Functionalized poly(aryl ether sulfone) copolymer

Abstract

The invention relates to a functionalized polyarylethersulfone copolymer (Pf) and to processes for preparing the functionalized copolymer (Pf). The functionalized copolymer (Pf) is derived from an unsaturated copolymer (Pu) which serves as polymeric scaffold containing C=C bonds which are permitted to react with a functionalization compound to form functional moieties in the copolymer (Pf). The copolymer (Pu) is made by polycondensation of an unsaturated aliphatic diol, another diol and a dihalodiarylsulfone. The present invention also relates to the use of the copolymer (Pf) in the preparation of an article, and to an article, such as membrane or chromatography material, comprising or made from the copolymer (Pf).

Description

[0001] Functionalized poly(aryl ether sulfone) copolymer

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to U.S. application No. 63 / 708156 filed on October 16, 2024, the entire content of this application being incorporated herein by reference for all purposes.

[0004] TECHNICAL FIELD

[0005] The present invention pertains to a functionalized poly(aryl ether sulfone) copolymer (Pf) and to processes for manufacturing such a copolymer (Pf). The copolymer (Pf) comprises functional groups, and to the use of the copolymer (Pf) for preparing functional articles such as membranes, composite materials, 3D printing applications, and coatings. BACKGROUND

[0006] Poly(aryl ether sulfone) (PAES) polymers are a class of thermoplastic polymers characterized by high glass-transition temperatures, good mechanical strength and stiffness, and outstanding thermal and oxidative resistance. By virtue of their mechanical, thermal, and other desirable characteristics, these polymers are used increasingly making products for a wide and diversified range of commercial applications, for instance in coatings, in membranes for wide field of use including medical market, due to their excellent mechanical and thermal properties, coupled with outstanding hydrolytic stability. PAES is a generic term used to describe any polymer containing at least one sulfone group (-SO2-), at least one ether group (-O-) and at least one arylene group.

[0007] These PAES resins are made by polycondensation reactions typically using 4,4’- dichlorodiphenylsulfone (the sulfone monomer) along with at least one aromatic diol such as bisphenol A, 4-4’-biphenol or bisphenol S. These resins are good solubility in polar aprotic solvents such as N-Methyl-2-pyrrolidone (NMP), N,N'-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), and hence are extensively used to make hollow fiber or flat sheet membranes mainly for filtration and also for blood purification (hemodialysis) processes along with separating complex biological mixtures such as proteins, enzymes, amino acids etc.

[0008] They are also used for water filtration and other food contact applications.

[0009] However due to the chemistry used in order to make them, these materials are essentially devoid of any reactive functional groups and also have an inherent hydrophobic nature.

[0010] In order to address the above issues, WO 2020 / 187684A1 , WO 2023 / 118302A1 , and WO 2023 / 139134A1 by Solvay Specialty Polymers USA (SYENSQO) describe a sidechain functionalizable PAES which had side-chain olefinic groups. These side-chain olefinic groups can be functionalized via a variety of chemical transformations such as hydrothiolation, grafting, hydrohalogenation - see for example WO 2022 / 171683A1 , EP3235854A1 by Solvay Specialty Polymers USA (SYENSQO). While the side-chain functionalizable PAES described in these patent references contain reactive ally l / viny I side chains, their manufacture uses two aromatic bisphenol monomers: BPA, BPS or BP with an olefinic bisphenol such as daBPA (2,2’-diallyl bisphenol A) or daBPS (2,2’-diallyl bisphenol S) as co-diol.

[0011] BPA and BPS are industrial chemicals that have been present in many articles, including plastic bottles and food and beverage cans since the 1960s. However in recent years, concerns have been raised about BPA and BPS's safety in many articles, including plastic bottles and food and beverage cans. BPS and BPA are suspected to be endocrine disruptive in nature, albeit without conclusive research, and their impact on the environment and human health is still under investigation. In view of this controversy, the market is looking for economically viable alternatives to BPA and BPS.

[0012] Because polymeric materials in contact with food and drugs must meet certain requirements mandated by for instance the FDA, the European Food Safety Agency and the Environmental Protection Agency (EPA) and due to the recent concerns regarding the potential endocrine disruption of some bisphenols, developing polymeric materials that are safe both for humans and environment for applications requiring contact with water, food, drugs and / or blood remains important.

