric blend with PES further enhanced the hydrophilization of the film (comparing film E8 vs. film E9, film E13 vs. film E14, and film E16 vs. film E17). [00336] Mechanical properties on the flat films were assessed at room temperature (23°C) following ASTM D 638 standard procedure using type V specimen, grip distance = 25.4 mm, initial length Lo = 21.5 mm). Each sample was tested 5 times. [00337] The tensile mechanical properties of the film E6 made with a blend of sPES copolymer (P1-B) and PES, of the film CE7 made with only the sPES copolymer (P1-B) and of the film CE1 made with solely PES are provided in Table 5. [00338] Table 5 Films CE1 E6 CE7 Film PES, wt.%* 100 80 0 compositio sPES copolymer 0 20 100 n (P1-B), wt.%* Film Thickness, mm 0.128 0.116 0.133 Mechanical Properties Tensile Modulus, MPa 2280 2240 2040 Tensile Stress at Break, MPa 77 58 56 Tensile Strain at break, % 7 9 9 * wt.% relative to the combined amounts of PES and sPES copolymer [00339] The mechanical properties of blend showed that the sPES additive [copolymer (P1-B)] did not compromise the PES film mechanical properties in terms of tensile modulus, and there was a slight increase in the tensile strain at break % with the film E6 compared to the film CE1 made with solely PES. [00340] Example 4: Leaching test [00341] This test was aimed at comparing the leaching properties and water uptake of the sPES copolymer samples P1-B and P1-D to a commercial sulfonated PES from Konishi having a 32% degree of sulfonation and a Mw of 140,000 g/mol (“Konishi sPES”). - 51 - SSPU 2022/035 [00342] A film CE19 was made from Konishi sPES according to the method provided in Example 2. [00343] The polymeric materials were first dried at 160oC for 3 hour under vacuum. The drying weight loss calculated in % from the initial weight to the weight after the 3- hour drying was reported in Table 6. [00344] Method for powder leaching testing [00345] A powder leaching test was carried out by subjecting a polymer powder (15 g) for 4 hours at 50oC in water (0.3 L). The weight loss calculated in % from the initial weight to the weight after 4 hours is reported for PES powder, sPES copolymer (P1-B) and (P1-D) powders and the commercial Konishi sPES powder in Table 6. [00346] Method for film leaching testing [00347] A leaching film test was carried out by subjecting a polymer film sample (ca.5 g ) for 48 hours at 35oC in water (80 mL). The weight loss calculated in % from the initial weight to the final weight after 48 hours is reported in Table 6 for a sample of the PES film CE1, of the film CE7 made from sPES (P1-B), of the film CE12 made from sPES (P1-D) and of the film CE19 made from commercial Konishi sPES. [00348] Table 6 Films CE1 CE7 CE12 CE19 PES, wt.% 100 - - - sPES copolymer Film (P1-B), wt.% - 100 - - composition sPES copolymer (P1-D), wt.% - - 100 - Konishi sPES, wt.% - - - 100 Drying Weight loss, % @160°C*3h*vacuum 0.2 1.0 1.6 0.7 LEACHING POWDER TEST Weight loss %, after 4h @50°C in H2O 0 0.4 0 3.9 LEACHING FILM TEST Weight loss %, after 48h @35°C in 0.2 - 0.5 8.3 80mL of H2O Water uptake, % 1.7 4.6 3.8 6.3 [00349] The leaching tests demonstrated that the sulfonated PES copolymers (which are used in blends according to the invention with other sulfone polymers such as PES or PPSU) had a much lower leaching tendency compared to a commercial sulfonated sPES made by direct sulfonation of PES with a sulfonating agent. - 52 - SSPU 2022/035 [00350] Therefore blends according to with the sulfonated copolymer (P1) and at least another sulfone polymer such as PES or PPSU are expected to have much lower leaching tendency compared to blends of same PES or PPSU with commercial sulfonated sPES (like the Konishi sPES) made by direct sulfonation of PES with a sulfonating agent. [00351] Example 5: Chemical Resistance testing [00352] 5.1 Method (1) for chemical resistance testing [00353] A chemical resistance testing (method 1) was carried out by submerging 5 separate film samples for each polymer material being tested. The tests were carried out on film pieces as described on ASTM D638-14. The dimension/size of the film pieces were cut by a type V specimen in an aqueous sodium hypochlorite solution (containing 5000 ppm NaClO) first for 72 hours at room temperature (T1) and then for 92 hours at 40°C (T2). [00354] The effect of the oxidant NaClO on the polymer film samples was evaluated by weight changes as well as changes in mechanical properties (similar testing as described in Example 3) of each polymer sample before treatment with NaClO and after the entire NaClO treatment (under conditions T1 and T2). [00355] Table 7 Film compositions CE1 E6 CE7 sPES copolymer (P1-B) wt.% - 20 100 PES wt.% 100 80 - Film properties untreated 2280 2240 2040 Tensile Modulus, treated 1980 2020 1540 MPa % change -13 % -10 % -25 % untreated 77 58 56 Tensile Stress at Break, MPa treated 57 67 40 % change -25 % +16% -29 % untreated 7.4 8.5 8.7 Tensile Strain at treated 6 17 11 break, % % change -22 % +100% 26% Weight % change -0.1% +0.3% +2.2% [00356] The results in Table 7 report the average of 3 separate tests: change in weight (%), tensile modulus (MPa), tensile stress at break (MPa) and tensile strain at break (%) before and after treatment and their calculated difference in % between the untreated samples and the treated sample subjected to NaClO treatment. - 53 - SSPU 2022/035 Films CE1, E6, CE7 made in 2 and characterized in Example 3 were used for the chemical resistance testing. [00357] The film E6 made from the blend of sPES copolymer and PES had surprisingly a much better chemical resistance compared to films made from solely the sPES copolymer and made solely from PES. [00358] It was also visually observed that there was no apparent color change during this chemical resistance testing for any of the samples CE1, E6 and CE7. [00359] 5.2 Method (2) for chemical resistance testing [00360] Films CE1, E9, CE10 made in Example 2 were used for this chemical resistance testing (method 2). [00361] A different chemical resistance testing (method 2) was carried out by submerging three (3) separate polymeric film samples per polymeric material being tested to compare the chemical resistance of films CE1 (PES), E9 (20 wt.% sPES P1- C+80 wt.% PES), and CE10 (sPES P1-C). [00362] The tests were carried out on film pieces as described on ASTM D638-14. The dimension/size of the film pieces were cut by a type V specimen in an aqueous sodium hypochlorite solution (containing 5000 ppm NaClO) at 40°C for 3 days, for 1 week and for 2 weeks (3 different time periods). The effect of oxidant NaClO on the samples was evaluated by weight and mechanical test of each sample test before and after the NaClO submersion for each time. The data: weight (%) , modulus (MPa), stress at break (MPa) and strain at break (%) difference between the untreated samples and the samples after a NaClO treatment are the average of the 3 test results are reported in Table 8 (3-day NaClO treatment), Table 9 (1- week NaClO treatment), and Table 10 (2-week NaClO treatment). [00363] The chemical resistance testing (method 2) clearly demonstrated that the film E9 made from the blend of PES + sPES (P1-C) not only had a higher tensile strain at break compared to the film CE1 made from PES after NaClO treatment, but also its tensile strain at break increased (by 25%) after a 2-week treatment in 5000 ppm NaClO while the tensile strain at break of film CE1 decreased (by 53%).
