Polyaryl ether sulfone copolymers with improved hydrophilicity

Abstract

A polyarylether sulfone ('PAES') copolymer, a process for preparing the PAES copolymer, an article, such as a film, fiber, film or a portion thereof, comprising the PAES copolymer, the use of the PAES copolymer in the preparation of an article, a polymer solution comprising the PAES copolymer and a method of using such an article for the treatment of aqueous media. The PAES copolymer is a random polymer comprising at least two types of repeating units, one of which is derived from the condensation of a diol and a dihaloalkylene oxide and the other of which is derived from the condensation of the same diol and dihalodiphenyl sulfone. The diol may be aromatic or alicyclic. The dihaloalkylene oxide preferably has up to 9 carbon atoms and / or up to 4 oxygen atoms.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Patent Application No. 63 / 415,044, filed Oct. 11, 2022, and European Patent Application No. 23157251.2, filed Feb. 17, 2023, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] This disclosure relates to a poly(aryl ether sulfone) (“PAES”) copolymer having improved hydrophilicity, to a method for manufacturing such a PAES copolymer, to articles comprising such a PAES copolymer, particularly films, hollow tubes, hollow fibers or porous membranes, and to the use of the PAES copolymer for the preparation of such articles. Background Art

[0004] Poly(aryl ether sulfone) (PAES) polymers are also high-performance polymers having high mechanical strength and high thermal stability; they are used in a variety of industrial applications. Their chemical resistance, heat resistance and mechanical resistance, combined with their excellent hydrolysis stability and relatively low production cost, make them suitable for widespread use in making membranes, particularly porous membranes, e.g., porous hollow-fiber polymer membranes. Porous hollow-fiber polymer membranes are used 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 having optimal selectivity as well as chemical, thermal and mechanical stability are desired.

[0005] Membranes made from PAES polymers are hydrophobic in nature and thus have water repellency, low water permeability and are subject to particle and protein fouling on their surfaces. Hydrophobicity hinders water penetration into the porous PAES membrane and thus higher pressure and more energy consumption are required for water permeability. In addition, the inherent hydrophobicity of PAES polymers makes the membranes made therefrom prone to fouling, which negatively affects their performance. Fouling is caused by hydrophobic interactions between the membrane material and contaminants (e.g., microorganisms, proteins or organic substances) from the aqueous fluid to be treated by the membrane. In particular, fouling is triggered by the adsorption of contaminants onto the membrane surface and / or its internal porous structure, resulting in pore blockage, cake layer formation and / or biofilm formation. Membrane fouling not only temporarily or permanently reduces the permeation flux of water through the membrane, e.g., in ultrafiltration or microfiltration processes, thereby reducing membrane permeability and overall lifetime, but also increases maintenance costs due to extensive and frequent cleaning to remove contaminants.

[0006] Although PAES polymers have many advantages and good physical properties, there are times when it is desirable to adjust one or more properties to improve performance in a particular application (e.g., hemodialysis, bioseparation, or water filtration), such as becoming less prone to fouling, having increased hydrophilicity, and / or having improved biocompatibility.

[0007] Since most commercial pressure-driven membranes are made from hydrophobic polymers (including polyethersulfone (PES) and polysulfone (PSU)), enhancing surface hydrophilicity can be achieved by increasing the density of hydrophilic groups at the membrane surface. It is generally believed that increasing the hydrophilicity of PAES membranes provides better fouling resistance because most proteins and other contaminants are hydrophobic in nature.

[0008] Several strategies have been adopted to make porous PAES membranes hydrophilic and thus highly water-permeable and highly fouling-resistant. Among the methods that have been employed, methods based on grafting hydrophilic substances onto the membrane surface, incorporating hydrophilic comonomers into the polymer chains of the main polyarylethersulfone polymer, incorporating hydrophilizing additives, etc. can be cited. These methods are reviewed, for example, in Rana et al., Surface Modifications for Antifouling Membranes, Chemical Reviews, 2010, Vol. 110, No. 4, pp. 2448-2471.

[0009] For example, PAES can be blended with highly hydrophilic polymers (such as polyvinylpyrrolidone or polyethylene oxide) to increase the hydrophilicity of PAES-based membranes, while PAES can be blended with zwitterionic polymers to impart fouling resistance to the membranes. Although this method may be straightforward, there are serious limitations because the two or more polymers that are usually blended are incompatible, which results in severe macroscopic phase separation in the final polymer blend. In addition, since these polymers are simply physical mixtures, the resulting polymer blend may change its composition over time after membrane use, and also change its performance due to the loss of one of the polymers by diffusion during membrane operation.

[0010] Another way to avoid such behavior is to covalently link the PAES homopolymer and another hydrophilic polymer such that the resulting material has a robust composition and does not change substantially during application. The hydrophilic modification can also be achieved by combining two homopolymers to prepare block copolymers that have a combination of the inherent properties of each individual homopolymer. In membrane applications, the PAES homopolymer can be covalently linked to a hydrophilic homopolymer to synthesize a new PAES-hydrophilic block copolymer that has superior membrane properties due to the enhanced wettability caused by the hydrophilic component while retaining the mechanical robustness and amorphous pore structure of the PAES component.

[0011] Several methods for preparing such aromatic sulfone-based block polymers are illustrated in the following references.

[0012] WO 2006 / 12453A1 (Solvay) describes block copolymers comprising: at least one block of a polymer (block (A)) comprising at least 50 mol% of repeating units (R1) which are formed by a polycondensation reaction between at least one aromatic dihalide comprising at least two -S(=O)2- groups and at least three aromatic rings and at least one aromatic diol; and at least one block of a polymer (block (B)) comprising at least 50 mol% of repeating units (R2) which are formed by the polymerization of at least one alkylene oxide. The method for synthesizing said block copolymer. WO'453 also describes an article, particularly a membrane, comprising such a block copolymer, and the use of such a membrane for purifying a liquid or for separating a gas.

[0013] US2016 / 07850A1 (Weber et al.) describes a method for preparing a PAES-polyalkylene oxide block copolymer, which method comprises an aromatic dihalogen compound, an aromatic dihydroxy compound, a polyalkylene oxide comprising at least two hydroxyl groups (usually 1 to 500 alkylene oxide units; most preferably 10 to 80 units, M n >200 g / mol), an aprotic solvent and a metal carbonate. US'850 specifies the absence of an azeotropic agent in the polymerization as it states that the absence of an azeotropic agent in the synthesis is associated with a longer polyaryl ether block and thus a higher Tg compared to comparative examples.

[0014] US2013 / 035457 (Weber et al.) describes a two-step method for preparing a block copolymer, in which an HO-terminated polyarylene ether (macromolecular initiator) reacts as a phenolate with a monomer alkylene oxide to obtain a block copolymer comprising a polyarylene ether and a poly(alkylene oxide). US'457 also relates to a triblock polymer having a polyalkylene oxide-polyaryl ether-polyalkylene oxide block.

[0015] Zhang et al. (1994) described the use of 1,2-bis(2-chloroethoxy)ethane (dichloroethylene oxide) in the synthesis of poly(ethylene oxide-co-ethylene sulfone) in “Synthesis and characterization of poly(ethylene oxide-co-ethylene sulfone)s and their precursors: poly(ethylene oxide-co-ethylene sulfide)s”, Journal of Polymer Sciences: Part A: Polymer Chemistry, Vol. 32, pp. 1323-1330. The polymer structure contains no aromatic rings.

[0016] Gronwald et al. (2020) explained the lower hydrophilicity of PPSU compared to PESU in “Hydrophilic poly(phenylene sulfone) membranes for ultrafiltration,” Separation & Purification Technology, Vol. 250, p. 117107, which affects the pore size and membrane fabrication, preventing the use of PPSU for ultrafiltration membranes. The paper described the synthesis of PPSU-poly(alkylene oxide) block copolymers as additives for dope solutions of PPSU membranes, which have enhanced hydrophilicity and hydraulic permeability and reduced fouling. The polymerization products of DCDPS and biphenol with three different commercial poly(alkylene oxides) having one or two hydroxyl end groups and an average molecular weight of about 3780 to 12,400 g / mol were described. Block oligomers with PPSU block sizes in the range of 2000 to 8000 g / mol were introduced as additives at a membrane polymer content of about 9 wt.%.

[0017] However, the preparation of block copolymers generally requires several synthetic steps involving the formation of various blocks.

[0018] Another method of modifying hydrophilicity can be achieved by preparing PAES copolymers using hydrophilic monomers, which can result in the incorporation of hydrophilic moieties in the PAES backbone and / or side chains. This method for preparing such PAES copolymers is illustrated in the following references.

[0019] US 4503212 (Dexheimer) describes the use of bisphenol S and ethylene oxide or propylene oxide in the preparation of sulfone polyethers used as heat-stable lubricants for fibers and rubbers. Such a method is based on the ring-opening polymerization of one or more alkylene oxides initiated by a salt of bisphenol S. The molar ratio of alkylene oxide to bisphenol S ranges from about 12 to 200, and each bisphenol S is attached to aliphatic polyether blocks of different lengths. US '212 does not use a dihalo monomer.

[0020] JP 2008266325 A (API Corp. and JUJO PAPER, Co., Ltd.) relates to the use of bisphenol S and 1,2-bis(2-chloroethoxy)ethane (dichloroethylene oxide) in the synthesis of diphenylsulfone derivatives. Such polymers are used as thermosensitive recording materials and exhibit improved characteristics for storage stability. JP '325 uses only two monomers for polymer synthesis.

[0021] KR 20160082913 A (Samyang Corp.) relates to a copolymer prepared by the polymerization of bisphenol A, ethoxylated isosorbide, and DCDPS. KR '913 uses two dihydroxy monomers, where ethoxylated isosorbide is selected to increase hydrophilicity, but only one dihalo monomer is used for polymer synthesis.

[0022] WO 2018131381 A1 (Toray) relates to epoxy group-terminated polysulfides / polythioethers. The trifunctional core of the polymer is formed by reacting 1,2,3-trichloropropane and 1,2-bis(2-chloroethoxy)ethane with Na(SH) and Na2(S x ) to form a thioether linkage which reacts with 2-(dichloromethyl)ethylene oxide and bisphenol A to obtain terminal epoxy groups. WO '381 does not use a dihydroxy monomer.

[0023] Accordingly, there is a desire to develop polyarylethersulfone polymers having increased hydrophilicity, having anti-fouling behavior, and in which the hydrophilic component does not leach out over time during use in articles containing the polyarylethersulfone polymer, such as highly permeable porous membranes. The membrane should exhibit high thermal and chemical stability, which can ensure durable characteristics.

[0024] It is also desirable to develop polyarylether sulfone polymers as dope solution additives for PAES membranes (e.g., PES membranes, PSU membranes), with the additives being dispersed in these PAES membranes, such PAES membranes having high mechanical, thermal and chemical stability, enhanced hydrophilicity, hydraulic permeability and reduced fouling. The polymer additive must be incorporated into the PAES polymer membrane easily and durably to enhance its hydrophilicity, water permeability and anti-fouling behavior over the long term without compromising the inherent properties of the PAES polymer, which are high mechanical, thermal and chemical properties. In addition, the polymer additive must be a very effective hydrophilic agent for economical use, thereby avoiding any adverse effects on the mechanical, heat resistance and chemical resistance of the porous PAES membrane due to its excessive presence. Summary of the Invention

[0025] Accordingly, the present invention relates to a new polyarylether sulfone [hereinafter "PAES"] copolymer having improved hydrophilicity and biocompatibility, which is based on the copolymerization of at least one diol and the following two halogenated monomers: dichlorides of monomers containing an alkylene oxide and dihalodiphenyl sulfone. The diol can be aromatic or alicyclic. The halogenated monomer containing an alkylene oxide contains at least one group represented by the formula -(CHR l ) y O-, where R l is H or an alkyl group, and y can be from 1 to 5. The PAES copolymer according to the present invention is preferably a random polymer prepared by a one-step polymerization method, which means that all monomers are present in the reaction mixture to form the polymer backbone of the PAES copolymer. The PAES copolymer of the present invention is particularly suitable for use as an aqueous membrane or a membrane additive.

[0026] Accordingly, a first aspect of the present invention relates to a PAES copolymer comprising a total of at least 80 mol.% of two different repeating units (R AO ) and (R PAES ), said mol.% being based on the total number of moles of repeating units in the copolymer. Preferably, at least 50 mol.% of the repeating units in the PAES copolymer are repeating unit (R PAES ).

[0027] The repeating unit (R AO ) can be a unit represented by any formula selected from the group consisting of the formulas (M1), (M’1), (M1a) to (M1i) described below, and the repeating unit (R PAES ) can be a unit represented by any formula selected from the group consisting of the formulas (N), (N’), (N”) described below.

[0028] A second aspect of the present invention relates to a process for preparing a PAES copolymer, the process comprising reacting a monomer mixture comprising at least one dihaloalkylene oxide compound [hereinafter dihalo monomer (AO)], at least one dihaloarylsulfone compound [hereinafter dihalo monomer (AS)] and at least one dihydroxy compound [hereinafter dihydroxy monomer (B)] in a reaction mixture comprising a polar aprotic solvent and in the presence of an alkali metal carbonate, wherein

[0029] - the monomer mixture contains at least 4 mol.%, or at least 5 mol.%, or at least 6 mol.%, or at least 8 mol.%, or at least 10 mol.%, or at least 12 mol.% and up to 50 mol.%, or up to 40 mol.%, or up to 30 mol.%, or up to 25 mol.% of the dihalo monomer (AO), said mol.% being based on the combined molar amount of the dihalo monomers (AO) and (AS);

[0030] - the total amount of halogen and hydroxyl groups of the monomers in the monomer mixture is substantially equimolar; and

[0031] - when expressed as the ratio of the equivalents of the alkali metal (Me) to the equivalents of the hydroxyl groups (OH) in the monomer (B) [eq.(Me) / eq.(OH)], the amount of the alkali metal carbonate used in the reaction mixture is greater than 1, preferably at least 1.05 and optionally up to 2, or up to 1.5, or up to 1.3.

[0032] The at least one dihalo (AO) monomer in the reaction mixture contains at least one epoxyalkyl group represented by the formula -(CHR l ) y O-, wherein R l is H or an alkyl group, preferably H or methyl; and y can be an integer of at least 2 and optionally up to 5; more preferably, y is equal to 2 and at least one R l is H. The at least one dihalo (AO) monomer in the reaction mixture preferably contains at least 2 and optionally up to 5 such epoxyalkyl groups. The dihalo (AO) monomer can have a total of 5 to 9 carbon atoms. The dihalo (AO) monomer can have a total of 1 to 4 oxygen atoms.

[0033] The at least one dihalo (AO) monomer in the reaction mixture is preferably at least one compound represented by a formula selected from the group consisting of formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih) and / or (Ii), such formulas being described hereinafter.

[0034] The at least one dihalo (AS) monomer in the reaction mixture has the formula (V) described hereinafter.

[0035] The at least one dihydroxy (B) monomer in the reaction mixture may be selected from the group consisting of:

[0036] · tetramethylbisphenol F,

[0037] · at least one 1,4:3,6-dianhydrohexitol, preferably isosorbide;

[0038] · at least one alicyclic diol,

[0039] · at least one aromatic diol preferably having the formula (VI) described below, more preferably selected from 4,4'-biphenol, bisphenol S and / or bisphenol A; and

[0040] · any combination thereof.

[0041] A third aspect of the present invention relates to a PAES copolymer obtainable by the method according to the second aspect.

[0042] A fourth aspect of the present invention relates to the use of a PAES copolymer according to the present invention for the preparation of non-porous articles such as dense (thick or thin) films or tubes, said use comprising a polymer solution casting or polymer melt processing method. The non-porous film may be referred to as a "dense" film. The PAES copolymer may be the sole polymer in the polymer solution or melt used to prepare the non-porous article, or the non-porous article may further comprise at least one other polymer.

[0043] A fifth aspect of the present invention relates to the use of a PAES copolymer according to the present invention for the preparation of porous articles (such as porous films, hollow fibers, hollow tubes or porous membranes), or a method for preparing such porous articles using a phase inversion technique selected from non-solvent induced phase separation or thermally induced phase separation. Such use or method comprises casting or spinning a polymer dope solution comprising a PAES copolymer, a solvent, optionally a co-solvent and optionally at least one pore former into such porous article and then cooling it or contacting it with a non-solvent to induce phase separation. The PAES copolymer may be the sole polymer in the polymer dope solution; or the dope solution may further comprise at least one other polymer.