[0013] Hence there is an urgent need to identify non-bisphenolic and / or allyl co-monomers which are endocrine safe, or at least which have a reduced endocrine disrupting activity compared to BPA, to make a functionalizable PAES containing olefinic groups universal polymer backbone with the use of dihalodiaryl sulfone monomer and at least one endocrine-safe diol monomer such as 4,4’-biphenol and / or isosorbide.

[0014] The present invention provides a functionalized copolymer and processes for preparing such a copolymer. These functionalized copolymers are complex polymer architectures useful in many different applications, notably to prepare functionalized membranes, composite materials and coatings.

[0015] SUMMARY

[0016] The present invention relates to a functionalized poly(aryl ether sulfones) (PAES) copolymer (Pf) which comprises poly(aryl ether sulfones) (PAES) recurring units (Rpf), as well as functionalized PAES recurring units (R*pf) having functional groups.

[0017] A parent unsaturated poly(aryl ether sulfones) (PAES) copolymer (Pu) comprising reactive allyl groups (or unsaturated groups) in its main polymeric chain and / or side chains is used as a polymeric scaffold to permit functionalization of the copolymer by reaction of at least some of the reactive allyl groups (or unsaturated groups) of the copolymer (Pu) with a functional compound.

[0018] Some functional groups such as amine groups in a functionalized copolymer (Pf) may be further reacted with another functional compound to obtain another functionalized copolymer (Pf).

[0019] The various aspects of the present invention are set out in the appended set of claims.

[0020] A first aspect of the invention relates to a functionalized polyarylethersulfone copolymer (Pf) defined in any one of claims 1-9.

[0021] A second aspect of the invention relates to a process defined in any one of claims 10-15 for manufacturing the functionalized copolymer (Pf).

[0022] A third aspect of the invention relates to the use defined in claim 16 of the copolymer (Pu) as a copolymeric scaffold comprising reactive allyl groups (or unsaturated groups) in its main polymeric chain and / or side chains to permit functionalization of the copolymeric scaffold by reaction of at least some of the reactive allyl groups (or unsaturated groups) of the copolymer (Pu) to attach these functional groups

[0023] More precisions and details about various embodiments, advantages, and features of the invention will be more readily understood and appreciated by reference to the detailed description and examples.

[0024] DETAILED DESCRIPTION

[0025] Definitions

[0026] In the present descriptive specification, some terms are intended to have the following meanings.

[0027] As used herein, the terminology “dihydroxy aliphatic allyl monomer (AA”)” may be simplified as “dihydroxy monomer (AA”)”.

[0028] The term “aliphatic” means, for the purpose of the present invention, non-aromatic, and an aliphatic monomer or moiety may be linear, branched, or cyclic.

[0029] The term “alicyclic” defines a structure that is both aliphatic and cyclic. An alicyclic structure (such as a diol or moiety) may contain one or more non-aromatic rings. An alicyclic structure may be unsaturated or saturated.

[0030] The terms "cycloaliphatic moiety" or "alicyclic moiety" are interchangeable and are intended to denote any moiety being both aliphatic (i.e., not aromatic) and cyclic (i.e., where atoms are connected in a ring). A cycloaliphatic moiety may be either unsubstituted or substituted. A cycloaliphatic moiety may be heterocyclic. When the cycloaliphatic moiety does not comprise any heteroatoms in the ring, the backbone of the cycle of the cycloaliphatic moiety is made only of interconnected carbon atoms. Similarly, the term “cyclic aliphatic diol” and “alicyclic diol” can be used interchangeably. In addition to the oxygen atoms of the two hydroxyl groups, an alicyclic diol may be heterocyclic, in that at least one ring comprises one or more heteroatoms.

[0031] The term “heteroatom” means a non-carbon atom, for example an atom of oxygen, nitrogen, and / or sulfur.

[0032] The term “acyclic” defines a structure which does not have any ring. The acyclic diol or moiety or group is preferably saturated. Linear aliphatic diols and branched aliphatic diols are acyclic diols. In addition to the oxygen atoms in the hydroxyl groups, the acyclic diol may comprise one or more heteroatoms (i.e. , non-carbon atoms, for example atoms of oxygen, nitrogen and / or sulfur) connected to at least one carbon atom, or may have a backbone made only of connected carbon atoms.