- 54 - SSPU 2022/035 [00364] Table 8 : 3-day NaClO Film compositions CE1 E9 CE10 sPES (P1-C) wt.% - 20 100 PES wt.% 100 80 - Properties untreated 2210 2330 1880 Tensile Modulus, treated 2320 2120 1790 MPa % change +5 % -9% -5 % untreated 69 82 52 Tensile Stress at Break, MPa treated 76 63 44 % change +10 % -24% -15 % untreated 11 5.3 9.6 Tensile Strain at treated 5.9 8 9.1 break, % % change -46 % +51% -5% Weight % change -2.7% +0.8% +1.0% [00365] Table 9 : 1-week NaClO treatment Film compositions CE1 E9 CE10 sPES (P1-C) wt.% - 20 100 PES wt.% 100 80 - Properties untreated 2210 2330 1880 Tensile Modulus, treated 1630 2160 1680 MPa % change -26% -7% -11% untreated 69.2 82 52.2 Tensile Stress at Break, MPa treated 40.9 69.4 44.8 % change -41% -15% -14% untreated 11 5.3 9.6 Tensile Strain at treated 3.2 6.5 12 break, % % change -71% +23% +25% Weight % change +1.2% +1.0% +1.5%
- 55 - SSPU 2022/035 [00366] Table 10 : 2-week NaClO Film compositions CE1 E9 CE10 sPES (P1-C) wt.% - 20 100 PES wt.% 100 80 - Properties untreated 2210 2330 1880 Tensile Modulus, treated 1940 2210 1770 MPa % change -12% -5% -6% untreated 69.2 82 52.2 Tensile Stress at Break, MPa treated 69.1 73.5 48.4 % change 0% -10% -7% untreated 11 5.3 9.6 Tensile Strain at treated 5.2 6.6 9.2 break, % % change -53% +25% -4% Weight % change +0.2% +2.2% +1.2% [00367] Example 6: Preparation of porous membranes made from polymeric solutions comprising 15 wt.% of blends of sPES copolymer (P1-B) and PES polymer (P2) [00368] Solution preparation for membrane manufacturing [00369] Dope polymeric solutions to make porous membrane were prepared by blending a sPES additive which was selected to be the sPES copolymer (P1-B) described above in Example 1, with the PES (Veradel® 3000MP) as the PAES polymer (P2) in NMP and stirring with a mechanical anchor stirrer at 70oC. The various amounts of sPES in the polymeric solutions were 5 wt.%, 10 wt.%, or 20 wt.%, said wt.% being relative to the combined weights of sPES and PES in the polymeric solution. [00370] When at least one pore forming agent was used in the polymeric solution, the solution (150 grams) was made by stirring the polymers, pore forming agents and NMP solvent, so as to obtain 15 wt.% of the blend of PES+sPES, 15 wt.% of PEG400, 5 wt.% of PVP with the remainder of weight being NMP in the polymeric solution. The stirring lasted for several hours at 65°C. Then the polymeric solution was left at rest under room temperature for 8 hours to remove eventual air bubbles. [00371] When no pore forming agent was used in the polymeric solution, the solution (150 grams) was made by stirring the polymers and NMP solvent, so as to contain 15 wt.% of the blend of PES+sPES in 85 wt.% NMP. [00372] Additionally, reference polymeric solutions were made with only PES (100 wt.% PES with no sPES additive) for making comparative membranes. [00373] Porous membrane preparation - 56 - SSPU 2022/035 [00374] A4 size flat sheet porous were prepared by filming 20 grams of a polymeric dope solution (polymers + solvent + optional pore formers) as described above, over a suitable smooth glass support by means of an automatized casting knife. [00375] Membrane casting was performed by holding dope solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the polymer. The knife gap was set to 250 µm. After casting, the polymeric porous films were immediately immersed in a coagulation bath at 25°C in order to induce phase inversion. The coagulation bath consisted of pure de-ionized water. After coagulation the porous films (membranes) were washed several times in pure water during several days to remove residual traces of solvent. The membranes were stored (wet) in water. [00376] Table 11 provides the compositions of the polymeric solutions used to make membrane samples. Reference polymeric solutions were made with only 15 wt.% PES (100 wt.% PES with no sPES) without or with pore forming agents in NMP for making comparative membranes. [00377] Table 11 Membranes CE23 E24 E25 E26 CE27 E28 E29 E30 sPES P1-B, wt.% relative - 5 10 20 - 5 10 20 to sPES+PES PES wt.% relative to 100 95 90 80 100 95 90 80 sPES+PES Compositions of polymeric solutions to make membranes, wt.% relative to entire weight of solution PES, wt.% 15 14.25 13.5 12 15 14.25 13.5 12 sPES P1-B copolymer - 0.75 1.5 3 - 0.75 1.5 3 (P1-B), wt.% PEG 400 (wt.%) - - - - 15 15 15 15 PVP k10, - - - - 5 5 5 5 wt.% NMP, wt.% 85 85 85 85 65 65 65 65 [00378] Three membranes E24-E26 according to the invention were made from polymeric solutions containing 15 wt.% of blends of PES + sPES P1-B additive without pore forming agents in NMP. A comparative membrane CE23 was made from a polymeric solution containing solely 15 wt.% PES in NMP without pore forming agent. - 57 - SSPU 2022/035 [00379] Three membranes E28-E30 to the invention were made from polymeric solutions containing 15 wt.% of a blend of PES + sPES P1-B with two pore forming agents (15 wt.% PEG 400, 5 wt.% PVP). A comparative membrane CE27 was made from a polymeric solution containing 15 wt.% PES (without sPES) and the same pore forming agents and same respective amounts as in membranes E28- E30. [00380] Example 7: Preparation of porous membranes made from polymeric solutions comprising 20 wt.% of blends of sPES copolymer (P1-B) and PES polymer (P2) [00381] Solution preparation for membrane manufacturing [00382] Dope polymeric solutions to make porous membranes were prepared by blending the sPES copolymer (P1-B) with the PES polymer (Veradel® 3000MP) as the PAES polymer (P2) and optionally pore forming agents in NMP and stirring with a mechanical anchor stirrer at 70oC, similarly as described in Example 6, except that the total content of PES+sPES was maintained at 20 wt.% in the polymeric solution. [00383] The selected amount of sPES was 10 wt.% relative to the combined weights of sPES and PES in the polymeric solution to make these membranes. [00384] When at least one pore forming agent was used in the polymeric solution, the dope polymeric solution contained 20 wt.% of the blend of PES+sPES, 25 wt.% of PEG400, 5 wt.% of PVP k10 with the remainder of weight being NMP in the polymeric solution. [00385] When no pore forming agent was used in the polymeric solution, the dope solution contained 20 wt.% of the blend of 90wt.%PES+10wt.%sPES in 80 wt.