[0044] A sixth aspect of the present invention relates to an article, preferably a fiber, film, tube, membrane or a part thereof (such as a membrane layer or coating), said article comprising a PAES copolymer according to the present invention. The article may be porous or non-porous. The porous article may be used for medical applications (such as hemodialysis membranes) or for aqueous media or water filtration, such as reverse osmosis membranes, ultrafiltration membranes, microfiltration membranes, nanofiltration membranes and / or ion exchange membranes. The article may be used for solid state battery applications, such as polymer electrolyte membranes or polymer or solid electrolytes. The PAES copolymer may be the sole polymer in the article, or the article may further comprise at least one other polymer.

[0045] The seventh aspect of the present invention relates to a polymer solution comprising the PAES copolymer according to the present invention. Such a polymer solution is particularly suitable for forming thin films, fibers, tubes, membranes or parts thereof (such as membrane layers or coatings).

[0046] The eighth aspect of the present invention relates to a method for purifying an aqueous medium (such as water, an aqueous solution (e.g., alkaline)), a biological fluid (e.g., blood, plasma or serum) and / or a food product (e.g., fruit juice, milk, beer), the method comprising at least a filtration step through a porous article (such as a porous membrane, one or more hollow fibers, one or more hollow tubes or one or more porous thin films), such a porous article comprising the PAES copolymer according to the present invention.

[0047] The ninth aspect of the present invention relates to a method for improving the flexibility of an aromatic sulfone polymer material with a high Tg, which preferably has a Tg ≥ 180 °C and is preferably selected from the group consisting of: polysulfone (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES), any copolymer thereof or any blend thereof. Such a method comprises blending the PAES copolymer according to the present invention with a bulk aromatic sulfone polymer with a high Tg to form a polymer blend with a higher flexibility than the aromatic sulfone polymer material. Such a polymer blend is preferably used to form a porous article suitable for filtration, such as a porous membrane, one or more hollow fibers, one or more hollow tubes or a porous thin film. Higher flexibility means that compared with the bulk sulfone polymer, when the polymer blend is bent, the ductility increases (a less brittle material) and the modulus decreases (a less rigid material). Detailed Description

[0048] In the present application:

[0049] - Even if any description described with respect to a particular embodiment is applicable to and interchangeable with other embodiments of the present disclosure, and each embodiment thus defined can be combined with another embodiment, unless otherwise specified or clearly incompatible;

[0050] - When 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 the relevant embodiments explicitly contemplated herein, the element or component can also be any one of these recited individual elements or components, or can also be selected from the group consisting of any two or more of the explicitly recited elements or components; any element or component listed in the list of elements or components can be omitted from this list;

[0051] - Any recitation of a numerical range by endpoints herein includes all the numbers included within the recited range, as well as the endpoints and equivalents of the range;

[0052] - The term "comprising" (comprising or comprise) includes "consisting essentially of" (consistingessentially of or consist essentially of) and "consisting of" (consisting of or consist of);

[0053] - As used herein, the singular "a" or "one" includes the plural unless otherwise expressly specified; and

[0054] - It should be understood that the elements, properties and / or characteristics of the (co)polymers, products or articles, methods or uses described in this specification can be combined explicitly or implicitly with other elements, properties and / or characteristics of such (co)polymers, products or articles, methods or uses in all possible ways, without departing from the scope of this specification.

[0055] The term "consisting essentially of" in relation to a composition, product, polymer, solution, process, method, etc. is intended to mean that any additional elements or characteristics that may not be explicitly described herein and that do not materially affect the basic and novel characteristics of such composition, product, polymer, solution, process, method, etc. can be included in such embodiments.

[0056] In this disclosure, the term "repeating unit" refers to the smallest unit of a PAES polymer that repeats in the chain and is composed of the condensation of a diol compound and a dihalide compound. The term "recurring unit" is synonymous with the terms "repeating unit" and "structural unit".

[0057] As used herein, the term "homopolymer" encompasses polymers having only one type of repeating unit.

[0058] As used herein, the term "copolymer" encompasses polymers that can have two or more different types of repeating units.

[0059] The term "solvent" is used herein in its ordinary meaning, which means a substance capable of dissolving another substance (solute) to form a mixture that is uniformly dispersed at the molecular level. In the case of a polymer solute, it is customary to refer to a solution of the polymer in a solvent when the resulting mixture is transparent and there is no visible phase separation in the system. The point at which phase separation occurs, commonly referred to as the "cloud point", is considered to be the point at which the solution becomes cloudy or turbid due to the formation of polymer aggregates.

[0060] The term "membrane" is used herein in its ordinary meaning and is a separation article. That is, it refers to a discrete, generally thin interface that attenuates the permeation of chemical substances in contact with it. The interface can be molecularly homogeneous, i.e., structurally completely uniform (dense or non-porous membrane), or it can be chemically or physically non-uniform, e.g., containing voids, holes or pores of limited size (porous membrane). A porous membrane generally has an outer surface and an inner surface within the pores in contact with chemical substances.

[0061] The weight-average molecular weight (M w ) and the number-average molecular weight (M n ) can be estimated by gel permeation chromatography (GPC) preferably calibrated with polystyrene standards. The mobile phase can be selected from any of the solvents described herein for PAES copolymers, such as dichloromethane, N-methyl-2-pyrrolidone (NMP), sulfolane or N,N'-dimethylacetamide (DMAc), preferably dichloromethane. The polydispersity index (PDI) is hereby expressed as the ratio of the weight-average molecular weight (M w ) to the number-average molecular weight (M n ).

[0062] As used herein, polyethersulfone (PES) denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 99 mol.% of repeating units (R PES ) having the formula (J):

[0063]

[0064] (mol.% is based on the total number of moles of repeating units in the PES polymer). PES can be prepared by known methods and is in particular available from Solvay Specialty Polymers USA, L.L.C under PES.

[0065] As used herein, polysulfone (PSU) denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 99 mol.% of repeating units (R PSU ) having the formula (K):

[0066]

[0067] (mol.% is based on the total number of moles of repeating units in the PSU polymer). PSU can be prepared by known methods and is available in particular from Solvay Specialty Polymers USA, LLC under PSU.

[0068] As used herein, polyphenylsulfone (PPSU) refers to any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 99 mol.% of repeating units of formula (L) (R PPSU ):

[0069]

[0070] (mol.% is based on the total number of moles of repeating units in the PPSU polymer). PPSU can be prepared by known methods and is available in particular from Solvay Specialty Polymers USA, LLC under PPSU.

[0071] The following advantages of the present invention are achieved:

[0072] 1) The 'one-pot' process in which the PAES copolymer synthesis is carried out in a single polymerization unit operation is easier to operate;

[0073] 2) It provides a simple way to adjust the hydrophilicity of the PAES copolymers of the present invention by controlling the amount of haloalkylene oxide comonomer used in the reaction mixture to control the water solubility of the PAES copolymer. Hydrophilicity and water solubility are particularly important control parameters because a) a polymer that is too hydrophilic may cause it to leach out of the membrane during use, and b) a polymer that is too hydrophilic may pose some challenges for separating the polymer via coagulation;

[0074] 3) It provides a simple way to improve the flexibility of the bulk aromatic sulfone polymer by adding a certain amount of haloethylene oxide comonomer to the reaction mixture during the polymerization of the reaction mixture to prepare an aromatic sulfone copolymer with a lower Tg. Higher flexibility means that compared to a polymer polymerized with sulfone, in the case where no haloalkylene oxide is inserted into the polymer chain, the ductility is improved (a less brittle material) when the copolymer is bent;

[0075] 4) Compared with methods in the prior art where an alkylene oxide having the general formula HO-AO-OH is used as a reactant in the manufacture of aromatic sulfone polymers, the method of the present invention, in which the alkylene oxide partial reactant (AO monomer in the reaction mixture of the present invention) is an aliphatic halogen (e.g., Cl-CH2-CH2-O-CH2-CH2-O-CH2-CH2-Cl having the formula (Ia)), has a distinct advantage in terms of the ability of the polymerization reaction to efficiently build molecular weight. This is important because molecular weight is proportional to viscosity, and maintaining viscosity is particularly desirable for film fabrication methods. Without wishing to be bound by this theory, it is generally understood that aliphatic halogens react with alcohol nucleophiles via the well-known nucleophilic substitution (SN2) mechanism. Under the reaction conditions for producing aromatic sulfone polymers, such reactions are highly productive and rapid. In contrast, when using an aliphatic HO-AO-OH compound (e.g., triethylene glycol) as a reactant, the reaction mechanism is based on nucleophilic aromatic substitution (SNAr) because HO-AO-OH acts as a nucleophile. Under the same reaction conditions for producing aromatic sulfone polymers, such an SNAr reaction between an aliphatic alcohol and an aromatic halide leaving group has a relatively low yield and is slow. Thus, in the present invention, when an alkylene oxide monomer is selected as an aliphatic AO halogen (rather than an aliphatic AO alcohol), the polymerization reaction relies on the SN2 mechanism (rather than SNAr) to form aromatic -O-CH2 ether bonds, and this mechanism is more productive and faster under the polymerization conditions for building the molecular weight of PAES copolymers.

[0076] Thus, the present invention provides a way to achieve adjustable hydrophilicity and / or increased flexibility of PAES copolymers in a one-step polymerization method for building and maintaining the molecular weight of PAES.

[0077] PAES copolymer

[0078] A first aspect of the present invention relates to a PAES copolymer comprising a total of at least 80 mol.%, or at least 85 mol.%, or at least 90 mol.%, or at least 95 mol.%, or at least 97 mol.%, or at least 98 mol.%, or at least 99 mol.% of two different repeating units (R AO ) and (R PAES ), where the mol.% is based on the total number of moles of repeating units in the PAES copolymer. The PAES copolymer can consist essentially of the repeating units (R AO ) and (R PAES ).

[0079] Within the framework of the present invention, the expression "PAES copolymer" is used to designate a copolymer comprising'sulfone' repeating units (usually as the main repeating units) derived from dihaloaromatic sulfone monomers. Thus, a PAES copolymer is generally a polymer comprising at least 50 mol% of sulfone repeating units (R PAES ), said mol% being based on the total number of moles of all repeating units in the PAES copolymer.

[0080] The PAES copolymer comprises at least 4 mol%, or at least 5 mol%, or at least 6 mol%, or at least 8 mol%, or at least 10 mol%, or at least 12 mol% and up to 50 mol%, or up to 40 mol%, or up to 30 mol%, or up to 25 mol% of repeating units (R EO ), said mol% being based on the combined number of moles of repeating units (R AO ) and (R PAES ).

[0081] The repeating units (R AO ) in the PAES copolymer can be selected from units having the formula (M1) and / or (M'1):

[0082]

[0083] In formulae (M1) and (M'1), each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently H or CH3.

[0084] In formulae (M1) and (M'1), each of m and q is independently an integer of at least 2 and optionally at most 5, preferably equal to 2, provided that at least one R 1 is H and at least one R 6 is H.

[0085] In formulae (M1) and (M'1), each of n and p is independently an integer of at least 1 and optionally at most 5, preferably equal to 1 or 2, provided that when n = 2, at least one R 2 or R 3 is H; and when p = 2, at least one R 4 or R 5 is H.

[0086] In formulae (M1) and (M'1), r is 0, 1, 2 or 3.

[0087] In formula (M1) and / or (M'1), m, n and q are preferably 2 and r is preferably equal to 0.

[0088] In formula (M1) and / or (M'1), when r is 1, 2 or 3, then p is preferably 2.

[0089] The alkylene oxide moiety of the repeating unit (R AO ) having formula (M1) and / or (M'1) in the PAES copolymer:

[0090]

[0091] Preferably has at least 5 carbon atoms and at most 9 carbon atoms and / or at least 2 oxygen atoms and at most 4 oxygen atoms.

[0092] The repeating unit (R AO ) in the PAES copolymer can preferably be any unit represented by a formula selected from the group consisting of formulas (M1a) to (M1i):

[0093]

[0094] More preferably selected from formulas (M1a), (M1b), (M1g), (M1h) and / or (M1i), still more preferably selected from formulas (M1a), (M1g), (M1h) and / or (M1i), and even more preferably selected from formula (M1a).

[0095] In any one of formulas (M1), (M'1), (M1a) to (M1i), -E- is derived from at least one dihydroxy (B) monomer selected from the group consisting of:

[0096] · Tetramethylbisphenol F,

[0097] · At least one 1,4:3,6-dianhydrohexitol;

[0098] · At least one alicyclic diol;

[0099] · At least one aromatic diol; and

[0100] · Any combination thereof.

[0101] In any one of formulas (M1), (M'1), (M1a) to (M1i), -E- is preferably represented by at least one of the following formulas (E1) to (E7):

[0102]

[0103] Wherein

[0104] - T in formula (E7) is selected from the group consisting of: a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CCl3)2-, -C(=CCl2)-, -CH2-, -O-, -C(O)-, -C(CH3)(CH2CH2COOH)-, -S-, -SO- and any combination thereof, preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(O)- and any combination thereof, more preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2- and any combination thereof, and

[0105] - Ar in formula (E7) 3 and Ar 4 are the same as or different from each other, and each time they appear, independently, is an aromatic moiety conforming to any one of formulas (J), (J') and (J"), preferably conforming to formula (J):

[0106]

[0107] ο where each R in formulas (J), (J') and (J") is the same as or different from each other, and is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and

[0108] ο where each j is the same as or different from each other, and independently is 0, 1, 2, 3 or 4, preferably j = 0 or 1.

[0109] In each of formulas (M1), (M'1), (M1a) to (M1i), -E is more preferably represented by a formula selected from the previously described formulas (E1) to (E6) and the following formulas (E7a), (E7b) and (E7c):

[0110]

[0111] Even more preferably, it is represented by a formula selected from formulas (E1), (E7a), (E7b) and / or (E7c). The repeating unit (R PAES ) in the PAES copolymer is represented by formula (N):

[0112]

[0113] where

[0114] · Each R' in formula (N) is the same as or different from each other, and is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;

[0115] · Each j' in formula (N) is the same as or different from each other, and independently is 0, 1, 2, 3 or 4, preferably j' = 0 or 1; and

[0116] · -E- in formula (N) is the same as that described for the repeating unit (R AO ) represented by any one of formulas (M1), (M'1), (M1a) to (M1i).

[0117] The repeating unit (R PAES ) in the PAES copolymer can preferably be represented by formula (N'):

[0118]

[0119] wherein for each R', j' = 0 or 1, and when j' = 1, R' is selected from the group consisting of alkali metal sulfonate, alkaline earth metal sulfonate and alkyl sulfonate, and wherein -E- in formula (N') is the same as that described for the repeating unit (R AO ) represented by any one of formulas (M1), (M'1), (M1a) to (M1i).

[0120] The repeating unit (R PAES ) in the PAES copolymer can be such that in some of the repeating units (R PAES ) having formula (N) or (N'), some R' are selected from sulfonic acid groups; alkali metal or alkaline earth metal sulfonate groups; and / or alkyl sulfonate groups, wherein the corresponding j' = 1, while in other repeating units (R PAES ) having formula (N) or (N'), j' = 0 (i.e., the phenyl group is unsubstituted). The benzene ring optionally substituted by such R' and having j' = 1 is preferably attached to the -SO2- linking group of the repeating unit (R PAES ).

[0121] The repeating unit (R PAES ) in the PAES copolymer can preferably be such that each j and j' are zero, which means that no phenyl group is substituted in formula (N) or (N'). In such a case, the repeating unit (R PAES ) in the PAES copolymer is more preferably represented by formula (N"):

[0122]

[0123] In the repeating unit (R PAES ) of the PAES copolymer, -E- in formula (N), (N'), or (N'') can be represented by at least one of formulas (E1) to (E7) described herein, preferably by at least one of formulas (E1) to (E6), (E7a), (E7b), and (E7c) described herein, more preferably by at least one of formulas (E1), (E7a), (E7b), and (E7c).

[0124] Preferably, the PAES copolymer comprises a total of at least 80 mol.%, or at least 85 mol.%, or at least 90 mol.%, or at least 95 mol.%, or at least 97 mol.%, or at least 98 mol.%, or at least 99 mol.% of the following, based on the total number of moles of the repeating units in the PAES copolymer:

[0125] - repeating units (R i ) having formula (M1a i ) shown below and / or (M'1a AO ) and repeating units (R PAES ) having formula (N1a) shown below:

[0126]

[0127] - repeating units (R ii ) having formula (M1a ii ) and / or (M'1a AO ) and repeating units (R PAES ) having formula (N1b) shown below:

[0128]

[0129] - repeating units (R iii ) having formula (M1a iii ) and / or (M'1a AO ) and repeating units (R PAES ) having formula (N1c) shown below:

[0130]

[0131] - repeating units (R iv ) having formula (M1a iv ) and / or (M'1a AO ) and repeating units (R PAES ) having formula (N1d) shown below:

[0132]

[0133] - having repeating units (R v ) of the following - shown formula (M1a v ) and / or (M’1a AO ) and having repeating units (R PAES ) of the following - shown formula (N1e):

[0134]

[0135] wherein, in the formulas (N1a), (N1b), (N1c), (N1d) and (N1e), for each R’, j’ = 0 or 1.