[0033] An allyl aliphatic monomer or moiety is unsaturated.

[0034] The term “aromatic” defines a structure (such as a diol or moiety) which contains at least one aromatic ring.

[0035] For the purpose of the present invention, the term “dihydroxy monomer” and “diol” can be used interchangeably. As used herein, the term “dihydroxy monomer” or “diol” refers to a monomer comprising at least two hydroxyl groups, preferably 2 or 3 hydroxyl groups, more preferably 2 hydroxyl groups.

[0036] The term “recurring unit” designates the smallest unit of a polyarylethersulfone which is repeating in the main chain, and which is composed of a condensation of a diol monomer and a dihalodiary I sulfone monomer.

[0037] The term “homopolymer” encompasses a polymer which only has one type of recurring unit. Meaning, a polyarylethersulfone homopolymer is obtained from the condensation of only one diol monomer and only one di halodiary I sulfone monomer.

[0038] The term “copolymer” encompasses a polymer which may have two or more different types of recurring units. The copolymer (Pu) may be obtained from polycondensation of at least two dihydroxy monomers and at least one dihalodiary I sulfone monomer.

[0039] “BPA” means Bisphenol A or 4,4'-isopropylidenediphenol; “BPS” or “DHDPS” means Bisphenol S or 4,4’-dihydroxydiphenyl sulfone; “BP” means 4,4’-biphenol; “TMPAE” means trimethylolpropane allyl ether; “DHB” refers to dihydroxy-butene; and “TMBPF” means tetramethyl Bisphenol F.

[0040] An endocrine-safe monomer means that such a monomer has an estrogenic activity which is less, preferably 50% less, 60% less, 70% less, 80% less, 90% less, or 95% less, than the estrogenic activity of Bisphenol A. BPA as well as most of its derivatives are recognized as endocrine disruptors. Indeed BPA has been found to bind to estrogen receptor (ER) isoforms: ERa and ERp and have estrogenic effects in laboratory studies.

[0041] The article by Rochester J (2013) Reproductive Toxicology vol. 42, pp. 132- 155 summarizes the health effects of BPA. Rochester JR, Bolden AL (2015) Environ. Health. Perspect. Vol 123, pp. 643-650 also evaluated the physiological effects and endocrine activities as well as the hormonal potency of the BPA substitutes: BPS and BPF by reviewing a plurality of studies and concluded that BPS and BPF are as hormonally active as BPA, and they have endocrine-disrupting effects. Their respective human health effects are summarized in this article. For the purpose of the present invention, the estrogenic activity of a monomer (e.g., diol) may be measured by receptor binding affinity for ERp. Receptor binding affinity for ERp is preferably evaluated by competitive binding assay using [3H] 17p-estradiol as a radioligand. According to Iwamoto M et al. (2021) Journal of Biological Chemistry, Vol. 297, Issue 5, 101173, Bisphenol A has a binding affinity (IC50) for ERp of 900 + / - 70 nM measured by competitive binding assay.

[0042] The terminology “Cj-Ck” or “Cj-Ck” in reference to an organic group (e.g., diol, monomer, alkene, moiety, ...) wherein i and k are integers, means that the organic group may contain from ‘j’ carbon atoms to ‘k’ carbon atoms per organic group.

[0043] The terminology “Cz+” or “Cz+” in reference to an organic group (e.g., diol, monomer, alkene, moiety ...) wherein z is an integer means that the organic group contains at least ‘z’ carbon atoms per organic group.

[0044] The term “bioactive” in relation to a compound or structure is intended to mean that such compound or structure has a biological activity. A “bioactive” compound may present a therapeutic potential; may elicit pharmacological effects; may modulate metabolic processes; may have beneficial physiological, behavioral, or immunological effects; may have anti-oxidant, anti-carcinogenic, anti-inflammatory, anti-thrombotic or anti-microbial properties; may elicit inhibition of receptor activities; may elicit inhibition or induction of enzymes such as protease inhibitor; may elicit induction and inhibition of gene expression; may have metal-chelating properties; may act as an adsorbent to remove specific compound(s) from a fluid; or may have a catalytic activity in the body. As an example, a bioactive carbonyl compound, which bears a carbonyl group, may be involved in reactions during food production processes, owing to their functional carbonyl group. As another example, heparin-modified membrane as a bioactive structure can prevent coagulation in the blood and / or on the surface of the membrane and / or may be useful in removing low-density lipoprotein (LDL cholesterol) from blood.