% NMP. [00386] Additionally, reference polymeric solutions were made with only PES (100 wt.% PES with no sPES) without or with pore forming agents for making comparative membranes. [00387] Porous membrane preparation [00388] The membranes were made in a similar manner as described in Example 6. [00389] Table 12 provides the compositions of the polymeric solutions used to make membrane samples. [00390] Membrane E32 according to the invention was made from a blend of 90 wt.% PES+10 wt.% sPES without pore forming agent, and a comparative membrane CE31 was made from solely PES. [00391] Membrane E34 according to the invention was made from a blend of 90 wt.% PES+10 wt.% sPES with pore forming agents (25 wt.% PEG 400, 5 wt.% PVP), and a comparative membrane CE33 was made from PES (without sPES copolymer) and same kind and amounts of pore forming agents. - 58 - SSPU 2022/035 [00392] Table 12 Membranes CE31 E32 CE33 E34 sPES (P1-B), wt.% relative to sPES+PES - 10 - 10 Compositions of polymeric solutions to make membranes, wt.% relative to entire weight of solution PES, wt.% 20 18 20 18 sPES (P1-B), wt.% - 2 - 2 PEG 400 (wt.%) - - 25 25 PVP k10, wt.% - - 5 5 NMP, wt.% 80 80 50 50 [00393] Example 8: Properties of porous membranes prepared in Examples 6 & 7 [00394] Methods [00395] Thickness measurement on wet membrane [00396] Thickness was measured on wet membranes by using ABSOLUTE Digimatic Thickness Gauges provided by Mitutoyo. The thickness of each flat membrane was referred to the average of at least 5 measures on different positions. [00397] Permeability measurements on flat membrane [00398] Water flux (J) through each membrane at given pressure, was defined as the volume which permeates per unit area and per unit time. The flux was calculated with the following equation: - V (L) is the volume of permeate, - A (m2) is the membrane area, and - Δt (h) is the operation time. [00399] Water flux measurements were conducted at room temperature using a dead-end configuration system under a constant nitrogen pressure of 1 bar using pure MilliQ water. Membrane discs with an effective area of 11.3 cm2 were cut from the membrane sheets (stored in water) and placed on a metal plate. For each sample, the flux was the average of measurements obtained on at least five different discs. The flux was expressed in LMH (liters/squared meter x hour or L/m2 h). [00400] Each permeability test was carried out by applying pressure for 30 minutes on wet membranes which were previously stored in water. The reported flux was obtained by collecting data measured from the 27th to the 30th minute of each test. - 59 - SSPU 2022/035 [00401] Gravimetric porosity on flat [00402] Gravimetric porosity of a porous membrane was defined as the volume of the pores divided by the total volume of the membrane. [00403] Membrane porosity (Ɛ) was determined according to the gravimetric method detailed below. [00404] Perfectly dry membrane pieces were weighed and impregnated in isopropyl alcohol (IPA) for 24h. After this time, the excess of the liquid was removed with tissue paper, and membrane weight was measured again. The porosities ^ were measured using IPA (isopropyl alcohol) as wetting fluid according to the procedure described in Appendix of the article by Smolders & Franken entitled “Terminology for Membrane Distillation”, in Desalination, vol.72 (1989) pp. 249-262. ^ ^^ ^^ ^^ െ ^^ ^^ ^^^ ^^^^^௨^ௗ 0 where ‘Wet’ is ‘Dry’ is the weight of dry membrane, ρpolymer is the density of PES (1.37 g/cm3) and ρliquid is the density of IPA (0.78 g/cm3). [00405] Bubble point measurement on flat membranes [00406] The membrane samples which were stored wet in water were submerged in IPA for 1 hour and then dried at room temperature. Membranes bubble points (i.e., the measure of the largest pores) were determined following ASTM F316 method, using a capillary flow porometer Porolux™ 1000 (Porometer-Belgium). In this method, the most constricted (bottleneck) diameters of through-pores are measured. This method is based on the measurement of the pressure necessary to blow gas through a liquid-filled porous membrane. As the pressure of gas increases to a point, the applied pressure overcomes surface tension of liquid in the pore and pushes liquid out of the pore. For each test, membranes samples were initially fully wetted for 1 hour using Fluorinert C 43 (fluorinated fluid with a surface tension of 16 dyn/cm). Nitrogen (inert gas) was used. [00407] Static (water) contact angle measurement on membrane [00408] The membrane samples stored in water were first submerged in IPA for 1 hour and then dried at room temperature. The contact angles analysis was carried out by depositing a drop of 2 μL of water Milli Q on the sample surface through a syringe. The drop image was stored by a video camera placed in the instrument OCA 20 (KSV) provided by DATA and an image analysis system (software called SCA20 version 5.0.17) calculated the contact angle (θ) from the shape of the water drop. - 60 - SSPU 2022/035 For each sample, the contact analysis was carried out for dry and wet samples. The wet samples are considered wet after submersion in water Milli Q overnight. Contact angles value were obtained as an average of 7 different static contact angle tests on same membrane surface, all measured in air at room temperature. [00409] Pure water flux (at 1 bar), wet membrane thickness, gravimetric porosity and static contact angle are reported in Table 13 for membranes made without pore forming agents and in Table 14 for membranes made with pore forming agents. [00410] Table 13– properties of membranes without pore forming agents Membranes CE23 E24 E25 E26 CE31 E32 sPES P1-B, wt.% relative to - 5 10 20 - 10 SPES+PES Total sPES+PES, wt.% 15 15 15 15 20 20 in solution PEG 400, wt.% 0 0 0 0 0 0 PVP k10, wt.% in solution 0 0 0 0 0 0 Properties of membranes liquid flow rate, L/m 2 h 16 247 645 621 0 65 wet membrane thickness, microns 181 220 267 221 160 253 Gravimetric porosity, % 88.5 88.8 89.9 91.1 78.9 85.1 Static (water) CA, o 68 50 40.8 - - - First bubble point porosimeter, 0.025 0.146 - 0.149 - - microns [00411] Based on the results in Table 13, the membranes (E24-26, E32) made without pore forming agents in which the sPES copolymer additive was added to the PES polymer showed a higher water flux than the respective comparative membranes (CE23, CE31) without the sPES copolymer additive.