[0136] In the formulas (N1a), (N1b), (N1c), (N1d) and (N1e), when j’ = 1, R’ is preferably selected from the group consisting of alkali metal sulfonates, alkaline earth metal sulfonates and alkyl sulfonates.

[0137] More preferably, the PAES copolymer consists essentially of the following:

[0138] - having repeating units (R i ) of the formula (M1a AO ) and having repeating units (R PAES ) of the formula (N1a); or

[0139] - having repeating units (R ii ) of the formula (M1a AO ) and having repeating units (R PAES ) of the formula (N1b); or

[0140] - having repeating units (R iii ) of the formula (M1a AO ) and having repeating units (R PAES ) of the formula (N1c); or

[0141] - having repeating units (R iv ) of the formula (M1a AO ) and having repeating units (R PAES ) of the formula (N1d); or

[0142] - having repeating units (R v ) of the formula (M1a AO ) and having repeating units (R PAES ) of the formula (N1e),

[0143] wherein for each R’ in the formulas (N1a), (N1b), (N1c), (N1d) and (N1e), j’ = 0 or 1.

[0144] The PAES copolymer is preferably a random polymer.

[0145] The PAES copolymer preferably excludes block copolymers containing at least one poly(alkylene oxide) block and at least one poly(aryl ether aryl sulfone) block, and more preferably excludes diblock AB or triblock ABA copolymers composed of one or two poly(ethylene oxide) as block A and poly(aryl ether aryl sulfone) as block B.

[0146] Based on the weight of the alkylene oxide present in the total weight of the copolymer, the weight content of the alkylene oxide (AO) in the PAES copolymer can be at least 1 wt.%, at least 1.2 wt.%, at least 2 wt.%, at least 2.5 wt.%, at least 3 wt.% and / or at most 22 wt.%, at most 20 wt.%, at most 18 wt.%, at most 15 wt.%, at most 12 wt.%, at most 10 wt.%, at most 8 wt.%, or at most 7 wt.%.

[0147] The PAES copolymer has a weight-average molecular weight Mw greater than 10,000 kDa, or at least 15,000 kDa, or at least 20,000 kDa, or at least 30,000 kDa, or at least 35,000 kDa and optionally up to 150,000 kDa, or up to 120,000 kDa, or up to 100,000 kDa, and the Mw is measured by GPC using dichloromethane as the mobile phase and using polystyrene standards for calibration.

[0148] The PAES copolymer can have a PDI of at least 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, at least 2.6, at least 2.7, or at least 3 and / or less than 4, at most 3.9, or at most 3.8.

[0149] The PAES copolymer preferably has a Tg of at least 95 °C, at least 100 °C, at least 110 °C, at least 120 °C, at least 125 °C, or at least 130 °C and / or at most 250 °C, at most 240 °C, at most 220 °C, at most 210 °C, or at most 200 °C, as measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0150] Method for preparing PAES copolymer

[0151] The second aspect of the present invention relates to a method for preparing a PAES copolymer by condensation of at least one aromatic dihydroxy compound with at least one dihaloaromatic sulfone compound and at least one dihaloalkylene oxide compound.

[0152] The method for preparing a PAES copolymer includes:

[0153] Reacting a monomer mixture in a reaction mixture comprising an aprotic polar solvent and in the presence of an alkali metal carbonate, said monomer mixture comprising:

[0154] - At least one dihaloalkylene oxide compound [hereinafter dihalo monomer (AO)], which comprises compounds selected from the group consisting of compounds having formula (I):

[0155]

[0156] Wherein

[0157] · X1 and X2 in formula (I) are the same or different from each other and are independently a halogen atom, preferably Cl, Br or F, more preferably Cl;

[0158] · R 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each of them is independently H or CH3;

[0159] · Each of m and q is independently an integer of at least 2 and optionally at most 5, preferably equal to 2, provided that at least one R 1 Is H and at least one R 6 Is H;

[0160] · Each of n and p is independently an integer of at least 1 and optionally at most 5, preferably equal to 1 or 2, provided that when n = 2, at least one R 2 Or R 3 Is H; and when p = 2, at least one R 4 Or R 5 Is H; and

[0161] · r in formula (I) is 0, 1, 2 or 3;

[0162] - At least one dihaloarylsulfone compound [hereinafter dihalo monomer (AS)], which comprises a compound having formula (V):

[0163] X-Ar 1 -SO2-Ar 2 -X’(V);

[0164] Wherein

[0165] - X and X’ in formula (V) are the same or different from each other and are independently a halogen atom, preferably Cl or F, more preferably Cl;

[0166] - Ar 1 And Ar 2Identical to or different from each other, and each occurrence in formula (V) is independently an aromatic moiety conforming to any one of the following formulas (H), (H'), and (H''):

[0167]

[0168] ο where each R' is identical to or different from each other and is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and

[0169] ο where each j' is identical to or different from each other and is independently 0, 1, 2, 3, or 4, preferably j' = 1 or 0;

[0170] - At least one dihydroxy compound [hereinafter dihydroxy monomer (B)], which includes diols selected from the group consisting of:

[0171] ο Tetramethylbisphenol F,

[0172] ο At least one 1,4:3,6-dianhydrohexitol selected from the group consisting of isosorbide (1,6-dianhydrosorbitol), isomannitol (1,6-dianhydromannitol), and isoidide (1,6-dianhydroiditol), preferably isosorbide,

[0173] ο At least one alicyclic diol selected from the group consisting of 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane dimethanol, adamantane diol, pentacyclopentadecane dimethanol, 1,3-cyclobutanediol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol ("CBDO"), preferably CBDO, and

[0174] ο An aromatic diol having formula (VI):

[0175] HO-Ar 3 -T-Ar 4 -OH (VI),

[0176] Preferably 4,4'-biphenol, bisphenol A, and / or bisphenol S, and

[0177] ο Any combination thereof,

[0178] Wherein:

[0179] -Ar 3 and Ar 4 Are identical to or different from each other, and each occurrence in formula (VI) is independently an aromatic moiety conforming to any one of the following formulas (J), (J'), and (J''):

[0180]

[0181] ο wherein each R in formula (VI) is the same as or different from each other and is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and

[0182] ο wherein each j is the same as or different from each other and is independently 0, 1, 2, 3, or 4, preferably j = 1 or 0,

[0183] - T in formula (VI) is selected from the group consisting of: a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CCl3)2-, -C(=CCl2)-, -CH2-, -O-, -C(O)-, -C(CH3)(CH2CH2COOH)-, -S-, and -SO-, preferably selected from a bond, -SO2-, and / or -C(CH3)2-, and

[0184] wherein

[0185] - The monomer mixture contains at least 4 mol.%, or at least 5 mol.%, or at least 6 mol.%, or at least 8 mol.%, or at least 10 mol.% and up to 50 mol.%, or up to 30 mol.%, or up to 25 mol.% of the dihalo monomer (AO), where the mol.% is based on the combined molar amounts of the dihalo monomer (AO) and (AS);

[0186] - The total amount of the halogen groups and hydroxyl groups of the monomers in the monomer mixture is substantially equimolecular; and

[0187] - When expressed as the ratio of the equivalents of the alkali metal (M) to the equivalents of the hydroxyl groups (OH) in the dihydroxy monomer (B) [eq.(M) / eq.(OH)], the amount of the alkali metal carbonate used in the reaction mixture is greater than 1, preferably at least 1.05 and optionally up to 2, or up to 1.5, or up to 1.3.

[0188] For the purposes of the present invention, the expression "substantially equimolecular" as used above in relation to the total amount of the halogen groups and hydroxyl groups of the monomers of the monomer mixture should be understood to mean that the molar ratio between the total amount of the hydroxyl groups of the monomer (B) of the monomer mixture and the total amount of the halogen groups of the monomers (AO) and (AS) of the monomer mixture is 0.95 to 1.05, or 0.98 to 1.02, or 0.99 to 1.01, or 0.995 to 1.005; good results have been obtained with a ratio of 0.995 to 1.000.

[0189] In formula (I), m, n and q are preferably 2 and r is preferably equal to 0.

[0190] In formula (I), when r is 1, 2 or 3, then p is preferably 2.

[0191] The alkylene oxide moiety in the dihalo monomer (AO) having formula (I) represented by:

[0192]

[0193] preferably has at least 5 carbon atoms and at most 9 carbon atoms and / or at least 2 oxygen atoms and at most 4 oxygen atoms.

[0194] The polymerization reaction mixture preferably excludes any polyalkylene oxide ("PAO") that does not contain halogen end groups, or may contain less than 1 wt.%, or less than 0.5 wt.%, or less than 0.1 wt.% of such PAO, such wt.% being based on the total weight of the monomer mixture. "Polyalkylene oxide" is understood to mean those polyalkylene oxides obtained by the polymerization of alkylene oxides such as ethylene oxide, 1,2-epoxypropane. "Polyalkylene oxide" can generally be represented by the formula: R e -[(CHR l ) y O] z -H, where R l is H or alkyl; y can be from 1 to 3; z can be from 2 to 500; and the end group R e can be hydroxy (OH), mesylate, tosylate and / or NH2. The PAO excluded from the reaction mixture is preferably selected from the group consisting of PAO having two hydroxy groups, monomethyl PAO and mesylated PAO. The PAO excluded from the reaction mixture is more preferably selected from the group consisting of: polyethylene glycol (PEG) having two hydroxy groups; polypropylene glycol (PPG) having two hydroxy groups; monomethyl PEG; monomethyl PPG; mesylated PEG; and mesylated PPG.

[0195] The polymerization reaction for preparing the PAES copolymer is preferably carried out in a reaction mixture comprising monomers (B), (AO), and (AS) and at least one solvent [S]. The solvent [S] is a polar aprotic solvent selected, for example, from the group consisting of: 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (commonly referred to as tetramethylene sulfone or sulfolane), N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropyleneurea (DMPU), dimethylformamide (DMF), tetrahydrothiophene-1-oxide, and mixtures thereof. The solvent [S] is preferably selected from the group consisting of: N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), sulfolane, and mixtures thereof. The polymerization reaction for preparing the PAES copolymer is more preferably carried out in sulfolane, DMI, DMSO, DMAc, or NMP.

[0196] The polymerization reaction (polycondensation) for preparing the PAES copolymer can be carried out in the presence of an alkali metal carbonate as the base. The base is used to deprotonate the dihydroxy monomer (B) during the polycondensation. The alkali metal carbonate preferably includes potassium carbonate and / or sodium carbonate, preferably includes potassium carbonate, and more preferably consists of potassium carbonate.

[0197] When expressed as the ratio [eq.(Me) / eq.(OH)] of the equivalent of the alkali metal (Me) to the equivalent of the hydroxyl group (OH) in the monomer (B), the amount of the alkali metal carbonate used in the reaction mixture is greater than 1, preferably at least 1.05, and optionally up to 2, or up to 1.5, or up to 1.3.

[0198] The polymerization reaction for preparing the PAES copolymer can be carried out at a monomer molar ratio (B) / [(AO)+(AS)] of 0.9 to 1.1, for example, 0.92 to 1.08.

[0199] The total amount of the halogen group and the hydroxyl group of the monomers in the monomer mixture is preferably substantially equimolar, such as the molar ratio of the hydroxyl group to the halogen group being 0.95 to 1.05, or 0.98 to 1.02, or 0.99 to 1.01, or 0.995 to 1.005.

[0200] To prepare the PAES copolymer of the present invention, the dihydroxy monomer (B) comprises at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of diols selected from the group consisting of: tetramethylbisphenol F; 1,4:3,6-dianhydrohexitols selected from isosorbide, isomannitol, and / or isoidide; alicyclic diols selected from any isomers of 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane dimethanol, adamantane diol, pentacyclopentadecane dimethanol, 1,3-cyclobutanediol, and / or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO); and aromatic diols having the formula (VI). The dihydroxy monomer (B) may preferably consist essentially of at least one diol selected from the group consisting of: biphenol, bisphenol A, bisphenol S, TMBPF, isosorbide (1,6-dianhydrosorbitol), cis-CBDO, and trans-CBDO and any combination thereof. The dihydroxy monomer (B) may more preferably consist essentially of at least one aromatic diol selected from the group consisting of: TMBBF, biphenol, bisphenol A, bisphenol S, and any combination thereof.

[0201] The monomer mixture preferably comprises at least one dihydroxy (B) monomer selected from the group consisting of:

[0202]

[0203]

[0204] and any combination thereof.

[0205] The monomer mixture may comprise tetramethylbisphenol F as the dihydroxy (B) monomer and optionally at least one other dihydroxy (B) monomer selected from the group consisting of: bisphenol A, bisphenol S, 4,4'-biphenol, isosorbide, and any combination thereof.

[0206] The monomer mixture may comprise tetramethylbisphenol F as the sole dihydroxy (B) monomer.

[0207] The monomer mixture may comprise bisphenol A, bisphenol S, or 4,4'-biphenol as the sole dihydroxy (B) monomer.

[0208] The monomer mixture may comprise isosorbide as the dihydroxy (B) monomer and optionally at least one other dihydroxy (B) monomer selected from the group consisting of: bisphenol A, bisphenol S, 4,4'-biphenol, tetramethylbisphenol F, and any combination thereof.

[0209] To prepare the PAES copolymer of the present invention, the dihalo monomer (AO) preferably includes at least one compound having the formula (I), wherein both X1 and X2 are Cl.

[0210] The dihalo monomer (AO) more preferably includes at least one compound represented by or consisting of any one of the formulas (Ia) to (Ii):

[0211] Cl-CH2-CH2-O-CH2-CH2-O-CH2-CH2-Cl (Ia)

[0212] 1,2-bis(2-chloroethoxy)ethane

[0213] Cl-CH2-CH2-O-CH2-O-CH2-CH2-Cl (Ib)

[0214] 1-chloro-2(2-chloroethoxymethoxy)ethane,

[0215] Cl-CH2-CH2-O-C(CH3)2-O-CH2-CH2-Cl (Ic)

[0216] 2,2-bis(2-chloroethoxy)propane,

[0217] Cl-CH2-CH2-O-CH2-O-CH2-O-CH2-CH2-Cl (Id)

[0218] 1,9-dichloro-2,5,7-trioxanonane,

[0219] Cl-CH(CH3)-CH2-O-CH2-O-CH2-CH2-Cl (Ie)

[0220] (2-chloroethoxy)(2-chloropropoxy)methane,

[0221] Cl-CH2-CH2-O-CH2-O-CH2-O-CH2-O-CH2-CH2-Cl (If)

[0222] 1,11-dichloro-3,5,7,9-tetraoxaundecane,

[0223] Cl-CH(CH3)-CH2-O-CH2-CH(CH3)-O-CH2-CH(CH3)-Cl (Ig)

[0224] 1,2-bis(2-chloropropoxy)propane,

[0225] Cl-CH(CH3)-CH2-O-CH2-CH2-O-CH2-CH(CH3)-Cl (Ih)

[0226] Bis(2-chloropropoxy)ethane,

[0227] Cl-CH2-CH2-O-CH(CH3)-CH2-O-CH2-CH2-Cl(Ii)

[0228] 2,2-Bis(2-chloroethoxy)propane.

[0229] The dihalo monomer (AO) more preferably further comprises at least one compound represented by or consisting of any one of formulas (Ia), (Ib), (Ig), (Ih), and / or (Ii), and even more preferably comprises at least one compound represented by or consisting of any one of formulas (Ia), (Ig), (Ih), and / or (Ii).

[0230] The dihalo monomer (AO) contains at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of at least one compound having a formula selected from formulas (I), (Ia) to (Ii) based on the total weight of the dihydroxy monomer (AO) in the reaction mixture. The dihalo monomer (AO) may more preferably consist essentially of a compound having a formula selected from formulas (I), (Ia) to (Ii), and even more preferably consists essentially of at least one compound having a formula represented by any one of formulas (Ia), (Ib), (Ig), (Ih), and / or (Ii). The dihalo monomer (AO) most preferably consists essentially of a compound having formula (Ia).