[0045] As used herein, heparin is a highly sulfated glycosaminoglycan and consists of variably sulfated repeating disaccharide units. This polysaccharide typically has a MW of 3- 30 kDa with an average of about 12-15 kDa, although a fractionated version of heparin also exists in a low-MW form (e.g., MW of about 3-7 kDa) such as dalteparin, enoxaparin. Without wishing to be bound by such theory, heparin is said to exert its anticoagulant activity by activating antithrombin. A derivative of heparin may be a salt form, such as sodium salt of heparin.

[0046] The term “biological medium” may be fermentation medium, cell culture, protein lysate, bacteria-containing fluid, virus-containing fluid, DNA-containing fluid (such as containing plasmid, DNA primer, or DNA fragment), RNA-containing fluid (such as containing mRNA or tRNA), antibody-containing fluid (e.g., containing monoclonal antibodies, polyclonal antibodies, or antibody fragments, wherein the antibody may be IgA, IgG or IgM immunoglobulin), vaccine-containing fluid, hormone-containing fluid, enzymecontaining fluid, or any combination thereof. A DNA primer is a short nucleic acid sequence that provides a starting point for DNA synthesis. A plasmid is a small circular DNA molecule within a cell (such as bacteria) that is physically separated from chromosomal DNA and can replicate independently.

[0047] As used herein, the term “body fluid” generally represents whole blood or blood products such as plasma or serum.

[0048] As used herein, the term “food product” generally represents a beverage, particularly fruit juices, milk, beer, wine, etc

[0049] The use of parentheses "( )" before and after names, symbols or numbers identifying formulae or parts of formulae, e.g., copolymer (Pf), recurring unit (Rpf), recurring unit (R*pf), formula (P), etc..., has the mere purpose of better distinguishing that name, symbol or number from the rest of the text; thus, said parentheses could also be omitted.

[0050] The symbol in a chemical structure represents a part at which the moieties Ea and Eb are connected to a carbon atom in the aliphatic moiety E of recurring unit (R*pf) of formula (N).

[0051] The symbol also represents a part at which the unsaturated moieties E’a and E’b are connected to a carbon atom in the unsaturated aliphatic moiety E’ of recurring unit (R*PU) of formula (P).

[0052] The symbol "**" in a chemical structure represents a part at which a group R is connected to the sulfur atom in the moieties Ea and Eb. The symbol "**" also represents a part at which a group R is connected to the sulfur atom in the compound of formula (J) : HS-R.

[0053] As used herein, the expression “substantially all” in relation to an amount of an element is hereby intended to mean that minor amounts (e.g., < 1 mol%, preferably < 0.5 mol%, or < 1 wt.%, preferably < 0.5 wt.%) of other elements) may be tolerated.

[0054] In the present specification, the choice of an element from a group of elements (such as a Markush group) also explicitly describes:

[0055] - the choice of two or the choice of several elements from the group, and

[0056] - the choice of an element from a subgroup of elements consisting of the group of elements from which one or more elements have been removed.

[0057] Where an element is selected from a list of elements, it should be understood that in related embodiments explicitly contemplated here, a single element may be selected as any one of the individual elements in the list, or may be selected from a group consisting of any two or more of the explicitly listed elements. Any element recited in the list may be omitted from such a list.

[0058] In the passages of the present specification which will follow, any description, even though described in relation to a specific embodiment or aspect of the invention, is applicable to and interchangeable with other embodiments or aspects of the present disclosure. Each embodiment thus defined may be combined with another embodiment, unless otherwise indicated or clearly incompatible. In addition, it should be understood that the features and / or the characteristics of a copolymer, a reaction medium, a composition, a solution, a product or article, a method, a process or a use, described in the present specification, may be combined in all possible ways with the other features and / or characteristics of the copolymer, reaction medium, composition, solution, product or article, method, process or use, explicitly or implicitly, this being done without departing from the scope of the present description.