- 61 - SSPU 2022/035 [00412] Table 14 – properties of with pore forming agents Membranes CE27 E28 E29 E30 CE33 E34 sPES P1-B, wt.% relative to 0 5 10 20 0 10 SPES+PES Total sPES+PES, wt.% in solution 15 15 15 15 20 20 PEG400 wt.% 15 15 15 15 25 25 PVP k10 wt.% 5 5 5 5 5 5 in solution Properties of membranes liquid flow rate, 318 314 340 360 84 185 L/m2 h Wet membrane 177 226 213 203 249 191 thickness, microns Gravimetric 83.9 88.4 89.9 91.0 83.7 83.9 porosity, % Static (water) CA, o 61.3 58.8 58.9 - - - [00413] Based on the results in Table 14, the membranes (E29-E30, E34) made with pore forming agents in which the sPES copolymer additive was added to the PES polymer showed a higher water flux than the respective comparative membranes (CE27, CE33) without the sPES copolymer additive. [00414] The sPES copolymer additive presence in the membranes (E24-E26) without pore formers and membranes (E28-30) with pore forming agents increased the gravimetric porosity compared to the PES-based membrane CE23 without pore forming agents and PES-based membrane CE27 with pore forming agents, respectively. Similarly, the sPES copolymer additive presence in the membrane (E32) without pore formers and membrane (E34) with pore forming agents increased the gravimetric porosity compared to the PES-based membrane CE31 without pore formers and the PES-based membrane CE33 with pore formers, respectively. This effect of increased liquid flux was even more pronounced in absence of pore forming agents- see for example the high liquid flux (247, 645 & 621 L/m2 h) for membranes (E24-E26) according to the invention compared to very low liquid flow rate (16 L/m2 h) for comparative PES-based membrane CE23. [00415] It is believed that the low viscosity of the polymeric solution containing solely PES (without sPES) resulted in a poorer gravimetric porosity because of macrovoid formation for the PES membrane CE23 made without pore formers. Unfortunately the increase to 20 wt.% PES in the solution to make the membrane CE31 not only reduced the gravimetric porosity (to 79%) but also the membrane water flux to 0. - 62 - SSPU 2022/035 [00416] The membranes E24-E326, 30 made with a blend of PES and the sPES copolymer additive had a higher thickness compared to the respective comparative PES-made membranes CE23, CE31, CE27 with or without pore formers. [00417] Example 9: Porous membrane preparation by combined VIPS/NIPS methods and coagulation in water bath at 25°C [00418] Flat sheet porous membranes were prepared by filming polymeric solution (polymers + solvent + pore formers), over a suitable smooth glass support by means of an automatized casting knife. Dope solution quantity was 20 grams. [00419] Membrane casting was performed by holding dope solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the polymer. The knife gap was set to 250 µm. After casting, in order to induce a first phase inversion, the polymeric films were immediately introduced in a climatic chamber set at 35°C and 60% of humidity (VIPS- vapor induce phase separation). After 5 minutes the membranes formed were immediately immersed in a coagulation bath in order to complete the phase inversion (NIPS- non solvent induce phase separation). The coagulation bath consisted of pure de-ionized water maintained at 25°C. After coagulation the membranes were washed several times in pure water during the following days to remove residual traces of solvent. The membranes were always stored (wet) in water. [00420] Table 15 provides the composition of the polymeric solution comprising a total 17 wt.% of polymers (90 wt.% PES + 10 wt.% sPES P1-B), 25 wt.% PEG400 + 5 wt.% PVP k10 in NMP used to make membrane sample E36 by combined VIPS/NIPS methods and coagulation in water. A comparative membrane CE35 was made from solely PES with same amounts and types of pore forming agents using same combined VIPS/NIPS methods and coagulation in water. [00421] The wet thickness, liquid flow rate and gravimetric porosity are reported in Table 15 and FIG.1. [00422] Based on the results in Table 15 and illustrated in FIG.1, the membrane E36 in which the sPES copolymer P1-B additive was added to the PES polymer showed a higher thickness, higher water flux and higher gravimetric porosity than the comparative PES membrane CE35 made without the sPES copolymer additive. [00423] Example 10: Porous membrane preparation by combined VIPS/NIPS methods and coagulation in a bath containing solvent/non-solvent mixture [00424] A flat sheet porous membrane was prepared by filming a polymeric solution (polymers + solvent + pore forming agents), over a suitable smooth glass support by means of an automatized casting knife. Dope solution quantity was 20 grams. [00425] Membrane casting was performed by holding dope solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of - 63 - SSPU 2022/035 the polymers. The knife gap to 250 µm. After casting, in order to induce a first phase inversion, the polymeric film was immediately introduced in a climatic chamber set at 35°C and 60% of humidity. After 5 minutes the membrane formed was immediately immersed in a coagulation bath containing 30 wt.% NMP (solvent) + 70 wt.% deionized water (non-solvent), in order to complete the phase inversion and induce the formation of a sponge structure. After 5 minute of immersion in the coagulation bath maintained at 25°C, the membrane was washed several times in pure water during the following days to remove residual traces of solvent. The membranes were stored (wet) in water. [00426] Table 15 provides the compositions of the polymeric solutions comprising a total 17 wt.% of polymers (90 wt.% PES + 10 wt.% sPES P1-B), used to make membrane samples E38 and E39 by combined VIPS/NIPS methods and coagulation in the 30w/70w NMP:water bath. The difference between E38 and E39 is that the polymeric solution to make membrane E38 had 25 wt.% PEG400 + 5 wt.% PVP k10 in NMP while the polymeric solution to make membrane E39 had 35 wt.% PEG400 + 5 wt.% PVP k10 in NMP. [00427] The water flux, gravimetric porosity and wet thickness for these membranes are reported in Table 15 and illustrated in FIG.2. The membranes E38 and E39 in which the sPES copolymer P1-B additive was added to the PES polymer showed a higher water flux than the comparative PES membrane CE37 made without the sPES copolymer additive. [00428] Table 15 Membranes CE35 E36 CE37 E38 E39 sPES P1-B, wt.