[0231] To prepare the PAES copolymer of the present invention, the dihalo monomer (AS) contains at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of at least one dihalodiphenyl sulfone having formula (V) based on the total weight of the monomer (AS). The dihalo monomer (AS) may preferably consist essentially of at least one 4,4-dihalodiphenyl sulfone selected from the group consisting of: 4,4'-dichlorodiphenyl sulfone (DCDPS), disulfonated 4,4'-dichlorodiphenyl sulfone (sDCDPS), 4,4'-difluorodiphenyl sulfone (DFDPS), disulfonated 4,4'-difluorodiphenyl sulfone (sDFDPS), and any combination thereof. The dihalo monomer (AS) more preferably consists essentially of DCDPS and / or disodium bis(4-chloro-3-sulfophenyl) sulfone (sulfonated DCDPS disodium), as shown below:

[0232]

[0233] The dihalogenated monomer (AS) may include two or more 4,4-dihalogenated diphenyl sulfones. In particular, the monomer (AS) may contain a combination of 4,4-dihalogenated diphenyl sulfone and sulfonated dihalogenated diphenyl sulfone of formula (V) based on at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of the total weight of the monomer (AS), wherein at least one R1 in the sulfonated 4,4-dihalogenated diphenyl sulfone of formula (V) is selected from the group consisting of alkali metal or alkaline earth metal sulfonates and alkyl sulfonates, and its corresponding j’ is equal to 1.

[0234] The monomer mixture preferably contains 4,4'-dichlorodiphenyl sulfone (DCDPS) and / or any sulfonated derivative of DCDPS as at least one dihalogenated (AS) monomer.

[0235] To prepare the PAES copolymer of the present invention, the monomers (B), (AS) and (AO) of the reaction mixture typically react simultaneously, which means that the reaction is carried out in a single synthesis stage (also referred to as 'one-pot' synthesis). The deprotonation of the monomer (B) and the condensation reaction between the monomers (AO)+(AS) and the monomer (B) are carried out in a single reaction stage without separation of intermediate products.

[0236] The polymerization can be carried out in a reaction mixture containing a polar aprotic solvent [S] and further containing a cosolvent that forms an azeotrope with water. The cosolvent that forms an azeotrope with water includes aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, etc. The cosolvent is preferably toluene or chlorobenzene, more preferably toluene. The cosolvent that forms an azeotrope and the polar aprotic solvent [S] are typically used in a weight ratio of about 1:100 to about 1:1, or about 1:50 to about 1:1, or about 1:20 to about 1:1, or about 1:10 to about 1:1. Water is continuously removed from the reaction mass as an azeotrope with the cosolvent that forms an azeotrope, so that substantially anhydrous conditions are maintained during the polymerization. After water is formed in the reaction, the cosolvent (e.g., chlorobenzene or toluene) that forms an azeotrope is typically removed from the reaction mixture by distillation, leaving the PAES copolymer dissolved in the polar aprotic solvent [S].

[0237] In a preferred embodiment of the method for preparing the PAES copolymer of the present invention, the reaction mixture preferably contains:

[0238] - a dihalogenated (AO) monomer represented by formula (Ia);

[0239] - 4,4'-dichlorodiphenyl sulfone (DCDPS) and / or any sulfonated derivative of DCDPS as at least one dihalogenated (AS) monomer or the only dihalogenated (AS) monomer;

[0240] -At least one dihydroxy (B) selected from TMBPF, isosorbide, bisphenol A, biphenol, bisphenol S, or any combination thereof,

[0241] -Potassium carbonate and / or sodium carbonate, preferably potassium carbonate as the alkali metal carbonate,

[0242] -A solvent selected from NMP, DMAc, sulfolane, DMSO, DMI, or a combination thereof;

[0243] -An optional cosolvent that forms an azeotropic mixture with water, preferably selected from benzene, toluene, xylene, ethylbenzene, chlorobenzene, or any combination thereof, more preferably toluene and / or chlorobenzene,

[0244] wherein

[0245] -The mol% content of the dihalo (AO) monomer having the formula (Ia) is 2 mol% to 25 mol% based on the total moles of monomers (AO), (AS), and (B) in the reaction mixture;

[0246] -The total amount of halogen groups and hydroxyl groups of the monomers in the monomer mixture is substantially equimolar; and

[0247] -When expressed as the ratio of the equivalents of alkali metal (Me) to the equivalents of hydroxyl groups (OH) in monomer (B) [eq.(Me) / eq.(OH)], the amount of potassium carbonate and / or sodium carbonate used in the reaction mixture is at least 1.05 and up to 1.5, or up to 1.3.

[0248] The temperature of the reaction mixture used to prepare the PAES copolymer is maintained at about 150 °C to about 250 °C, preferably about 165 °C to about 250 °C, for about 1 to 24 hours or 4 to 16 hours. When NMP and / or sulfolane is used as the solvent [S], the preferred temperature of the reaction mixture can be about 180 °C to about 220 °C. When DMAc is used as the solvent [S], the preferred temperature of the reaction mixture can be about 160 °C to about 175 °C.

[0249] Before or after the isolation (isolation or separation) of the PAES copolymer, inorganic components (such as sodium chloride or potassium chloride or excess base) can be removed by suitable methods (such as dissolution and filtration, sieving, or extraction).

[0250] At the end of the condensation, the amount of the copolymer is at least 25 wt.%, or at least 30 wt.% and / or at most 50 wt.%, at most 45 wt.%, or at most 40 wt.% based on the total weight of the PAES copolymer and the polar aprotic solvent [S].

[0251] At the end of the polymerization reaction, the PAES copolymer is separated from the other components (salts, bases, etc.) to obtain a solution. Filtration can be used, for example, to separate the PAES copolymer from the other components.

[0252] Then, the optionally filtered solution containing the PAES copolymer can be used 'as is' to prepare the articles described later.

[0253] Alternatively, the PAES copolymer in solid form can be recovered from the solvent [S] (used during the condensation) by, for example, condensation or devolatilization of the solvent [S].

[0254] The PAES copolymer in solid form can be dissolved in a solvent [Sp] (the same as or different from [S]) to prepare the articles.

[0255] The method for preparing the PAES copolymer of the present invention according to the present invention may further include at least one of the following steps between the polymerization step and the PAES copolymer separation step:

[0256] i. Cooling: reducing the temperature of the reaction mixture;

[0257] ii. Quenching: adding a solvent (S q ) that can be the same as or different from the polar aprotic solvent (S) to quench the reaction mixture, so as to generally stop the reaction and dilute the reaction mixture to reduce its viscosity; and / or

[0258] iii. Capping: adding a capping agent to convert the hydroxyl end groups of the formed PAES copolymer into less reactive end groups.

[0259] Step (i): Cooling can be affected by stopping the heating of the reaction mixture. Cooling can be achieved by directly adding an additional amount of the polar aprotic solvent (S) or another polar aprotic solvent to the reaction mixture, which is at a temperature at least 50 °C lower, at least 60 °C lower, or at least 70 °C lower than the temperature of the reaction mixture. The solvent added to the reaction mixture for cooling is preferably at ambient temperature. The solvent added for cooling is preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, NMP, and any combination thereof. Alternatively, cooling can be affected by passing a cooling fluid (not mixed with the reaction mixture) through the inside of the cooling tube or using a cooling jacket of the reactor vessel used for polymerization inside it.

[0260] Step (ii): Quenching can be carried out at the end of the reaction to reduce the polymer content of the reaction mixture to a value of 20 wt.% or less based on the total weight of the quenched reaction medium. The solvent (S q)Preferably the same as the polar aprotic solvent (S) used during the reaction, but not necessarily so. Solvent (S q ) is preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, NMP, and any combination thereof. After quenching, the polymer content of the quenched reaction mixture is preferably 5 wt.% to 20 wt.%, more preferably 8 wt.% to 18 wt.%, and most preferably 10 wt.% to 16 wt.% based on the total weight of the quenched reaction mixture.

[0261] The cooling and quenching steps (i) and (ii) can be carried out simultaneously at the end of the polymerization by using a solvent (S q ) having a temperature colder than the reaction temperature of the reaction mixture.

[0262] Step (iii): Capping (also known as termination) preferably converts the reactive hydroxyl end groups of the formed PAES copolymer into less reactive end groups. The capping agent is preferably chloromethane (“MeCl”). Chloromethane gas can be passed through the reaction mixture. The capping step (iii) can be carried out before or after cooling of the reaction mixture. Thus, the capping step (iii) can be carried out at the reaction temperature or at a temperature lower than the reaction temperature at the end of the polycondensation reaction. If it is desired to obtain a final PAES copolymer product having reactive (-OH) end groups, the capping step (iii) is preferably omitted in the process of the present invention.

[0263] The PAES copolymer obtained by this method

[0264] Another aspect of the present invention relates to a PAES copolymer obtained by the method according to the present invention.

[0265] The description related to the PAES copolymer (including its previously described preferred embodiments) equally applies to the PAES copolymer obtained by such a method.

[0266] Use of the PAES copolymer

[0267] Another aspect of the present invention provides the use of the PAES copolymer of the present invention for preparing an article (or a part thereof) as described herein. This aspect also relates to a method for preparing an article (or a part thereof) comprising the PAES copolymer of the present invention.

[0268] The article can be made from a polymer solution or a polymer melt comprising the PAES copolymer of the present invention.

[0269] The PAES copolymer according to the present invention can be used to prepare non-porous articles, such as dense films. Such dense films can be thick or thin films. Such uses can include polymer solution casting or polymer melt processing methods, such as injection molding or extrusion. In such cases, the PAES copolymer of the present invention can be the sole polymer in the non-porous article; alternatively, the non-porous article can further comprise at least one other polymer.

[0270] The PAES copolymer according to the present invention can be used to prepare porous articles, such as porous films, hollow fibers, hollow tubes or porous membranes, using phase inversion techniques selected from non-solvent induced phase separation or heat induced phase separation. Such uses can include casting or spinning a polymer dope solution comprising the PAES copolymer, a solvent, optionally a co-solvent and optionally at least one pore former (such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG)) into a porous article, and then cooling it or contacting it with a non-solvent. In such cases, the PAES copolymer can be the sole polymer in the dope solution; alternatively, the dope solution can further comprise at least one other polymer preferably selected from the group consisting of PSU, sulfonated PSU, PPSU, sulfonated PPSU, PES, sulfonated PES, polyvinylidene fluoride (PVDF) and any combination thereof.

[0271] When at least one other polymer is used to prepare a non-porous or porous article, such other polymer is preferably selected from the group consisting of PSU, sulfonated PSU, PPSU, sulfonated PPSU, PES, sulfonated PES, PVDF and any combination thereof.

[0272] Articles comprising a PAES copolymer

[0273] Another aspect of the present invention provides an article comprising a PAES copolymer according to the present invention, or made therefrom (preferably a shaped article).

[0274] Articles comprising a PAES copolymer can be porous or non-porous.

[0275] Articles comprising a PAES copolymer can preferably be porous articles, such as porous films, hollow fibers, hollow tubes, porous membranes or a part thereof (such as an (inner) porous layer or a porous coating).

[0276] As used herein, a "coating" according to the present invention should generally be understood as a layer fixed to the surface of a substrate, in particular adhered thereto. The coating can be a thin or thick layer, and / or can be multiple layers. The substrate used can be made of any suitable known material, such as metals, insulating materials, semiconductor materials, crystalline or amorphous polymeric materials, textile fabrics or films.

[0277] As used herein, a "fiber" according to the present invention is generally understood to be a flexible structure that is thin in width compared to its length. The fiber preferably has a thickness of from 0.5 to 100 microns.

[0278] As used herein, a "membrane" according to the present invention is a separating article. The membrane can be non-porous, partially porous, selectively permeable, such as a membrane permeable in one direction, or can preferably be porous.

[0279] The PAES copolymer can be the only polymer in the article.

[0280] The PAES copolymer can form all or substantially all of the article.

[0281] Alternatively, an article comprising a PAES copolymer can further comprise at least one other polymer different from the PAES copolymer. In such a case, the article can further comprise at least one other polymer selected from the group consisting of another aromatic sulfone polymer that can optionally be sulfonated, such as polysulfone (PSU), sulfonated polysulfone (sPSU), polyethersulfone (PES), sulfonated polyethersulfone (sPES), poly(biphenyl ether sulfone) (PPSU), sulfonated poly(biphenyl ether sulfone) (sPPSU), polyvinylidene fluoride (PVDF), polyphenylene sulfide (PPS), poly(aryl ether ketone) (PAEK) (such as poly(ether ether ketone) (PEEK), poly(polyether ketone ketone) (PEKK), poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer)), polylactide (PLA), polyetherimide (PEI), polycarbonate (PC), polyphenylene oxide (PPO), polyvinylpyrrolidone (PVP) and / or polyalkylene oxide (PAO) (such as PEG). The article can further comprise at least one other polymer preferably selected from the group consisting of PSU, sPSU, PES, sPES, PPSU, sPPSU, PVDF and combinations thereof.

[0282] When the article comprises at least one other polymer, the PAES copolymer can be present in the article in an amount ranging from 1 wt.% to 99 wt.%, such as 2 wt.% to 98 wt.%, 3 wt.% to 97 wt.% or 4 wt.% to 96 wt.%, based on the total weight of the polymers. Based on the combined weight of the PAES copolymer and one or more other polymers in the article, the weight fraction of the PAES copolymer is preferably at least 5 wt.%, at least 6 wt.%, at least 7 wt.%, at least 8 wt.%, at least 9 wt.%, or at least 10 wt.% and / or up to 50 wt.%, up to 45 wt.%, up to 40 wt.%, up to 35 wt.%, up to 30 wt.%, up to 25 wt.%, up to 20 wt.%, up to 17 wt.%, or up to 15 wt.%. In a preferred case, the weight fraction of the PAES copolymer in the article can be 5 wt.% to 25 wt.%, or 7 wt.% to 20 wt.%, or 8 wt.% to 17 wt.%, or 10 wt.% to 15 wt.%, based on the combined weight of the PAES copolymer and one or more other polymers.

[0283] When the article is porous (such as a porous film, hollow fiber, hollow tube, porous membrane or a part thereof), the article can comprise the PAES copolymer as a polymer additive to at least one matrix polymer, which matrix polymer is preferably selected from the group consisting of PSU, sulfonated PSU, PPSU, sulfonated PPSU, PES, sulfonated PES, PVDF and any combination thereof. In a preferred case, the PAES copolymer is a polymer additive to the matrix (other) polymer, and the weight fraction of the PAES copolymer in the article can be 5 wt.% to 25 wt.%, or 7 wt.% to 20 wt.%, or 8 wt.% to 17 wt.%, or 10 wt.% to 15 wt.%, based on the combined weight of the PAES copolymer and the matrix (other) polymer.

[0284] The PAES copolymer of the present invention used as a polymer additive in a hydrophobic matrix polymer improves the wettability of such a hydrophobic matrix polymer (such as PSU, PPSU or PES), which hydrophobic matrix polymer is typically used to form porous membranes for hemodialysis and for water filtration (such as ultrafiltration and microfiltration applications).

[0285] When the PAES copolymer of the present invention is added as a polymer additive to a bulk polymer with a high Tg, the flexibility of the resulting blended polymer material can also be improved. The bulk polymer with a high Tg preferably having Tg ≥ 180 °C can be a sulfone polymer selected from polysulfone (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES), any copolymer thereof, or any blend thereof. Such sulfone polymers are typically used to form porous articles such as membranes (e.g., hollow fiber membranes) suitable for hemodialysis or water filtration (such as ultrafiltration, nanofiltration, and microfiltration applications). In fact, since the PAES copolymer of the present invention generally has a lower Tg than that of PSU, PPSU, or PES, using the PAES copolymer of the present invention as an additive in a PSU, PPSU, or PES bulk polymer provides a way to increase the flexibility of the resulting blended polymer material. That is, compared with the Tg of the bulk polymer, the Tg of the polymer blend is reduced, and compared with the bulk polymer, its ductility when bent is improved (a less brittle material) and the modulus is reduced (less rigid).