[0059] In the present specification, the description of a range of values for a variable, defined by a bottom limit, or by a top limit, or by a bottom limit and a top limit, also comprises the embodiments where the variable is chosen, respectively, within the range of values: excluding the bottom limit, or excluding the top limit, or excluding the bottom limit and the top limit. Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents.

[0060] The term "comprising" (or “comprise”) includes "consisting essentially of (or “consist essentially of) and also "consisting of (or “consist of).

[0061] The term “consisting essentially of in relation to a polymer, composition, product, polymer, solution, process, method, etc. is intended to mean that any additional element or feature which may not be explicitly described herein and which does not materially affect the basic and novel characteristics of such a polymer, composition, product, polymer, solution, process, method, etc. can be included in such an embodiment. In the particular context of the copolymer (Pf), the expression ‘consisting essentially of is used for defining constituents of the copolymer (Pf) to take into account end chains, defects, irregularities and monomer rearrangements which might be comprised in said copolymer (Pf) in minor amounts, without this modifying essential properties of the copolymer (Pf).

[0062] The use of the singular ‘a’ or ‘one’ herein includes “at least one” and also the plural “more than one”, unless specifically stated otherwise. The disclosure of all patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein. Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0063] Description of the invention and its preferred embodiments

[0064] The inventor has surprisingly found that certain aliphatic allyl monomers which have low or no endocrine disruption potential, some of which originate from bio-based compounds, can be used to successfully prepare, using an inorganic base in a polar aprotic solvent, an unsaturated copolymer (Pu) containing C=C moieties present in the main polymeric chain and / or on side chains and which presents appropriate set of characteristics and properties. This unsaturated copolymer (Pu) serves as polymeric scaffold to attach functional groups by reaction with these C=C moieties to form the functionalized copolymer (Pf) according to the invention.

[0065] Such a copolymer (Pu) and consequently such a functionalized copolymer (Pf) provide an improvement over previous polyarylethersulfone (PAES) polymers made from condensation of dichlorodiphenylsulfone with only bisphenolic monomers having high endocrine safety risk.

[0066] Functionalized copolymer (Pf)

[0067] The functionalized copolymer (Pf) according to the invention comprises collectively at least 60 mol%, or at least 70 mol.%, or at least 80 mol.%, or at least 90 mol.%, or at least 95 mol.%, or at least 98 mol.%, or at least 99 mol.%, based on the total amount of moles of recurring units in the copolymer (Pf), of

[0068] - at least one recurring unit (Rpf) of formula (M):

[0069] [-Ar-SO2-Ar’-O-W-O-] (M),

[0070] - at least one functionalized recurring unit (R*pf) of formula (N):

[0071] [-Ar-SO2-Ar’-O-E-O-] (N), wherein

[0072] • Ar-SO2-Ar’ is a diaryl sulfone moiety derived from at least one dihalodiaryl sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group;

[0073] • W is a moiety derived from at least one diol (BB) being selected from the group consisting of aromatic diols, saturated alicyclic diols and saturated acyclic diols;

[0074] • E is a functionalized aliphatic moiety derived from at least one dihydroxy aliphatic allyl monomer (AA’), and • E comprises at least one functionalized end moiety Ea represented by following formula (Ea1) and / or formula (Ea2), at least one functionalized divalent moiety Eb represented by following formula (Eb1) and / or formula (Eb2), or combination thereof, the formulae (Ea1), (Ea2), (Eb1), (Eb2) being as follows: in which R is a functional group, and in which the symbol represents a part at which the moieties Ea and Eb are connected to a carbon atom in the aliphatic moiety E of recurring unit (R*pf) of formula (N).

[0075] The recurring units of the copolymer (Pf) preferably consist essentially of recurring units (Rpf), recurring units (R*pf) and optionally recurring units (R*pu), said recurring units (R*pu) being defined in relation to unsaturated copolymer (Pu) described later.