% relative to sPES+PES - 10 - 10 10 Compositions of polymeric dope solutions to make membranes PES, wt.% 17 15.3 17 15.3 15.3 sPES copolymer - 1.7 - 1.7 1.7 (P1-B), wt.% PEG 400 (wt.%) 25 25 25 25 35 PVP k10, wt.% 5 5 5 5 5 NMP, wt.% 53 53 53 53 43 Membrane Casting VIPS yes Coagulation bath (NIPS) Water at 25oC 30w/70w NMP:water at 25oC Membrane properties Wet thickness, microns 181 206 191 150 211 Water flux, L/m2 h 0 257 129 840 403 Gravimetric porosity, % 83.9 84.7 85.5 84.2 86.3 - 64 - SSPU 2022/035 [00429] Based on the results in Table was also observed that the membranes E38 and E39 which were made by VIPS/NIPS technique followed by coagulation in the NMP:water bath (30:70 w/w) at 25°C had a higher water flux than the membrane E36 made from the same polymeric solution using the same VIPS/NIPS technique, but with a coagulation in a water bath (without the initial presence of the NMP solvent). [00430] Example 11: Porous membrane preparation by NIPS method (without VIPS) and coagulation bath with solvent/non-solvent mixture [00431] A flat sheet porous membrane was prepared by filming a polymeric dope solution (polymers + solvent + pore forming agents), over a suitable smooth glass support. [00432] Membrane casting was performed by holding each dope solution, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the sulfone polymer(s). The knife gap was set to 250 µm. After casting, in order to induce a first phase inversion, the polymeric films were immediately immersed in a coagulation bath containing 30 wt.% NMP (solvent) + 70 wt.% deionized water (non-solvent) in order to initiate the phase inversion and induce the formation of a sponge structure. After 5 minutes of immersion in the coagulation bath maintained at 25°C, each membrane was washed several times in pure water during the following days to remove residual traces of solvent. The membranes respectively obtained from the different dope solutions were stored (wet) in water. In Example 11, the membrane was not introduced in a climatic chamber. [00433] Table 16 provides the composition of the polymeric dope solutions, each comprising a total 17 wt.% of sulfone polymers and two pore forming agents (5 wt.% PVP k10 ; 25 wt.% PEG 400) used to make membrane samples CE40 and E41-E44 by NIPS method (without VIPS) and coagulation in the 30:70 v/v NMP:water bath. The dope solution to make membrane CE40 only contained PES as the sulfone polymer. Each of the dope solutions to make membranes E41-E44 contained a blend of PES + sPES P1-B with a PES:sPES weight ratio of 9:1, 8:2, 7:3 and 1:1, respectively. [00434] The water flux, gravimetric porosity and wet thickness for these membranes are reported in Table 16. These properties are also illustrated in FIG.3 for membranes CE40 and E41. - 65 - SSPU 2022/035 [00435] Table 16 Membranes CE40 E41 E42 E43 E44 sPES P1-B, wt.% relative to sPES+PES - 10 20 30 50 Compositions of polymeric solutions to make membranes PES, wt.% 17 15.3 13.6 11.9 8.5 sPES copolymer (P1-B), wt.% - 1.7 3.4 5.1 8.5 PEG 400 (wt.%) 25 25 25 25 25 PVP k10, wt.% 5 5 5 5 5 NMP, wt.% 53 53 53 53 53 Membrane Casting VIPS no Coagulation bath (NIPS) 30w/70w NMP:water at 25oC Membrane properties Wet thickness, microns 157 166 186 146 224 Water flux, L/m2 h 225 383 411 381 364 Gravimetric porosity, % 85.8 85.8 - - - [00436] Based on the results in Table 16 and illustrated in FIG.3, the membranes E41- E44 according to the invention in which the sPES copolymer P1-B additive was blended with the PES polymer showed a higher water flux and a higher gravimetric porosity than the comparative PES membrane CE40 made without the sPES copolymer additive. [00437] The membranes E41, E42 and E44 according to the invention also showed a higher thickness than the comparative PES membrane CE40. [00438] Additionally it was observed that the membrane E41 which was made by NIPS technique (without VIPS) followed by coagulation in the NMP:water bath (30:70 w/w) at 25oC had a slightly lower water flux than the membrane E38 made from the same polymeric solution and formed by VIPS/NIPS technique and using same coagulation conditions (30w:70w NMP:water bath). [00439] The gravimetric porosity of membrane E41 using only NIPS was higher than the membrane E38 made using combined VIPS/NIPS. [00440] The data above reported in Table 16 for membranes E41-E44 made from sPES+PES blends using NIPS shows that the sPES additive addition to PES increased the water flux compared to membrane CE40 made solely from PES. The water flux performance enhancement reaches an optimum for membranes made from sPES+PES blends using NIPS when the polymer blend PES:sPES weight ratio was 80:20 (membrane E42). [00441] Example 12: Rejection testing - 66 - SSPU 2022/035 [00442] A person skilled in the art of manufacturing may correlate an increased permeate flow to an increase of the dimensions of the pores. In order to verify that the increased water flux observed in membranes made from PES+sPES blends was not compromising rejection properties, membrane rejection tests were performed by measuring the retention of the membranes of specific molecules (bovine serum albumin (“BSA”) or dextran 4kDa) with well-defined dimensions. [00443] The hydrodynamic diameter of BSA is about 14 nm – see Ragheb F. Atmeh et al. (2007). Albumin Aggregates: Hydrodynamic Shape and Physico-Chemical Properties”, Jordan Journal of Chemistry (JJC), 2(2), pages 169-182. Retrieved from https://jjc.yu.edu.jo/index.php/jjc/article/view/383. [00444] In an article by Ragheb F. Atmeh et al. (2007). Albumin Aggregates: Hydrodynamic Shape and Physico-Chemical Properties”, Jordan Journal of Chemistry (JJC), Issue 2(2), pages 169-182, the hydrodynamic diameter (“Dh”) of BSA was reported to be about 14 nm. [00445] In an article by Pierre Aimar et al. (1991) “A contribution to the translation of retention curves into pore size distributions for sieving membranes” Journal of Membrane Science, Vol 54 (3), pages 321-338, is provided a correlation on page 333 to calculate the hydrodynamic radius Rh (in Angstrom) from the molar mass (in g/mol) of dextran: Rh =0.33*M0.46. [00446] Using this correlation with M=4000 g/mol and 1 nm = 10 Angstroms, the hydrodynamic diameter Dh (= 2 x Rh) for dextran 4 was calculated to be about 3 nm. [00447] In an article by James J. Choi et al. (2010) “Molecules of Various