[0286] In some embodiments of the present invention, when the article contains at least another polyarylethersulfone polymer and when the PAES copolymer of the present invention has a repeating unit (R PAES )(where -E- is represented by formula (E7) as described above: -Ar 3 -T-Ar 4 -), the sulfone repeating unit of the other PAES polymer is also represented by -E- having formula (E7), where the -T- linking group is the same as the -T- in the repeating unit (R PAES ) of the PAES copolymer. For example, when the repeating unit (R PAES ) of the PAES copolymer of the present invention has formula (N1e) (where -T- is -SO2- and each of the R' groups is unsubstituted (j' = 0) or sulfonated (i.e., j' = 1 and R' is selected from the group consisting of alkali metal sulfonates, alkaline earth metal sulfonates, and alkyl sulfonates)), then the other polyarylethersulfone polymer used in the article is preferably polyethersulfone (PES) and / or sulfonated PES. Alternatively, when the repeating unit (R PAES ) of the PAES copolymer of the present invention has formula (N1e) (where -T- is -C(CH3)2- and each of the R' groups is unsubstituted (j' = 0) or sulfonated (i.e., j' = 1 and R' is selected from the group consisting of alkali metal sulfonates, alkaline earth metal sulfonates, and alkyl sulfonates)), then the other polyarylethersulfone polymer used in the article is preferably polysulfone (PSU) and / or sulfonated PSU.

[0287] In alternative embodiments of the present invention, when the article contains at least another polyarylethersulfone polymer and when the PAES copolymer of the present invention has a repeating unit (RPAES When -E- is represented by any one of the formulas (E1) to (E6) as described above, the main sulfone repeating unit of the other polyarylether sulfone polymer is preferably represented by -E- having the formula (E7), where -T- is selected from a bond, -SO2-, or -C(CH3)2-.

[0288] The article may further comprise at least one non-polymeric component, such as a solvent, a filler, a lubricant, a mold release agent, an antistatic agent, a flame retardant, an antifogging agent, a matting agent, a pigment, a dye, a UV light stabilizer, a heat stabilizer, and / or an optical brightener. Alternatively, the article may exclude one or more non-polymeric components selected from the following: a filler, a lubricant, a mold release agent, an antistatic agent, a flame retardant, an antifogging agent, a matting agent, a pigment, a dye, a UV light stabilizer, a heat stabilizer, and / or an optical brightener.

[0289] The PAES copolymer of the present invention may be included in at least a portion of the surface of an article, such a surface being intended to come into 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).

[0290] The PAES copolymer of the present invention may be incorporated into an article having a polymer layer. One of ordinary skill in the art will know, based on the intended application of the article, which layer is intended to come into contact with fluids 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 a food product (e.g., fruit juice, milk, beer). The polymer layer may be the outer layer or the inner layer of the article. At least a portion of the layer may be in direct contact with the fluid in its intended application setting. For example, a medical device may have an outer layer intended to come into direct contact with a biological fluid. A thin film composite device (such as a reverse osmosis membrane or a nanofiltration membrane) may have a layer intended to come into direct contact with an aqueous medium or water. In particular, the article may include a thin selective layer disposed on a bottom layer or a porous substrate. The thin selective layer may comprise or be made of the PAES copolymer, while the bottom layer or the porous substrate has a composition excluding the PAES copolymer. Alternatively, the bottom layer or the porous substrate may comprise or be made of the PAES copolymer, while the thin selective layer may have a composition excluding the PAES copolymer. Alternatively, both the thin selective layer and the bottom layer or the porous substrate contain the PAES copolymer.

[0291] A film, tube, coating, or layer comprising the PAES copolymer of the present invention may have an average thickness of from about 25 μm to about 1 mm.

[0292] The porous membrane may be a microporous membrane, which may be characterized by its average pore size and porosity (i.e., the fraction of the entire membrane that is porous).

[0293] The porous membrane may have a weight porosity of 20% to 90% (%) and contain pores, at least 90% by volume of which have an average pore diameter of less than 5 μm. The weight porosity of the porous membrane is defined as the volume of the pores divided by the total volume of the membrane.

[0294] From an architectural perspective, the porous membrane containing the PAES copolymer can be provided in the form of a flat structure (e.g., having multiple thin films or sheets), a corrugated structure (such as a corrugated sheet), a tubular structure (e.g., having multiple tubes), or hollow fibers. Tubular porous membranes are classified based on their size as tubular membranes having a diameter greater than 3 mm; capillary membranes having a diameter included between 0.5 mm and 3 mm; and hollow fibers having a diameter less than 0.5 mm. Capillary membranes are also referred to as hollow fibers. Hollow fibers are particularly advantageous in applications where a compact module with a high surface area is required.

[0295] In terms of pore size, it is advantageously possible to fabricate various membranes (non-porous and porous, including those for microfiltration, ultrafiltration, nanofiltration, ion exchange, and reverse osmosis) with the PAES copolymer; the pore distribution can be isotropic or anisotropic.

[0296] A membrane having a uniform structure throughout its thickness is generally referred to as a symmetric membrane; a membrane having non-uniformly distributed pores throughout its thickness is generally referred to as an asymmetric membrane. 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, an asymmetric membrane can include a thin selective layer containing or made of the PAES copolymer, which is disposed on a bottom layer or substrate having a composition different from the PAES copolymer. Alternatively, an asymmetric membrane can include a support layer containing or made of the PAES copolymer, on top of which is disposed a thin selective layer having a composition excluding the PAES copolymer.

[0297] A polymer solution for preparing an article (e.g., a membrane, fiber, or film)

[0298] Another aspect of the present invention relates to a polymer solution for preparing an article (such as a membrane, fiber, or film), the polymer solution containing the PAES copolymer according to the present invention in a solvent [solvent (S P )].

[0299] The solvent (S P ) in the polymer solution can be selected from the list of solvents provided previously for polar aprotic solvents [S] described in the method for preparing the PAES copolymer. Preferably, the solvent (S P) can be N,N′-dimethylacetamide (DMAc), sulfolane, DMSO, NMP, or any combination thereof, and such a solvent (Sp) is particularly suitable for preparing articles such as fibers, membranes, or films.

[0300] Exemplary solvents (S P ) that can be used alone or in combination in the polymer solution are described in Patent Application US2019 / 054429 A1 (Solvay Specialty Polymers Italy S.p.A.) (especially the solvents described in paragraphs

[0057] -

[0129] ) and WO 2019 / 048652 (Solvay Specialty Polymers USA, LLC), and these documents are incorporated herein by reference.

[0301] The concentration of the solvent (S P ) in the polymer solution can be at least 20 wt.%, at least 30 wt.%, or at least 40 wt.% based on the total weight of the polymer solution and / or at most 80 wt.%; at most 70 wt.%; or at most 60 wt.% based on the total weight of the polymer solution.

[0302] The polymer solution can further comprise at least one other polymer different from the PAES copolymer. The other polymer different from the PAES copolymer can be selected from the group consisting of: PSU, sPSU, PES, sPES, PPSU, sPPSU, PVDF, PPS, PAEK polymers (such as PEEK, PEKK, PEK, or a copolymer of PEEK and PEK-PEDEK), PLA, PEI, PC, PPO, PVP, and / or PEO; preferably selected from the group consisting of: PSU, sPSU, PES, sPES, PPSU, sPPSU, PVDF, and combinations thereof.

[0303] The total concentration of the PAES copolymer and optionally one or more other polymers in the polymer solution can be at least 8 wt.%, or preferably at least 10 wt.% based on the total weight of the polymer solution and / or at most 70 wt.%; or at most 60 wt.%; or at most 50 wt.%; or at most 40 wt.%; or at most 30 wt.% based on the total weight of the polymer solution. A concentration of all polymers in the polymer solution in the range of between 10 wt.% and 30 wt.%, and more preferably between 15 wt.% and 30 wt.%, based on the total weight of the polymer solution is particularly advantageous.

[0304] The polymer solution can contain a pore former such as PVP and / or PEG having a formula weight of at least 200.

[0305] Alternatively, the polymer solution can exclude a pore former, such as PVP and / or PEG having a formula weight of at least 200, can be excluded.

[0306] The polymer solution may contain additional components such as nucleating agents, fillers, etc. Alternatively, the polymer solution may exclude additional components such as nucleating agents, fillers, etc.

[0307] Method for preparing an article (fiber, film, membrane or part thereof)

[0308] An article (such as a fiber, film, membrane or part thereof such as a layer or coating) according to the present invention can be prepared using any of the conventionally known preparation methods (by way of non-limiting examples, by a polymer solution casting method, a solution polymer spinning method or a polymer melt processing method such as extrusion casting). Depending on the final form of the article to be manufactured, different shaping techniques can be used.

[0309] The method may include casting or spinning a polymer solution (sometimes referred to as a "PAES copolymer stock solution") into a preformed article (such as a film, fiber, membrane, coating or layer), and then cooling and / or contacting it with a non-solvent. The polymer stock solution contains the PAES copolymer of the present invention, a solvent (S P ) for the PAES copolymer and optionally at least a pore former. The pore former can be PVP and / or PEG having a formula weight of at least 200.

[0310] The PAES copolymer can be the only polymer in the polymer solution; or the polymer solution further contains at least one other polymer preferably selected from the group consisting of: PSU, sulfonated PSU, PPSU, sulfonated PPSU, PES, sulfonated PES, PDVF and any combination thereof. The solvent (S P ) can be selected from the list of solvents provided for solvent [S]. The pore former can be PVP or PEG having a formula weight of at least 200.

[0311] A porous fiber, film, membrane or part thereof (such as a layer or coating) according to the present invention can be prepared using a phase inversion technique selected from non-solvent induced phase separation and / or thermally induced phase separation.

[0312] When the final article is a flat film, the polymer solution can typically be cast into a film on a flat support substrate (typically a plate, belt or fabric, or a microporous support membrane) by means of a casting knife, a draw bar or a slot die.

[0313] Alternatively, the polymer solution can be spun in the form of a tubular film. The tubular film can be manufactured using a spinneret, a technique which is additionally commonly referred to as the "spinning method". Hollow fibers and capillary membranes can be manufactured according to the spinning method. The term "spinneret" shall hereby be understood to mean an annular nozzle comprising at least two concentric capillaries: a first outer capillary for the polymer solution to pass through and a second inner (commonly referred to as "lumen") for a support fluid (also called "hole fluid") to pass through.

[0314] For non-solvent induced phase separation, the preform is brought into contact with a non-solvent medium (medium [NS]) to provide a porous article. This step of contacting with the medium [NS] is generally effective for precipitating and coagulating the PAES copolymer constituting the preform into a porous article. The PAES copolymer can be precipitated in the medium [NS] by immersion in a coagulation bath containing the non-solvent medium [NS]. Alternatively (or generally before immersion in the coagulation bath), contacting the preform with the medium [NS] can be accomplished by exposing the preform to the gas phase containing the vapors of such medium [NS].

[0315] For the purposes of the present invention, the term "non-solvent" [NS] is intended to mean a medium consisting of one or more liquid substances that cannot dissolve the PAES copolymer and which advantageously promotes the coagulation / precipitation of the PAES copolymer from the polymer solution. The medium (NS) typically comprises water and / or at least one alcohol or polyol, preferably an aliphatic alcohol having a short chain, e.g., 1 to 6 carbon atoms, more preferably methanol, ethanol, isopropanol, and / or ethylene glycol.

[0316] For thermally induced phase separation, the coagulation / precipitation of the PAES copolymer can be promoted by cooling. In this case, the cooling of the preform can typically be carried out using any conventional technique. Generally, when thermally induced coagulation / precipitation occurs, the solvent (Sp) in the polymer solution is advantageously a "latent" solvent (solvent (LT)), i.e., a solvent that is only active towards the PAES copolymer when heated above a certain temperature and cannot dissolve the PAES copolymer below this temperature. When the polymer solution contains a latent solvent, the preforming step (e.g., casting) for preparing the article is typically carried out at a high enough temperature to maintain the polymer solution as a homogeneous solution. Cooling can be achieved by bringing the preform into contact with a cooling fluid, which can be a gaseous fluid (i.e., cooled air or a cooled modified atmosphere) or can be a liquid fluid. In the latter case, the non-solvent medium [NS] detailed above is typically used, such that the techniques of non-solvent-induced and thermally induced precipitation can occur simultaneously. However, it should generally be understood that even in cases where thermally induced precipitation of the PAES copolymer occurs, an additional step of non-solvent-induced precipitation (i.e., contact with the non-solvent medium [NS]) is carried out, for example, to complete the copolymer precipitation and facilitate the removal of one or more solvents.

[0317] In cases where the polymer solution contains both a solvent (Sp) for the copolymer and a non-solvent, at least partial selective evaporation of the solvent (Sp) can be used to promote the coagulation / precipitation of the copolymer. In this case, the solvent (Sp) and the non-solvent are typically selected such that the solvent (Sp) has a higher volatility than the non-solvent, such that stepwise evaporation of the solvent (Sp) under controlled conditions typically results in copolymer precipitation and thus actual contact of the preform with the non-solvent medium.

[0318] When present in the polymer solution, the pore former is typically at least partially (if not completely) removed from the porous article in the non-solvent medium [NS] during this step of the article manufacturing method.

[0319] The method can further include additional processing steps after shaping and precipitation, such as steps of rinsing and / or stretching the porous article and / or drying the porous article, especially when the article is a porous membrane.

[0320] For example, the porous article can be additionally rinsed.

[0321] Furthermore, the porous article can be advantageously stretched to increase its average porosity.

[0322] The porous article can be dried at a temperature of at least 30 °C advantageously. The drying can be carried out in air or in a modified atmosphere, such as in an inert gas, typically removing moisture (water vapor content less than 0.001% v / v). The drying can alternatively be carried out under vacuum.

[0323] Suitable examples of methods for forming porous membranes from polyarylethersulfone polymers are described in US2019 / 054429 A1 (Solvay Specialty Polymers USA, LLC), which is incorporated herein by reference.

[0324] The non-porous (or dense) fibers, films, membranes or parts thereof (such as layers or coatings) according to the invention can be prepared using polymer solution casting or polymer melt processing methods such as extrusion casting. In such cases, the PAES copolymer can be the sole polymer in the non-porous article; or the non-porous article further comprises at least one other polymer.

[0325] After casting the polymer solution onto a substrate to form a film, the solvent is typically evaporated to produce a non-porous film.

[0326] Typically, the production of non-porous articles from solutions containing PAES copolymers does not involve the use of a non-solvent medium.

[0327] The non-porous article can be produced by classical melt processing techniques such as film, tube or pipe extrusion, wire coating, injection molding, etc. In all these methods, the common feature is the use of equipment (extruder, injection molding machine) in which the polymer feed (in powder or pellet form) is melted and then formed into the desired shape. The shaped article is then cooled in air or water.

[0328] The non-porous article can also be produced via a solvent medium (as in coating or casting). In such cases, the solvent is allowed to evaporate. In a typical industrial method for preparing a free-standing cast film, the polymer solution is fed via a gear pump through a slot die and cast onto a moving support (belt). After casting, the solvent is evaporated in an oven chamber. The polymer film is then separated 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: pp. 1-14, Springer publisher.

[0329] A variety of techniques for fabricating articles can be found in the book titled "Rheology and Processing of Polymeric Materials" by Chang Dae Han, Volume 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).

[0330] Applications

[0331] The PAES copolymers according to the present invention are particularly suitable for manufacturing articles intended to come into contact with an aqueous medium. The aqueous medium can include biological fluids (such as blood, serum), food products such as beverages (e.g., fruit juice, milk, beer), water, wastewater, or any aqueous industrial process stream (such as process water, cooling water).

[0332] In particular, the articles can be used for medical applications (such as hemodialysis membranes), for solid-state battery applications, for polymer electrolyte membranes, for polymer or solid electrolytes, for filtering aqueous media (such as reverse osmosis membranes, ultrafiltration membranes, microfiltration membranes, nanofiltration membranes, and / or ion exchange membranes). Filtering of aqueous media can include filtering of food and beverages, filtering for water purification, filtering for wastewater treatment, and filtering for industrial process separation involving aqueous media.

[0333] In the applications in use, health care applications, particularly medical applications, can be mentioned, where articles containing the PAES copolymers can be advantageously used for single use or can be reusable.

[0334] Method for purifying an aqueous medium

[0335] A further aspect of the present invention can relate to a method for purifying an aqueous medium, the method comprising at least a filtration step through a membrane, one or more fibers, or one or more films comprising the PAES copolymers according to the present invention or made therefrom.

[0336] In fact, the PAES copolymers of the present invention can be used in different filtration membrane geometries. For example, the PAES copolymers can be used in flat membranes and / or capillary-shaped hollow fiber membranes. The aqueous medium flowing towards these membranes can take the form of dead-end flow or cross-flow.

[0337] In particular, the purification method can be used to purify human biological fluids, preferably blood products such as whole blood, plasma, serum, fractionated blood components or mixtures thereof. The purification is carried out in an extracorporeal circuit which can include at least one filtering device (or filter) comprising at least one membrane, fiber or film as described above.

[0338] As contemplated herein, a blood purification method through an extracorporeal circuit can include hemodialysis (FD) by diffusion, hemofiltration (HF), hemodiafiltration (HDF) and / or blood concentration. In HF, blood is filtered by ultrafiltration, whereas in HDF, blood is filtered by a combination of FD and HF.

[0339] A blood purification method through an extracorporeal circuit is typically carried out by means of a hemodialyzer, i.e., a device designed to carry out any one of FD, HF or HFD. In such methods, blood is filtered from waste solutes and fluids (such as urea, potassium, creatinine and uric acid), thus providing blood free of waste solutes and fluids.

[0340] Typically, a hemodialyzer for carrying out a blood purification method includes a cylindrical bundle of hollow fibers of a membrane, the bundle having two ends, each of the ends being fixed in a so-called potting compound which is usually a polymeric material acting as a glue for holding the bundle ends together. Potting compounds are known in the art and notably include polyurethanes. By applying a pressure gradient, blood is pumped through the bundle of the membrane via a blood port, and the filtration product ("dialysate") is pumped through the space around the filter.

[0341] Method for increasing the flexibility of a bulk aromatic sulfone polymer

[0342] Another aspect of the present invention relates to a method for improving the flexibility of an aromatic sulfone polymer material with a high Tg, the method comprising adding the PAES copolymer of the present invention to a bulk aromatic sulfone polymer with a high Tg to form a polymer blend having increased flexibility compared to the bulk aromatic sulfone polymer. That is, the polymer blend has a lower Tg than the Tg of the bulk aromatic sulfone polymer. The resulting polymer blend is preferably used to form membranes (e.g., hollow fiber membranes) suitable for hemodialysis or water filtration (such as ultrafiltration, nanofiltration and microfiltration applications). The bulk polymer with a high Tg is preferably selected from PSU, PPSU, PES, copolymers or blends thereof having a Tg ≥ 180 °C. Higher flexibility means that, compared to the bulk aromatic sulfone polymer, when the polymer blend is bent, the ductility is improved (a less brittle material).

[0343] The present invention will now be described in more detail with reference to the following examples, which are for illustrative purposes only and do not limit the scope of the present invention.

[0344] Example

[0345] In these examples, short-chain (6-C) ethylene oxide segments were incorporated into PES, PSU, and PPSU polymer chains via copolymerization of 1,2-bis(2-chloroethoxy)ethane (DCEO) and dichlorodiphenyl sulfone (DCDPS) with diols according to a one-pot synthesis procedure.

[0346] Raw materials

[0347] DCEO (1,2-bis(2-chloroethoxy)ethane or triglycol dichloride), CAS No. 112-26-5, is available from TCI America.

[0348] DCDPS (4,4'-dichlorodiphenyl sulfone), CAS No. 80-07-9, is available from Solvay Specialty Polymers USA, LLC.

[0349] BP (4,4'-biphenol), CAS No. 92-88-6, is available from TCI America.

[0350] Bis A (2,2-bis(4-hydroxyphenyl)propane), CAS 80-05-7, is available from Aldrich.

[0351] Bis S (4,4'-dihydroxydiphenyl sulfone), CAS No. 80-09-1, is available from Acros (now Thermo Scientific).

[0352] TMBPF (tetramethylbisphenol F), CAS No. 5384-21-4, is available from TCI America.

[0353] TGE (triglycol), CAS No. 112-27-6, is available from TCI America.

[0354] K2CO3 (potassium carbonate), CAS No. 584-08-7, is available from Fisher or Aldrich.

[0355] Sulfolane (tetrahydrothiophene 1,1-dioxide), CAS No. 126-33-0, is available from Alfa Aesar or Acros (now Thermo Scientific).

[0356] DMAc (dimethylacetamide), CAS No. 127-19-5, is available from Alfa Aesar or Acros (now Thermo Scientific).

[0357] NMP (N-Methylpyrrolidone), CAS No. 872-50-4, is available from Acros Organics (now Thermo Fisher Scientific).

[0358] Toluene, CAS No. 108-88-3, is available from Acros Organics (now Thermo Fisher Scientific) or Fisher Scientific.

[0359] Methanol, CAS No. 67-56-1, is available from Fisher Scientific.

[0360] PES: PES 3300, CAS No. 25608-63-3, is available from Solvay Specialty Polymers USA, LLC.

[0361] PSU: P-3500LCD MB7, CAS No. 25154-01-2, is available from Solvay Specialty Polymers USA, LLC.

[0362] PPSU: R-5000 CAS No. 31833-61-1, is available from Solvay Specialty Polymers USA, LLC.

[0363] Test Methods

[0364] GPC method (sulfone method) for measuring molecular weights (Mn, Mw)

[0365] Molecular weight (number-average molecular weight Mn and weight-average molecular weight Mw) was measured by gel permeation chromatography (GPC) using dichloromethane as the mobile phase. Separation was carried out using two 5 μ mixed D size exclusion chromatography (SEC) columns with a guard column from Agilent Technologies. A UV detector at 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml / min and an injection volume of 20 μL of a 0.2 w / v% solution in the mobile phase were selected. Calibration was performed with 10 or 12 narrow molecular weight polystyrene standards from Agilent Technologies (peak molecular weight range: 371,000 to 580 g / mol).

[0366] Calibration Curve:

[0367] 1) Type: Calibration with relative narrow calibration standards

[0368] 2) Fitting: Third-order regression.

[0369] Integration and calculation: Empower Pro GPC software manufactured by Waters was used to acquire data, calibration, and molecular weight calculation. The start and end points of peak integration were determined manually from a significant difference from the overall baseline.

[0370] DSC

[0371] According to ASTM D3418, differential scanning calorimetry (DSC) was used to determine the glass transition temperature (Tg) and the melting temperature (Tm), if any. The DSC experiments were performed using a Q100 from TA Instrument. The DSC curves were recorded by heating, cooling, reheating, and then 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. Unless otherwise noted, the second heating curve was used to provide the reported Tg (and Tm, if any) values.

[0372] Measurement of liquid contact angle (CA)

[0373] One way to characterize surface hydrophilicity is to measure the contact angle. According to ASTM D 5725-99, the contact angles of water and hexadecane on dry, dense polymer films were evaluated at 25 °C using a contact angle system OCA Dataphysics. The values were the average of at least 10 measurements. The drop volume was always 2 μL. Using this CA method, the contact angle decreases with increasing hydrophilicity.

[0374] Measurement of air contact angle via the captured air bubble method (CAB)

[0375] As described above, the contact angle can be measured to characterize surface hydrophilicity. Due to absorption phenomena, this method is not suitable for measuring the contact angle of porous hydrophilic samples, so the contact angle was measured by the captive bubble (CAB) method. In fact, this method measures the contact angle of a bubble at the surface immersed in a liquid (in this case water). The CAB method has several advantages for membrane characterization. Since the membrane is already wet, swelling and absorption are suppressed. In addition, this avoids surface contamination, chemical reorganization, and drying-induced degradation. Moreover, the sample surface is in contact with a saturated and well-controlled environment, thus improving reproducibility.

[0376] Air contact angle measurements were performed at room temperature by the CAB method using an adapted environmental control chamber filled with deionized water. The measurements were carried out on an optical tensiometer (Attension Theta Flex from BIOLIN) equipped with a high-quality monochromatic cold-light LED and a high-resolution (1984×1264) digital camera. Before analysis, the wet (in water) samples were wrapped with double-sided tape on a 15×15 mm glass substrate fixed to a holder and then immersed in DI water. Then, 2 μL of air bubbles were dropped onto the sample surface using a J-shaped syringe, and the ACA was measured. The presented contact angle values are the average of 10 measurements on the same sample. With this CAB method, higher values mean higher hydrophilicity of the sample.

[0377] Example 1 (According to the present invention)

[0378] One-pot synthesis of PPSU-EO using DCEO+DCDPS (with a 50:50 molar ratio) and BP as diols

[0379] The polymerization used to prepare the PPSU-EO copolymer E1 is illustrated in Scheme 1. For copolymer E1, in this scheme T is a bond and m = n = 0.5.

[0380] The polycondensation was carried out in a 2-L reaction kettle with a 4-neck lid equipped with a mechanical stirrer, a nitrogen inlet, and an internal thermocouple. The kettle was charged with

[0381] - A monomer mixture containing DCDPS (90.06 g, 0.3136 mol) as the dihalo monomer (AS), 1,2-bis(2-chloroethoxy)ethane (28.67 g, 0.3136 mol) as the dihalo monomer (AO), and bisphenol (116.25 g, 0.6243 mol) as the dihydroxy monomer (B),

[0382] - Potassium carbonate (90.60 g, 0.6555 mol) as the alkali metal carbonate, and

[0383] - Sulfolane (1067.4 g) as the solvent [S] and toluene (15 mL) as the azeotrope-forming cosolvent,

[0384] To obtain a reaction mixture containing 25 wt.% solids.

[0385] The molar ratio of dihydroxy (B) / [dihalo (AO)+(AS)] is 0.9954.

[0386] The molar ratio of the equivalent of potassium (alkali metal) / the equivalent of hydroxyl (OH) in diol (B) [eq.(K) / eq.(OH)] is 1.05.

[0387] The molar ratio of dihalide (AS) relative to the combination dihalide (AO) + (AS) is 50 mol%.

[0388] The reactants were dried via azeotropic distillation of an aqueous toluene solution. The reaction mixture was heated to 210 °C and maintained at this temperature under nitrogen overnight.

[0389] The reaction mixture was then diluted with NMP (1247.01 g) to obtain 15 wt.% solids, and the diluted reaction mixture was pressure filtered through a 2.7 micron glass fiber filter at about 40 psi. The diluted reaction mixture containing a mixture of NMP and sulfolane was coagulated in a blender containing room temperature deionized water (non-solvent), then washed 4 times in room temperature water (about 20 °C - 25 °C), washed three times with methanol, and then dried overnight in an oven at 100 °C.

[0390] The ethylene oxide content of the PPSU-EO copolymer E1 corresponds to 17 wt.%.

[0391] Example 2 (According to the Invention)

[0392] One-pot synthesis of PES-EO copolymer E2 using DCEO + DCDPS (with a 50:50 molar ratio) and Bis S as the diol

[0393] The polymerization used to prepare the PES-EO copolymer E2 is illustrated in Scheme 1. For copolymer E2, in this scheme T is SO2 and m = n = 0.5.

[0394] Charge the 2-L reactor described above with:

[0395] - A monomer mixture containing DCDPS (90.06 g, 0.3136 mol) as the dihalide monomer (AS), 1,2-bis(2-chloroethoxy)ethane (28.67 g, 0.3136 mol) as the dihalide monomer (AO), and bisphenol S (156.24 g, 0.6243 mol) as the dihydroxy monomer (B),

[0396] - Potassium carbonate (90.60 g, 0.6555 mol) as the alkali metal carbonate, and

[0397] - Sulfolane (923.26 g) as the solvent [S] and toluene (15 mL = 13 g) as the azeotrope-forming co-solvent,

[0398] To obtain a reaction mixture with 30 wt.% solids.

[0399] The molar ratio of dihydroxy (B) / [dihalide (AO) + (AS)] is 0.9954.

[0400] The molar ratio of the equivalent of potassium (alkali metal) to the equivalent of hydroxyl group (OH) in diol (B) [eq.(K) / eq.(OH)] is 1.05.

[0401] The molar content of dihalide (AS) in the reaction mixture relative to the combined dihalide (AO)+(AS) is 50 mol.%, or the AO / AS molar ratio is 50 / 50.

[0402] The reaction mixture was heated to 220 °C and maintained at this temperature for 4 hours.

[0403] The steps for drying the reaction mixture and separating the polymer are the same as those described in Example 1.

[0404] The weight content of the ethylene oxide segment of the PES-EO copolymer E2 corresponds to 14 wt.%.

[0405] Comparative Example 1 (not according to the present invention)

[0406] One-pot synthesis of PPSU-EO copolymer CE1 using DCEO+DCDPS (with a molar ratio of 75:25) and BP as diol

[0407] The polymerization used to prepare the PPSU-EO copolymer CE1 is illustrated in Scheme 1. For copolymer CE1, in this scheme T is a bond; m = 0.75; n = 0.25.

[0408] For this comparative example, the same one-pot procedure as described in Example 1 was carried out, except that the molar ratio of DCEO = dihalide (AS) to the combined dihalide DCEO+DCDPS in the reaction mixture was 75 mol%.

[0409] The weight content of the ethylene oxide segment constitutes 27 wt% of the PPSU-EO copolymer CE1.

[0410] Example 3 (according to the present invention)

[0411] One-pot synthesis of PPSU-EO copolymer E3 using DCEO+DCDPS (with a molar ratio of 75:25) and Bis S as diol

[0412] The polymerization used to prepare the PES-EO copolymer E3 is illustrated in Scheme 1. For copolymer E3, in this scheme T is SO2; m = 0.75; n = 0.25.

[0413] The same one-pot procedure as described in Example 2 was carried out, except that the molar ratio of dihalide (AS) to the combined dihalide (AO)+(AS) in the reaction mixture was 75 mol% or the molar ratio AO / AS = 1 / 3.

[0414] The weight content of the ethylene oxide segment constitutes 22 wt% of the PPES-EO copolymer E3.

[0415] Example 4 (according to the present invention)

[0416] Using DCEO + DCDPS (with a molar ratio of 4:96) and Bis A as diols, the PSU-EO copolymer E4 was synthesized in one pot

[0417] The polymerization used to prepare the PSU-EO copolymer E4 is illustrated in Scheme 1. For copolymer E4, in this scheme T is C(CH3)2; m = 0.04; n = 0.96.

[0418] The following were charged into the reactor described above:

[0419] - A monomer mixture containing DCDPS (155.62 g, 0.5419 mol) as the dihalo monomer (AS), 1,2-bis(2-chloroethoxy)ethane (4.23 g, 0.02261 mol) as the dihalo monomer (AO), and bisphenol A (128.26 g, 0.5618 mol) as the dihydroxy monomer (B),

[0420] - Potassium carbonate (81.54 g, 0.59 mol) as the alkali metal carbonate, and

[0421] - NMP (873.81 g) as the solvent [S] and toluene (20 mL) as the azeotrope-forming cosolvent,

[0422] To obtain a reaction mixture with 30 wt.% solids.

[0423] The molar ratio of dihydroxy (B) / [dihalo (AO)+(AS)] is 0.9952.

[0424] The molar ratio of the equivalent of potassium (alkali metal) / the equivalent of hydroxyl (OH) in diol (B) [eq.(K) / eq.(OH)] is 1.05.

[0425] The molar content of dihalo (AS) relative to the combined dihalo (AO)+(AS) in the reaction mixture is 4 mol.%, or the molar AO / AS molar ratio is 4 / 96.

[0426] The reactants were dried by azeotropic distillation with toluene and then stirred overnight at 120 °C. The reaction mixture was heated to 180 °C and maintained at this temperature for 6 hours. The polymer separation step was the same as described in Example 1.

[0427] Based on the total copolymer weight, the weight content of the ethylene oxide segment constitutes 1.2 wt% of the PSU-EO copolymer E4.

[0428] Characterization of PAES copolymers E1, CE1, E2, E3, E4

[0429] The Mw and Tg of the PAES copolymers (E1), (E2), (E3), (E4) and (CE1) were measured by the method described previously and are provided in Table 1.

[0430] Table 1

[0431]

[0432] * Relative mol.% DCEO is based on the combined molar amounts of DCEO and DCDPS in the reaction mixture

[0433] ** mol.% DCEO is based on the combined molar amounts of DCEO + DCDPS + diol in the reaction mixture

[0434] *** wt.% EO is based on the weight of EO present in the total copolymer weight

[0435] The PPSU-EO copolymer E1 and the PES-EO copolymer E2, which constitute a 50 / 50 molar ratio of DCEO / DCDPS, exhibit good molecular weights (M w = 59200, 44400 g / mol) and thermal properties (Tg = 120 °C, 134 °C).

[0436] The PSU-EO copolymer E4, which constitutes a 4 / 96 DCEO / DCDPS molar ratio, exhibits good molecular weight (M w = 51200 g / mol) and thermal properties (Tg = 183 °C).

[0437] The PES-EO copolymer E3, which utilizes Bis S, DCEO and DCDPS and constitutes a 75 / 25 DCEO / DCDPS molar ratio, exhibits good molecular weight (M w = 36900 g / mol), but has a low Tg (98 °C); this low Tg increases the flexibility of copolymer E3 and can provide advantages in membrane applications when increased polymer ductility is desired.