Pharmacologically-Relevant Sizes Can Cross the Ultrasound-Induced Blood-Brain Barrier Opening in vivo” in Ultrasound in Medicine & Biology vol.36, Issue 1, pages 58-67, it was reported that the hydrodynamic diameter Dh of the 3kDa dextran measured using a Zetasizer (Nano-ZA, Malvern Instrument Ltd., Malvern, Worcestershire, UK) was 2.33±0.38. In this method, particle motion induced by laser illumination was used in the Stokes-Einstein relationship to estimate the hydrodynamic diameter. Being that the molecular size correlates to the molecular weight of dextrans, and since the molecular weight of dextran 4kDa is slightly higher than dextran 3kDa, this estimated Dh value of 3 nm for dextran 4kDa is reasonable compared to the value of 2.33 nm reported for dextran 3kDa. [00448] Rejection measurement method: A dead-end stirred cell filtration system was designed to characterize the filtration performance of membranes. The system consisted of a 180 ml filtration cell (model 8200, Amicon, W.R. Grace, Beverly, MA). All filtration experiments were conducted at a constant driven pressure of 1 bar (by N2 gas line) and a stirring rate of 200 rpm at room temperature with : - 67 - SSPU 2022/035 - a feed of 0.3 g/L bovine albumin (BSA) in phosphate buffered saline (PBS) at pH 7.4; or - a feed of 0.3 g/L dextran 4kDa in phosphate buffered saline (PBS) at pH 7.4. [00449] The permeate flux was calculated by gravimetric method versus time considering a membrane sample area equal to 26.41 cm2. All the rejection % values are referred to the sampling after the first 7.5 minutes. [00450] 2 mL of permeate sample were collected to determine the COD (chemical oxygen demand). [00451] COD Analysis: The COD was measured using an oven HT 200 S (15 minutes at 170°C) and a spectrophotometer DR 3900 VIS from Hach, using LCK 314 and LCK 514 cuvettes. [00452] The BSA rejection ratio was calculated by the following equation: R%= ( Cf-Cp)/Cf*100 wherein Cp and Cf are the COD concentrations in mg/L in the permeate and in the feed, respectively. [00453] The retention test was carried out on the membranes CE31 and E32 made from a polymer dope solution in NMP containing 20 wt.% polymers (PES+sPES P1-B with 9:1 weight ratio), 25wt.% PEG 400 and 5 wt.% PVP k10 which was coagulated in a 30:70 w/w NMP/water bath. [00454] The retention test was carried out on the membranes CE40 and E41-E44 made from a polymer dope solution in NMP containing 17 wt.% polymers (PES+sPES P1-B with weight ratios being from 9:1 to 1:1), 25wt.% PEG 400 and 5 wt.% PVP k10 which was coagulated (NIPS) in a 30:70 w/w NMP/water bath. [00455] The BSA and dextran 4 retentions were reported in Table 17. [00456] Table 17 Membrane CE31 E32 CE40 E41 E42 E43 E44 sPES P1-B, wt.% relative to SPES+PES - 10 - 10 20 30 50 Dope solution composition Total sPES+PES, 20 20 17 17 17 17 17 wt.% in solution PEG400, wt.% in 25 25 25 25 25 25 25 solution PVP k10, wt.% in 5 5 5 5 5 5 5 solution Membrane Properties liquid flow rate, L/m2/h 84 185 225 383 411 381 364 BSA rejection, % 94 94 97 94 93 97 96 dextran 4 rejection, % 0 0 0 0 0 0 0 - 68 - SSPU 2022/035 [00457] The BSA rejection values (93 to can be considered equivalent. Since the liquid flow rate observed with membranes E32 and E41-E44 containing the sPES additive was much higher compared to comparative PES membranes CE31 and CE40 respectively, this demonstrated that the higher liquid flux observed for the membranes E32 and E41-E44 according to the invention was not related to an enlargement of the pores and hence rejection properties were preserved. The enhanced performance can be attributed to the sPES additive presence. [00458] By comparing the rejection value to the probe Dextran 4 and BSA, the pore size diameter of the membrane samples can be considered higher than about 3 nanometers (nm). [00459] Example 13: SEM analysis of porous membranes prepared in Examples 6, 7, 9 & 10 [00460] Microscopic observation of the membrane surfaces and cross-section were performed by using a scanning electron microscope (SEM) Hitachi, TM400 Plus II at an accelerating voltage of 10kV. To realize the cross-section samples, the membranes wet in IPA were freeze-fractured in liquid nitrogen instead the surfaces after drying from IPA, were directly placed on the holder. All surfaces and cross- section were coated with Au before use. [00461] The SEM pictures in Fig.4-13 for membrane samples CE23, E24-E26, CE31, E32, E34, CE35, E36, E38 were obtained with a magnification of 2000x. [00462] Fig. 4 to 6 represent SEM pictures of membranes E24-E26 according to the invention. [00463] Fig.7 and 8 represent SEM pictures of two comparative membranes CE23 & CE31 made from PES. [00464] Fig.9 represents a SEM picture of the membrane E32 according to the invention, which was made from a polymeric solution containing 20 wt.% of a blend of 10 wt.% sPES/90 wt.% PES without pore forming agents. [00465] Fig.10 represents a SEM picture of the membrane E34 according to the invention, which was made from a polymeric solution containing 20 wt.% of a blend of 10 wt.% sPES/90 wt.% PES with pore forming agents. [00466] Fig.11 represents a SEM picture of the comparative membrane CE35 made from a polymeric solution containing 17 wt.% PES with pore forming agents using VIPS/NIPS technique using a climatic chamber followed by coagulation at 25oC in a water bath. [00467] Fig.12 represents a SEM picture of the membrane E36 according to the invention, which was made from a polymeric solution containing 17 wt.% of a blend of 10 wt.% sPES/90 wt.% PES with pore forming agents using combined VIPS/NIPS technique using a climatic chamber followed by coagulation at 25oC in a water bath. - 69 - SSPU 2022/035 [00468] Fig.13 represents a SEM membrane E38 according to the invention, which was made from a polymeric solution containing 17 wt.% of a blend of 10 wt.% sPES/90 wt.% PES with pore forming agents using combined VIPS/NIPS technique using a climatic chamber followed by coagulation at 25oC in a NMP:water bath (30:70 w/w). [00469] As shown in Fig.7 and 8, the membranes CE23 and CE31 made from solely PES (without sPES additive and without pore formers) showed a closed layer structure compared to membranes E24-E26, E32 without pore forming agents, and membrane E34 with pore forming agents according to the invention (see Fig.4-6 & 9-10). [00470] For the membranes made using a climatic chamber in VIPS/NIPS technique, the SEM picture showed a spongy structure without macrovoid formation. By adding the sPES P1-B to PES (10 wt.% sPES), this created an open structure for the membranes E36 and E38 (see Fig.12 & 13), and there was an increase in water permeation (as shown in Table 15 and Fig.1-2 with higher water flux) compared to PES membranes CE35 and CE37. [00471] The SEM picture in Fig, 11 for the comparative membrane CE35 (17 wt.% of PES with pore forming agents) showed a close structure of membrane and was consistent with the water permeability test in which the flux was 0, despite having a spongy structure. [00472] Example 14: Compatibility test of PPSU and sPES (P1-B) [00473] Blending of polymers is widely accepted in the industry for the production of a polymeric materials with specific applications through an inexpensive route which otherwise not attainable with a single polymer. One of the important controlling parameter in this case is the degree of compatibility of the polymers blended. [00474] A test for polymers compatibly was carried out by preparing a polymeric solution comprising a total 20 wt.% of polymers (PPSU + sPES with a PPSU:sPES weight ratio of 95:5) in NMP as solvent. The PPSU polymer was Radel® 5000NT and the sPES copolymer (P1) was the copolymer (P1-B) described in Example 1. The resulting solution was homogenous and clear, confirming the compatibility of PPSU and the sulfonated PES. [00475] Example 15: PPSU membranes preparation (15wt.% sulfone polymers in solution with pore forming agents made by NIPS and coagulation in 50w/50w NMP/water at 50°C) [00476] Flat sheet porous membranes were prepared by filming polymeric solution (polymers + solvent + pore formers), over a suitable smooth glass support by means of an automatized casting knife. Dope solution quantity was 20 grams. - 70 - SSPU 2022/035 [00477] Membrane casting was holding polymeric solutions, the casting knife and the support temperatures at 30°C, in order to prevent premature precipitation of the polymer. The knife gap was set to 250 µm. After casting, in order to induce phase inversion, the polymeric films were immediately immersed in a coagulation bath in order to complete the phase inversion (NIPS- non solvent induce phase separation). The coagulation bath consisted of 50 wt.% in pure de- ionized water and 50 wt.% of NMP and was maintained at 50°C. After 5 minutes, the coagulated membranes were washed for 5 minutes in pure de-ionized water and then washed several times in pure water during the following days to remove residual traces of solvent. The membranes were stored (wet) in water. [00478] Table 18 provides the compositions of the polymeric solutions comprising a total 15 wt.% of sulfone polymers (PPSU alone or a blend of PPSU + sPES with a weight ratio PPSU:sPES = 9:1 w/w), 25 wt.% PEG400 and 5 wt.% PVP k10, used to make membrane samples CE45 (PPSU) and E46 (90w PPSU+10w sPES) by using NIPS method and coagulation in the 50:50 w/w NMP/water bath at 50oC. [00479] The liquid flow rate, gravimetric porosity and BSA rejection % are reported for membranes CE45 and E46 in Table 18. [00480] Based on the results in Table 18 and as illustrated in FIG.14, the membrane E46 in which the sPES copolymer additive was added to the PPSU polymer showed a higher water flux, higher rejection and higher gravimetric porosity than the comparative membrane CE45 made with PPSU and without the sPES copolymer additive. [00481] Table 18 CE45 E46 sPES P1-B, wt.% relative to - 10 sPES+PPSU Dope solution composition PPSU, wt.% in solution 15 13.5 sPES copolymer - 1.5 (P1-B), wt.% in solution PEG 400 (wt.%) in solution 25 25 PVP k10, wt.% in solution 5 5 NMP, wt.% in solution 55 55 Membrane Casting VIPS no Coagulation bath (for NIPS) 50w/50w NMP/water at 50oC Membrane properties liquid flow rate, L/m2 h 477 607 Gravimetric porosity, % 87.1 88.2 BSA Rejection, % 83 88 - 71 - SSPU 2022/035 [00482] Example 16: PPSU (19wt.% sulfone polymers in solution with pore forming agents made by NIPS and coagulation in 50w/50w NMP/water at 50°C [00483] The preparation of the membranes In this example was carried out as described in Example 15, except that : - The sulfone polymer(s) content (PPSU or PPSU+sPES) in the polymeric solution was increased from 15 wt.% to 19 wt.%; - the content of sPES (P1-B) relative to the total weight of PPSU and sPES was increased from 10 wt.% to 20 wt.%; - the pore forming agents in the polymeric solution (25 wt.% PEG400 and 5 wt.% PVP k10) were substituted with 5 wt.% glycerol and 4 wt.% PVP k90. [00484] Table 19 provides the compositions of the polymeric solutions comprising a total 19 wt.% of polymers (PPSU alone or a blend of PPSU + sPES with a weight ratio PPSU:sPES = 80:20) used to make membrane samples CE47 and E48 by NIPS technique and coagulation in the 50:50 w/w NMP/water bath at 50oC. [00485] The liquid flow rate is reported for membranes CE47 and E48 in Table 19. [00486] Table 19 Membranes CE47 E48 sPES P1-B, wt.% relative to - 20 sPES+PPSU Dope solution composition PPSU, wt.% in solution 19 15.2 sPES copolymer (P1-B), wt.% in solution - 3.8 Glycerol wt.% in solution 5 5 PVP k90, wt.% in solution 4 4 NMP, wt.% in solution 72 72 Membrane casting VIPS no Coagulation bath 50w/50w NMP/water at 50oC Membrane properties liquid flow rate, L/m2 h 0 510 [00487] Even in this example, the membrane E48 in which the sPES copolymer additive was added to the PPSU polymer showed a higher water flux. [00488] What is claimed is:

Claims