[0438] The PPSU-EO copolymer CE1, which utilizes bisphenol, DCEO and DCDPS and constitutes a 75 / 25 DCEO / DCDPS molar ratio, exhibits a low molecular weight (M w = 19800 g / mol) and is semi-crystalline, with a melting temperature of 164 °C detected.

[0439] Solubility test of PAES copolymers E1, E2

[0440] Samples of the PAES copolymers E1 and E2 were tested for solubility in NMP and DMAc. For the solubility study, polymer samples were dissolved at 5 wt.%, 10 wt.%, 15 wt.%, and 20 wt.% in NMP and DMAc, heated to 65 °C, cooled to ambient conditions and held for 7 days, after which observations of transparency were recorded. The results of the solubility of the PAES copolymers E1 and E2 are provided in Tables 2 and 3, respectively.

[0441] Table 2

[0442]

[0443] Table 3

[0444]

[0445] Tables 2 and 3 show that homogeneous solutions were obtained in the range of PPSU-EO and PES-EO copolymer contents (5 wt% - 20 wt%).

[0446] Compared with the PPSU-EO copolymer E1, the PES-EO copolymer E2 showed better solubility.

[0447] Compatibility test of PAES copolymers E1 and E2

[0448] The solution compatibility of the PAES copolymers E1 and E2 was also evaluated in DMAc and NMP solvents and compared with PSU and PES homopolymers.

[0449] For the following weight ratio ranges of PAES copolymers to homopolymers: 5 / 95, 10 / 90, 20 / 80, 50 / 50, 80 / 20, 90 / 10, and 95 / 5, the compatibility of blends of a total of 20 wt.% polymer in the solvent / polymer mixture was evaluated. The solvent / polymer mixture was heated to 65 °C and then cooled to ambient temperature. Observations of transparency and phase separation were recorded at the initial cooling and after standing at ambient temperature for 7 days.

[0450] The results of the compatibility of the PPSU-EO copolymer E1 with PSU and PES are provided in Tables 4 and 5, respectively.

[0451] Table 4: Binary solutions with PPSU-EO copolymer E1 + PSU

[0452]

[0453] Table 5: Binary solutions with PPSU-EO copolymer E1 + PES

[0454]

[0455]

[0456] The compatibility results of the PES-EO copolymer E2 with PSU and PES are provided in Tables 6 and 7, respectively.

[0457] Table 6: Binary solutions with PES-EO copolymer E2 + PSU

[0458]

[0459] Table 7: Binary solutions with PES-EO copolymer E2 + PES

[0460]

[0461] The solutions of the blends exhibited varying degrees of clarity, turbidity, and haziness. None showed separation into distinct layers.

[0462] The PES-EO copolymer E2 showed good homogeneity at room temperature.

[0463] The PPSU-EO copolymer E1 showed homogeneity and turbidity and needed to be heated to 40 °C for film preparation.

[0464] The data in Tables 3, 6, and 7 indicate that the PES-EO copolymer E2 and the blend of the PES-EO copolymer E2 with PES provide a more stable solution for membrane coagulation compared to other combinations.

[0465] Example 5 - Dense film (non-porous article)

[0466] Dense film preparation (solvent DMAc)

[0467] The dense film was prepared from a polymer solution comprising a 20% wt.% polymer concentration in DMAc (wt% is based on the total solution weight).

[0468] In Test No. Q, the polymer in the polymer solution was the PPSU-EO copolymer E1. In Test No. R, the polymer in the polymer solution was a blend of the PPSU-EO copolymer E1 and PPSU using 14.3 wt% of the PPSU-EO copolymer E1 based on the combined weight of the copolymer E1 + PPSU. In Test No. S, the polymer in the polymer solution was the PES-EO copolymer E2. In Test No. T, the polymer in the polymer solution was a blend of the PES-EO copolymer E2 and PES using 14.3 wt% of the PES-EO copolymer E2 based on the combined weight of the copolymer.

[0469] The dense film made from the PES-EO copolymer E2 was prepared from a 30% w / w% polymer concentration solution in DMAc.

[0470] The procedure for preparing a flat and dense polymer film is as follows. A polymer solution containing a polymer and DMAc solvent is cast at 40 °C on a suitable smooth glass support by means of an automated casting knife. The knife gap is set to 500 μm. After casting the film, the solvent is evaporated in a vacuum oven at 130 °C for 4 hours.

[0471] Characterization of dense films

[0472] Table 8

[0473]

[0474]

[0475] The dense films incorporated as the sole or blend component in PES-EO copolymer E2 in Test No. S (Table 8) exhibited higher hydrophilicity compared to PES-based films and compared to films based on PPSU-EO copolymer E1.

[0476] Example 6 - Porous Membrane (Porous Article)

[0477] Porous film preparation (solvent DMAc)

[0478] The porous membrane was prepared from PES (using a polymer stock solution with a polymer concentration of 20 w / w% in DMAc) and a blend of PES + PES-EO copolymer E2 using a PES:E2 mass ratio of 3:1 (using a polymer stock solution with a polymer concentration of 20 w / w% in DMAc).

[0479] Flat sheet porous membranes were prepared by casting the polymer stock solution on a suitable smooth glass support by means of an automated casting knife. Membrane casting was carried out by keeping the stock solution, casting knife, and support at a temperature of 25 °C to prevent premature precipitation of the polymer. The knife gap was set to 250 μm. After casting, the film of the porous membrane was immediately immersed in a coagulation bath to induce phase inversion (polymer precipitation). The coagulation bath consisted of pure deionized water. After coagulation, the membrane was washed several times in pure water over the following days to remove residual solvent. The membrane was stored (wet) in water and then dried for further analysis.

[0480] Characterization of porous films

[0481] Table 9

[0482]

[0483] The porous film from Test No. V (Table 9) exhibits higher hydrophilicity than the film based only on PES homopolymer (see Test No. W), and this porous film incorporates the PES-EO copolymer E2 as a blend component at a weight ratio of 1:3 (E2:PES) with PES [or 25 wt% E2 based on the combined weight of E2 + PES].

[0484] Example 7 - Blood Compatibility Test

[0485] The porous membrane made of the PES-EO copolymer E2 (see Test No. V in Example 5) was also used for blood compatibility tests [activated partial thromboplastin time (aPTT) and prothrombin time (PT)].

[0486] Coagulation test

[0487] This test measures the clotting time of plasma.

[0488] It should be noted that the control sample is blood that does not come into contact with the specimen.

[0489] It should be noted that the test performed (activated)

[0490] The activated partial thromboplastin time (aPTT) and prothrombin time (PT) tests were performed after contact with the porous flat sheet membrane. The procedure is as follows:

[0491] Fresh human whole blood (blood from randomly selected patients not treated with anticoagulant therapy) was placed in a vial containing sodium citrate.

[0492] Contact was made by immersing the membrane in the vial with whole blood to achieve a surface / volume ratio of 6 cm2 / ml and incubating for 30 minutes at a temperature of 37 °C ± 1 °C under dynamic conditions (orbital shaker).

[0493] Then the blood was centrifuged at 3000 G for 20 minutes. The supernatant plasma obtained in this way was subjected to aPTT and PT.

[0494] In the case of the aPTT test, finally the plasma was mixed with a colloidal activator (aluminum magnesium silicate), followed by the addition of calcium chloride (a solution with a concentration of 0.025 mol / l) and the clotting time was measured.

[0495] In the case of the PT test, finally the plasma was mixed with thromboplastin (rabbit brain thromboplastin), followed by the addition of calcium chloride (a solution with a concentration of 0.025 mol / l) and the clotting time was measured.

[0496] The results of both the aPTT and PT tests (clotting time in seconds) are reported in Table 10.

[0497] Table 10

[0498]

[0499] Plasma extracted from blood in contact with these membranes coagulates at approximately the same rate as plasma not in contact with any membrane, and thus the PES-EO copolymer E2 has no negative impact on the blood coagulation cascade compared to that observed with PES membranes.

[0500] Counterexample 2 (not according to the present invention)

[0501] This counterexample was generated to compare the polymerization performance of using a polyalkylene oxide with two hydroxyl groups: HO-AO-OH monomer (such as PEG) as taught in the prior art instead of the Cl-AO-Cl monomer used in the present invention. Triethylene glycol (TEG) was chosen for this counterexample because it has the same ethylene oxide structure (-CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-) as 1,2-bis(2-chloroethoxy)ethane (DCEO).

[0502] Use TEG + Bis S (with a 25:75 molar ratio) and DCDPS as the sole dihalide for the one-pot synthesis of the PES-EO copolymer CE2

[0503] The polymerization used to prepare the PES-EO copolymer CE2 is illustrated in Scheme 3.

[0504] This counterexample 2 was carried out in a manner similar to Example 3 in US2016 / 0075850 A1, where PEG2050, bisphenol S, and DCDPS were reacted in NMP at about 50 wt.% solids in NMP without an azeotropic mixture-forming solvent and with 5 mol% excess (relative to the diol) of potassium carbonate at 190 °C for 6 hours, except that in this counterexample PEG2050 was replaced by triethylene glycol (TEG). The resulting ethylene oxide weight content in the copolymer CE2 relative to all monomers (using 12.5 mol.% TEG, 37.5 mol.% Bis S, 50 mol.% DCDPS) is 7.3 wt.%, similar to the 7.2 wt.% ethylene oxide weight content (PEG2050) in Example 3 of US2016 / 07850A1.

[0505] Characterization of sample (CE2)

[0506] The Mw, Mn, PDI, and Tg of the resulting copolymer CE2 were measured by the methods described previously and are provided in Table 11.

[0507] It was observed that the preparation method using triethylene glycol taught in US2016 / 07850A1 resulted in the production of a sample (CE2) with a very low molecular weight (Mw = 4550 g / mol). This oligomer would not be suitable for the preparation of articles such as films because its viscosity would be insufficient (due to its low Mw).

[0508] Table 11

[0509] Testing of copolymer CE2 PES-EO DCDPS mol% 50 Bis S mol% 37.5 TEG mol%** 12.5 EO wt.%** 7 <![CDATA[M w ,g / mol]]> 4550 <![CDATA[M n , g / mol]]> 3090 PDI 1.47 <![CDATA[T g , °C]]> 147

[0510] **mol.% TEG is based on the combined molar amount of TEG + DCDPS + Bis S in the reaction mixture

[0511] ***wt.% EO is based on the weight of EO present in the total copolymer weight

[0512] Example 8 (according to the present invention)

[0513] One-pot synthesis of TMBPF-EO sulfone copolymers E5 to E10 using DCEO + DCDPS (molar ratios 12 / 88, 25 / 75, 50 / 50) and TMBF as diols

[0514] Copolymer samples E5 to E10 were prepared according to the general procedure described below.

[0515] General procedure for preparing TMBPF-EO sulfone copolymers:

[0516] The polymerization used to prepare TMBPF-EO copolymer samples E5 to E10 is illustrated in Scheme 2. For copolymers E5 to E10, m' varies from 0.12 to 0.50 in this scheme, while n' = 1 - m'.

[0517] The polycondensation was carried out in a 500 mL round-bottom flask (reactor) equipped with an overhead mechanical stirrer, a nitrogen inlet, and a Dean-Stark water separator with a reflux condenser.

[0518] The reactor was charged with

[0519] - a monomer mixture containing DCDPS as a dihalo monomer (AS), 1,2-bis(2-chloroethoxy)ethane as a dihalo monomer (AO), and tetramethylbisphenol F as a dihydroxy monomer (B),

[0520] - potassium carbonate as an alkali metal carbonate, and

[0521] - sulfolane or NMP or DMAc as a solvent [S] and toluene as an azeotrope-forming cosolvent,

[0522] The amounts of the monomers were thus selected to achieve a polymer content of 30 wt% in the reaction mixture.

[0523] When expressed as the ratio of the equivalents of alkali metal (Me) to the equivalents of hydroxyl group (OH) [eq.(Me) / eq.(OH)], the amount of potassium carbonate used in the reaction mixture is generally 1.05 to 1.30 eq.(K) / eq.(OH).

[0524] The molar ratio between the total amount of hydroxyl groups from TMBPF [monomer (B)] and the total amount of halogen groups from DCEO and DCDPS [monomers (AO)+(AS)] in the monomer mixture is 1.0.

[0525] Before starting heating via an external oil bath, a nitrogen stream is established and the reaction mixture is purged with nitrogen for 15 minutes. The reaction mixture containing the monomers is stirred with an overhead mechanical stirrer and heated using an oil bath controlled at the target azeotropic distillation temperature to remove water and toluene at 155 °C. This temperature is maintained for 60 - 90 minutes while collecting the azeotropic distillate, which is then drained from the water separator. The bath temperature is increased from 155 °C to the appropriate reaction temperature (175 °C when using DMAc, 190 °C when using NMP, or 210 °C when using sulfolane) within 30 - 60 minutes. Water (a by-product of the polymerization reaction) is continuously stripped from the reactor and collected in a Dean - Stark water separator. After reaching the target internal temperature, the reaction is maintained at this temperature for a suitable reaction period until the desired M w . Depending on the reaction temperature / medium, the reaction period varies from 4 to 16 hours.

[0526] Once the desired molecular weight is reached, the polymerization is terminated by diluting to 15 wt.% solids with a solvent (NMP, DMAc, or NMP), reducing the internal temperature back to ambient temperature (21 °C), and adding acetic acid to convert the sodium phenoxide chain ends back to phenol. The diluted polymer solution is filtered under pressure through a 2.7 μm glass fiber filter pad to remove salts. The polymer solution is poured into a Waring blender containing a non-solvent (water, methanol, or 50 / 50 vol. / vol. methanol / water) to precipitate the copolymer using a ratio of 1:5 polymer solution to non-solvent, to obtain a white solid (polymer precipitate). The separated white solid is then washed 6 times with the same non-solvent, filtered between each wash, then vacuum filtered, and dried in a vacuum oven at 100 °C - 120 °C for 12 hours.

[0527] Comparative Example 3 (not according to the present invention)

[0528] One-pot synthesis of TMBPF sulfone homopolymer CE3 using DCDPS as the sole dihalo monomer and TMBPF as the sole diol

[0529] The homopolymer CE3 made from TMBPF and DCDPS was prepared according to the general procedure for preparing the TMBPF-EO sulfone copolymer (E5)-(E6) in sulfolane, except that DCEO was omitted.

[0530] The initial reaction mixtures and reaction conditions for the copolymer samples (E4)-(E9) and the homopolymer sample (CE3) are provided in Table 12.

[0531] Table 12

[0532]

[0533]

[0534] *Contains 30 wt.% solids; monomer molar ratio TMBPF / (DCEO + DCDPS) = 1

[0535] The molecular weights Mn and M measured by GPC w , PDI and Tg are provided in Table 13.

[0536] Table 13

[0537]

[0538] *Relative mol.% DCEO is based on the total moles of DCEO + DCDPS in the reaction mixture

[0539] **mol.% DCEO is based on the combined moles of DCEO + DCDPS + Bis S in the reaction mixture

[0540] ***wt.% EO is based on the weight of EO present in the total copolymer weight

[0541] Comparative Example 4 (not according to the present invention)

[0542] This comparative example was generated to compare the polymerization performance using the HO-EO-OH monomer taught in the prior art instead of the Cl-EO-Cl monomer (DCEO) used in the present invention. Triethylene glycol (TEG) was selected for this comparative example because it has the same ethylene oxide structure (-CH2-CH2-O-CH2-CH2-O-CH2-CH2-O-) as 1,2-bis(2-chloroethoxy)ethane (DCEO).

[0543] PES-EO copolymer CE4 was synthesized in one pot using TEG + TMBPF (with a 25:75 molar ratio) and DCDPS as the only dihalide

[0544] The polymerization used to prepare the TMBPF-EO copolymer CE4 is illustrated in Scheme 4.

[0545] This counterexample was conducted in a manner similar to Example 3 in US2016 / 0075850 A1, where PEG2050, BisS, and DCDPS were used in NMP with approximately 50 wt.% solids in NMP and without an azeotropic mixture-forming solvent, and potassium carbonate in a 5% molar excess (relative to the diol) was reacted at 190 °C for 6 hours, except that in this counterexample, PEG2050 was replaced by triethylene glycol (TEG) and Bis S was replaced by TMBPF. The resulting weight content of ethylene oxide in copolymer CE5 relative to all monomers (using 12.5.% TEG, 37.5 mol.% TMBPF, 50 mol.% DCDPS) was 7.3 wt.%, similar to the 7.2 wt.% ethylene oxide weight content (PEG2050) in Example 3 of US2016 / 07850A1.

[0546] Characterization of sample CE4

[0547] The Mw, Mn, PDI, and Tg of the resulting copolymer CE4 were measured by the methods described previously and are provided in Table 14.

[0548] It was observed that the preparation method using triethylene glycol taught in US2016 / 07850A1 resulted in a sample (CE4) with a very low molecular weight (Mw of approximately 4000 g / mol; Mn of approximately 2550 g / mol) when using TMBPF as the sole diol. This oligomer CE4 would not be suitable for preparing articles such as films because its viscosity would be insufficient due to its low molecular weight.

[0549] Table 14

[0550] Copolymer CE4 DCDPS mol% 50 TMBPF mol% 37.5 TEG mol%** 12.5 EO wt.%** 7 <![CDATA[M w , g / mol]]> 3989 <![CDATA[M n , g / mol]]> 2553 PDI 1.56 <![CDATA[T g , °C]]> 159

[0551] Characterization of dense films

[0552] **mol.% TEG is based on the combined molar amount of TEG + DCDPS + TMBPF in the reaction mixture

[0553] ***wt.% EO is based on the weight of EO present in the total copolymer weight

[0554] Example 9 - Dense film (non-porous article)

[0555] Dense film preparation (solvent DMAc)

[0556] The dense films prepared were prepared in the same manner as described in Example 5 using a 20 w / w% polymer concentration solution in DMAc. The polymer samples used were a blend of TMBBF-EO copolymer sample E7 [prepared from 6 mol% DCEO relative to the total moles of all monomers] and also TMBBF-EO copolymer samples E5 and E8 [both prepared from 12.5 mol% DCEO relative to the total moles of all monomers].

[0557] Table 15

[0558]

[0559] The dense films (Table 15) made from the TMBPF-EO copolymer in Test Nos. X and Y exhibited higher hydrophilicity than the dense films made from PES.

[0560] If the disclosures of any patents, patent applications, and publications incorporated by reference herein conflict with the description of the present application to the extent that the terms may become unclear, the description of the present invention shall control.

[0561] Accordingly, the scope of protection is not limited by the descriptions listed above, but only by the following claims. Each claim is incorporated into the specification as an example of the present invention. Accordingly, the claims are a further description and an addition to the preferred embodiments of the present invention.

[0562] Claims:

[0563]

[0564]

Claims

1. A poly(aryl ether sulfone) ("PAES") copolymer comprising a total of at least 80 mol.% of the repeating units (R AO ) and (R PAES ), where the mol.% is based on the total number of moles of repeating units in the copolymer, The repeating unit (R AO ) is selected from the group consisting of units having formula (M1), (M'1) and any combination thereof: The repeating unit (R PAES ) has the formula (N): Wherein · R in formulas (M1) and (M'1) 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently H or CH3; · Each of m and q is independently an integer of at least 2 and optionally at most 5, preferably equal to 2, provided that at least one R 1 is H and at least one R 6 is H; · Each of n and p is independently an integer of at least 1 and optionally at most 5, preferably equal to 1 or 2, provided that when n = 2, at least one R 2 or R 3 is H; and when p = 2, at least one R 4 or R 5 is H; and · r in formulae (M1) and (M'1) is 0, 1, 2 or 3; · Each R' in formula (N) is the same as or different from one another, and is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; · Each j' in formula (N) is the same as or different from one another, and independently is 0, 1, 2, 3 or 4, preferably j' = 1 or 0; · -E- in formulae (N), (M1) and (M'1) is represented by at least one of formulae (E1) to (E7): Wherein - T in formula (E7) is selected from the group consisting of: a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CCl3)2-, -C(=CCl2)-, -CH2-, -O-, -C(O)-, -C(CH3)(CH2CH2COOH)-, -S- and -SO-, preferably selected from a bond, -SO2- or -C(CH3)2-; and -Ar 3 and Ar 4 are the same as or different from each other, and each occurrence in formula (E7) is independently an aromatic moiety conforming to any one of the following formulas (J), (J') and (J''): ○ Each R in formulae (J), (J') and (J") is the same as or different from one another, and is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and ○ Each j in formulae (J), (J') and (J") is the same as or different from one another, and independently is 0, 1, 2, 3 or 4, preferably j = 1 or 0; and wherein the PAES copolymer comprises at least 4 mol%, or at least 5 mol%, or at least 6 mol%, or at least 8 mol%, or at least 10 mol%, or at least 12 mol% and up to 50 mol%, or up to 40 mol%, or up to 30 mol%, or up to 25 mol% of repeating unit (R EO ), said mol% being based on the combined molar number of repeating unit (R AO ) and (R PAES ).

2. The PAES copolymer according to claim 1, wherein, These repeating units (R PAES ) are represented by formula (N'): Wherein For each R', j' = 0 or 1, and when j' = 1, R' is selected from the group consisting of alkali metal sulfonate, alkaline earth metal sulfonate and alkyl sulfonate; and -E- is represented by a formula selected from at least one of formulae (E1) to (E6) and the following formulae (E7a), (E7b) and (E7c):

3. The PAES copolymer according to claim 1 or 2, wherein The alkylene oxide moiety of the repeating unit (R AO ) having the formula (M1) and / or (M'1) in the PAES copolymer represented by the following: Having at least 5 carbon atoms and at most 9 carbon atoms and / or at least 2 oxygen atoms and at most 4 oxygen atoms.

4. The PAES copolymer according to any one of claims 1 to 3, wherein The repeating unit (R AO ) comprises units selected from the group consisting of units having the formulae (M1a) to (M1i): Preferably selected from units having formulae (M1a), (M1b), (M1g), (M1h) and / or (M1i), more preferably selected from units having formulae (M1a), (M1g), (M1h) and / or (M1i).

5. The PAES copolymer according to any one of claims 1 to 4, which consists essentially of these repeating units (R AO ) and (R PAES ).

6. The PAES copolymer according to any one of claims 1 to 5, which has an Mw greater than 10,000 kDa, or at least 15,000 kDa, or at least 20,000 kDa, or at least 30,000 kDa and optionally up to 150,000 kDa, or up to 120,000 kDa, or up to 100,000 kDa, and the Mw is measured by GPC using dichloromethane as the mobile phase and using polystyrene standards for calibration.

7. The PAES copolymer according to any one of claims 1 to 6, which is a random copolymer.

8. A method for preparing a polyarylether sulfone ("PAES") copolymer, the method comprising Reacting a monomer mixture in a reaction mixture comprising an aprotic polar solvent and in the presence of an alkali metal carbonate, the monomer mixture containing: - at least one dihaloepoxyalkane compound [hereinafter dihalo(AO) monomer], selected from the group consisting of compounds having formula (I): - at least one dihaloarylsulfone compound having formula (V) [hereinafter dihalo(AS) monomer]: X-Ar 1 -SO2-Ar 2 -X’(V); - at least one dihydroxy compound [hereinafter dihydroxy(B) monomer], selected from the group consisting of: ○ tetramethylbisphenol F, ○ at least one 1,4:3,6-dianhydrohexitol, selected from the group consisting of isosorbide (1,6-dianhydro-D-sorbitol), isomannitol (1,6-dianhydro-D-mannitol) and isoidide (1,6-dianhydro-D-iditol), ○ at least one alicyclic diol, selected from the group consisting of: 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane dimethanol, adamantane diol, pentacyclopentadecane dimethanol, 1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol ("CBDO"), ○ An aromatic diol having the formula (VI): HO-Ar 3 -T-Ar 4 -OH (VI), and ○ any combination thereof, wherein: - X1 and X2 in formula (I) are the same or different from each other and are independently a halogen atom, preferably Cl, Br or F, more preferably Cl; - R in formula (I) 1 、R 2 、R 3 、R 4 、R 5 and R 6 each independently is H or CH3; - In formula (I), each of m and q is independently an integer of at least 2 and optionally at most 5, preferably equal to 2, provided that at least one R 1 is H and at least one R 6 is H; - In formula (I), each of n and p is independently an integer of at least 1 and optionally at most 5, preferably equal to 1 or 2, provided that when n = 2, R 2 and R 3 at least one of which is H; and when p = 2, R 4 and R 5 at least one of which is H; - r in formula (I) is 0, 1, 2 or 3; - Ar in formula (V) 1 and Ar 2 are the same as or different from each other, and Ar in formula (VI) 3 and Ar 4 are the same as or different from each other and independently are an aromatic moiety conforming to any one of the following formulas (J), (J') and (J''): ○ wherein each R is the same or different from each other and is selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and ○ wherein each j is the same or different from each other and is independently 0, 1, 2, 3 or 4, preferably j = 1 or 0, - X and X' in formula (V) are the same or different from each other and are independently a halogen atom, preferably Cl, Br or F, more preferably Cl; - T in formula (VI) is selected from the group consisting of: a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CCl3)2-, -C(=CCl2)-, -CH2-, -O-, -C(O)-, -C(CH3)(CH2CH2COOH)-, -S- and -SO-, preferably selected from a bond, -SO2- and / or -C(CH3)2-; and wherein - the monomer mixture contains at least 4 mol.%, or at least 5 mol.%, or at least 6 mol.%, or at least 8 mol.%, or at least 10 mol.% and up to 50 mol.%, or at most 30 mol.%, or at most 25 mol.% of the dihalo(AO) monomer, said mol.% being based on the combined molar amount of the dihalo(AO) and (AS) monomers; - the total amount of the halogen groups and the hydroxyl groups of these monomers in the monomer mixture is substantially equimolar; and - When expressed as the ratio of the equivalents of the alkali metal (M) / the equivalents of the hydroxyl groups (OH) in the dihydroxy (B) monomer [eq.(M) / eq.(OH)], the amount of the alkali metal carbonate used in the reaction mixture is greater than 1, preferably at least 1.05 and optionally up to 2.

9. The method according to claim 8, wherein, The dihalo (AO) monomer has a total of 5 to 9 carbon atoms and / or has a total of 1 to 4 oxygen atoms.

10. The method according to claim 8 or 9, wherein The monomer mixture comprises at least one dihalo (AO) monomer represented by any one of the formulas (Ia) to (Ii): Cl-CH2-CH2-O-CH2-CH2-O-CH2-CH2-Cl (Ia) Cl-CH2-CH2-O-CH2-O-CH2-CH2-Cl (Ib) Cl-CH2-CH2-O-CH(CH3)-O-CH2-CH2-Cl (Ic) Cl-CH2-CH2-O-CH2-O-CH2-O-CH2-CH2-Cl (Id) Cl-CH(CH3)-CH2-O-CH2-O-CH2-CH2-Cl (Ie) Cl-CH2-CH2-O-CH2-O-CH2-O-CH2-O-CH2-CH2-Cl (If) Cl-CH(CH3)-CH2-O-CH2-CH(CH3)-O-CH2-CH(CH3)-Cl (Ig) Cl-CH(CH3)-CH2-O-CH2-CH2-O-CH2-CH(CH3)-Cl (Ih) Cl-CH2-CH2-O-CH(CH3)-CH2-O-CH2-CH2-Cl (Ii), preferably represented by any one of these formulas (Ia), (Ib), (Ig), (Ih) and / or (Ii), more preferably represented by any one of these formulas (Ia), (Ig), (Ih) and / or (Ii).

11. The method according to any one of claims 8 to 10, wherein, The monomer mixture comprises 4,4'-dichlorodiphenylsulfone (DCDPS) and / or any sulfonated derivative of DCDPS as at least one dihalo (AS) monomer.

12. The method according to any one of claims 8 to 11, wherein The monomer mixture comprises at least one dihydroxy (B) monomer selected from the group consisting of: and any combination thereof.

13. The method according to any one of claims 8 to 12, wherein The monomer mixture comprises - tetramethylbisphenol F, as at least one dihydroxy (B) monomer, and - optionally at least one other dihydroxy (B) monomer selected from the group consisting of: bisphenol A, bisphenol S, 4,4'-biphenol, isosorbide and any combination thereof.

14. The method according to any one of claims 8 to 13, wherein The monomer mixture contains 10 mol.% to 25 mol.% of the dihalo (AO) monomer based on the combined molar amounts of the dihydroxy monomer (B) and these dihalo (AO) and (AS) monomers.

15. The method according to any one of claims 8 to 14, wherein The polar aprotic solvent in the reaction medium is selected from the group consisting of: 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (also known as sulfolane), N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N′-dimethylacetamide (DMAc), N,N′-dimethylpropyleneurea (DMPU), dimethylformamide (DMF), tetrahydrothiophene-1-oxide and any combination thereof; preferably selected from the group consisting of: sulfolane, DMSO, DMAc, DMI, NMP and any combination thereof; more preferably selected from the group consisting of: sulfolane, DMSO, DMAc, NMP and any combination thereof.

16. The method according to any one of claims 8 to 15, wherein, The reaction mixture further comprises a cosolvent that forms an azeotrope with water.

17. The method according to any one of claims 8 to 16, wherein The alkali metal carbonate includes potassium carbonate or sodium carbonate, preferably potassium carbonate. Use of a PAES copolymer according to any one of claims 1 to 7 or obtained by a method according to any one of claims 8 to 17 for the preparation of non-porous articles such as films, which comprises casting of a polymer solution or polymer melt processing such as extrusion casting, wherein the PAES copolymer is the sole polymer in the non-porous article, or wherein the non-porous article further comprises at least one other polymer. Use of a PAES copolymer according to any one of claims 1 to 7 or obtained by a method according to any one of claims 8 to 16 for the preparation of porous articles such as porous films, hollow fibers, hollow tubes or porous membranes using a phase inversion technique selected from non-solvent induced phase separation or thermally induced phase separation, the use comprising: casting or spinning a polymer dope solution comprising the PAES copolymer, a solvent, optionally a cosolvent and optionally at least one pore former such as PVP and PEG into the porous article and then cooling it or contacting it with a non-solvent, wherein the PAES copolymer is the sole polymer in the dope solution, or wherein the dope solution further comprises at least one other polymer preferably selected from the group consisting of: PSU, sulfonated PSU, PPSU, sulfonated PPSU, PES, sulfonated PES, PVDF and any combination thereof. An article for use in solid state battery applications such as polymer electrolyte membranes and / or polymer or solid electrolytes, said article comprising a PAES copolymer according to any one of claims 1 to 7 or obtained by a method according to any one of claims 8 to 16.

21. An article, which is porous, preferably hollow fiber, hollow tube, porous film or porous membrane, for medical applications such as hemodialysis membrane and / or for aqueous media or water filtration such as reverse osmosis membrane, ultrafiltration membrane, microfiltration membrane, nanofiltration membrane and ion exchange membrane, the porous article comprising a PAES copolymer according to any one of claims 1 to 7 or obtained by the method according to any one of claims 8 to 16.

22. The article according to claim 21, which is a hemodialysis membrane, wherein the PAES copolymer is the only polymer in the hemodialysis membrane, or wherein the hemodialysis membrane further comprises at least one other polymer preferably selected from the group consisting of PSU, sulfonated PSU, PPSU, sulfonated PPSU, PES, sulfonated PES, PDVF and any combination thereof.

23. The article according to any one of claims 20 to 22, wherein, The PAES copolymer is the only polymer in the article, or wherein the article further comprises at least one other polymer preferably selected from the group consisting of PSU, sulfonated PSU, PPSU, sulfonated PPSU, PES, sulfonated PES, PDVF and any combination thereof.

24. The article according to any one of claims 20 to 23, wherein, The article is a membrane comprising a support layer or a thin selective layer, and wherein at least one of the support layer and the thin selective layer contains or is made of the PAES copolymer.

25. A method for purifying a fluid, such as an aqueous solution (e.g., alkaline), water, a biological fluid (e.g., blood, plasma or serum) and / or a food product (e.g., juice, milk, beer), the method comprising at least a filtration step using a porous article such as a porous membrane, one or more hollow fibers, one or more hollow tubes or one or more porous membranes, the porous article comprising a PAES copolymer according to any one of claims 1 to 7 or obtained by a method according to any one of claims 8 to 16.

26. The method according to claim 25, wherein The fluid is blood and wherein the porous article is a hemodialysis membrane.

27. A method for improving the flexibility of a high Tg aromatic sulfone polymer material, the polymer material preferably having a Tg ≥ 180°C and preferably selected from the group consisting of polysulfone (PSU), polyphenylsulfone (PPSU), polyethersulfone (PES), copolymers thereof or blends thereof, This method comprises adding a PAES copolymer according to any one of claims 1 to 7 or obtained by the method according to any one of claims 8 to 16 to the high Tg bulk aromatic sulfone polymer to form a polymer blend, which is preferably used to form a porous article such as a porous membrane, a hollow fiber, a hollow tube or a porous film, and the porous article is used in filtration such as ultrafiltration, nanofiltration and microfiltration applications.

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