72 SSPU 2022/035 Claims Claim 1. A polymeric composition comprising from 1 to 50 parts by weight of a sulfonated and/or carboxylated sulfone copolymer (P1) (hereinafter “copolymer (P1)”) and from 50 to 99 parts by weight of a polyarylethersulfone polymer (P2) (hereinafter “PAES polymer (P2)”), said parts by weight being based on combined weights of the copolymer (P1) and the PAES polymer (P2), said copolymer (P1) comprising collectively at least 80 mol.% of: - sulfone recurring units (RP1) of formula (M1): , - , and said units (RP2) of formula (M2): , - each R1 is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; 73 SSPU 2022/035 - each R4 is independently the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, ester, amide, imide, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i and m are independently 0 or an integer from 1 to 4, preferably i=0 and m=0; - GN is selected from the group consisting of at least one of the following formulae (GN1), (GN2), (GN3), (GN4), (GN5), (GN6): - - each j is independently an integer from 3 to 7; - each of T1, T2, and W is independently selected from the group consisting of a bond, -CH2-; -O-; -SO2-; -S-; -C(O)-; -C(CH3)2- ;-C(CF3)2-; -C(=CCl2)-; - C(CH3)(CH2CH2COOH)-; -N=N-; -RaC=CRb-, where each Ra and Rb, independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; - (CH2)n- and -(CF2)n- with n being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof, 74 SSPU 2022/035 - each ─R2 is independently selected the group consisting of ─ (CH2)u – COO-M+, ─ (CH2)q – SO3-M+, and any combination thereof, with u, q being integers independently selected from 1 to 5 and M+ being a cation, preferably selected from H+, alkali metal cations, alkali earth metal cations, NH4+ or any combination thereof, more preferably selected from H+, K+, Li+, Na+ and/or NH4+, and wherein the molar ratio of recurring units (RP1)/recurring units (R*P1) varies between 100/1 and 1/1, preferably between 50/1 and 2/1, more preferably between 40/1 and 3/1. Claim 2. The polymeric composition of claim 1, wherein: T1 in recurring units (RP1) is selected from the group consisting of a bond, -SO2- and - C(CH3)2-, T2 in recurring units (RP2) is selected from the group consisting of a bond, -SO2- and - C(CH3)2-., and W in any of the formulae (GN1), (GN2), (GN3), (GN4), (GN5), (GN6) of recurring units (R*P1) is selected from the group consisting of a bond, -SO2- and -C(CH3)2-. Claim 3. The polymeric composition of any of claims 1 to 3, wherein i is zero for each R1 of recurring units (RP1) and recurring units (R*P1), and m is zero for each R4 of recurring units (RP2). Claim 4. The polymeric composition of any of claims 1 to 6, wherein T1 in recurring units (RP1) and T2 in recurring units (RP2) are the same and preferably are either -SO2- or -C(CH3)2-. Claim 5. The polymeric composition of any one of claims 1 to 4, wherein the recurring units (RP1) and the recurring units (RP2) are represented by at least one of the following formulae (M1a), (M1b), or (M1c): 75 SSPU 2022/035 . (RP1a) and the recurring units (RP2) are represented by the same formula, preferably represented by the same formula (M1a), or wherein the recurring units (RP1a) are represented by the formula (M1a) and the recurring units (RP2) are represented by the formula (M1b) or (M1c). Claim 7. The polymeric composition of any one of claims 1 to 6, wherein k is 0 and j is 3 in the recurring units (R*P1). Claim 8. The polymeric composition of any one of claims 1 to 7, wherein each ─R2 in any of the formulae (GN1), (GN2), (GN3), (GN4), (GN5), (GN6) of recurring units (R*P1) is ─ (CH2)q – SO3M, with q being an integer from 1 to 5 and M being H, NH4 or an alkali metal, preferably each ─R2 is – (CH2)3 – SO3H and/or – (CH2)3 – SO3Na. Claim 9. The polymeric composition of any one of claims 1 to 8, wherein the copolymer (P1) is a sulfonated copolymer with a degree of sulfonation from 4 to 50 mol% or a carboxylated copolymer with a degree of carboxylation from 4 to 50 mol%. Claim 10. The polymeric composition of any one of claims 1 to 9, comprising - from 5 to 40 parts by weight, preferably from 10 to 40 parts by weight, more preferably from 10 to 30 parts by weight, of the copolymer (P1), and - from 60 to 95 parts by weight, preferably from 60 to 90 parts by weight, of the PAES polymer (P2), said parts by weight being based on the combined weights of the copolymer (P1) and the PAES polymer (P2). Claim 11. A polymeric solution, comprising the polymeric composition of any one of claims 1 to 10, and further comprising at least a solvent suitable to dissolve the copolymer (P1) and the PAES polymer (P2), wherein the combined weights of the copolymer (P1) and polymer (P2) in the polymeric solution is from 5 wt.% to 40 wt.%, preferably from 8 wt.% to 35 wt.%, more preferably from 10 wt.% to 25 wt.%, yet more preferably from 10 wt.% to 20 wt.% or from 12 wt.% to 18 wt.%, said wt.% being based on the total weight of the polymeric solution. 76 SSPU 2022/035 Claim 12. The polymeric solution of claim 11, wherein the solvent is selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2- pyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl isosorbide (DMIso), methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv® Polar-clean), cyrene, ε-caprolactam, butyrolactone, N,N-dimethylformamide (DMF), N,N- dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, sulfolane, and any combination of two or more thereof. Claim 13. The polymeric solution of claim 11 or 12, further comprising a pore forming agent selected from the group consisting of at least one polyvinylpyrrolidone preferably having a molecular weight of at least 5,000 g/mol to 100,000 g/mol; at least one polyalkylene glycol with a formula weight ≥ 200, preferably from 200 to 900; at least one (poly)hydroxyl aliphatic alcohol having from 1 to 6 carbon atoms, preferably at least one glycerol compound, at least one carboxylic acid comprising at least 3 carbon atoms, and any combination thereof. Claim 14. Use of the polymeric composition of any one of claims 1 to 10 or of the polymeric solution of any one of claims 11 to 13, in the preparation of an article, preferably a film, tube, fiber or membrane. Claim 15. An article, such as a film, tube, fiber or a membrane, comprising the polymeric composition of any one of claims 1 to 10, or made from the polymeric solution of any one of claims 11 to 13. Claim 16. The article of claim 15, being porous and selected from a hollow fiber, hollow tube, porous film or porous membrane, to be used for medical applications such as hemodialysis membranes and/or for water filtration, such as reverse osmosis membranes, ultrafiltration membranes, microfiltration membranes, nanofiltration membranes, and ion-exchange membranes. Claim 17. The article of claim 15 or 16, being a hemodialysis membrane or water filtration membrane, wherein the copolymer (P1) is a sulfonated or carboxylated PES or PSU copolymer and further wherein the polymer (P2) is a PES, PSU or PPSU polymer.
EP23836508.4A 2022-12-21 2023-12-20 Polymeric composition comprising a blend of poly(aryl ether sulfone) polymers suitable for manufacturing articles Pending EP4638602A1 (en)

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