[0076] The functionalized copolymer (Pf) may particularly collectively at least 60 mol.%, or at least 70 mol.%, or at least 80 mol.%, or at least 90 mol.%, or at least 95 mol.%, or at least 98 mol.%, based on the total amount of moles of recurring units in the functionalized copolymer (Pf), of :

[0077] -a combination of functionalized recurring unit (R*pf) of formula (N) and recurring unit (R’pf) of formula (M’);

[0078] - a combination of functionalized recurring unit (R*pf) of formula (N) and recurring unit (R”pf) of formula (M”);

[0079] - a combination of functionalized recurring unit (R*pf) of formula (N) and recurring unit (R”’Pf) of formula (M’”);

[0080] - a combination of functionalized recurring unit (R*pf) of formula (N), recurring unit (R’pf) of formula (M’) and recurring unit (R”pf) of formula (M”);

[0081] - a combination of functionalized recurring unit (R*pf) of formula (N), recurring unit (R’pf) of formula (M’) and recurring unit (R”’pf) of formula (M’”); or

[0082] - a combination of functionalized recurring unit (R*pf) of formula (N), recurring unit (R”pf) of formula (M”) and recurring unit (R”’pf) of formula (M’”); wherein the formula (N) and its functionalized aliphatic moiety E are the same as previously described; wherein the formulae (M’), (M”) and (M’”) are as follows :

[0083] [-Ar-SO2-Ar’-O-W’-O-] (M’),

[0084] [-Ar-SO2-Ar’-O-W”-O-] (M”),

[0085] [-Ar-SO2-Ar’-O-W”’-O-] (M’”), wherein • Ar-SO2-Ar’ is a diaryl sulfone moiety derived from at least one dihalodiaryl sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group;

[0086] • W’ is an aromatic moiety derived from at least one aromatic diol (BB’);

[0087] • W” is a cycloaliphatic moiety derived from at least one saturated alicyclic diol (BB”); and

[0088] • W’” is an acyclic moiety derived from at least one saturated acyclic diol (BB’”).

[0089] The recurring units (R*pf) and (Rpf) in the ffunctionalized copolymer (Pf) are such that the molar ratio r1 of the functionalized recurring units (R*pf) to the recurring units (Rpf) is:

[0090] • at most 45:55, preferably at most 40:60, more preferably at most 35:65, still more preferably at most 30:70, and

[0091] • at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88.

[0092] Functional group R in moieties Ea and Eb

[0093] The functional group R is connected to a sulfur atom S in moieties Ea and Eb.

[0094] The functional group R in any of the formulae (Ea1), (Ea2), (Eb1), (Eb2) may be selected from the group consisting of:

[0095] • group R110 represented by formula (110) : **- (CH2)a - COCH3 with a being an integer from 0 to 10,

[0096] • group R120 represented by formula (120) : **- C(O)Rmwith Rmbeing a C1-C6 alkyl or H, preferably H,

[0097] • group R130 represented by formula (130) : **- (CH2)b - OH with b being an integer from 1 to 5,

[0098] • group R140 represented by formula (140) : **- (CH2)d - SOs- M+with d being an integer from 1 to 5, and with M+being H+or an alkali metal cation, preferably H+, Na+, K+or Li+,

[0099] • group R150 represented by formula (150) : **- (CH2)e - Si (OCH3)3 with e being an integer from 1 to 5,

[0100] • group R160 represented by formula (160) : **- (CH2)f - (CF2)g - CF3 with f being an integer from 1 to 5 and with g being an integer from 1 to 10,

[0101] • group R170 represented by formula (170) : (CH2)h - COOH with h being an integer from 1 to 5,

[0102] • group R180 represented by formula (180) :: **- (CH2)k- CH3 with k being an integer from 5 to 30,

[0103] • group R190 represented by formula (190) : **- (CH2)I - Ar1with I being an integer from 1 to 10 and with Ar1comprising one or two aromatic or heteroaromatic rings; and • group R200 represented by formula (200) : **- (CH2)h - NRaRb with h being an integer from 1 to 5, and with Raand Rb being independently H or a C1- C6 alkyl, preferably being independently H or CH3; in which the symbol represents a part at which each group R is connected to the sulfur atom in the moieties Ea and Eb.

[0104] The functional group R in any of the formulae (Ea1), (Ea2), (Eb1), (Eb2) preferably is selected from the group consisting of:

[0105] **- (CH2)2- COCH3,

[0106] **- C(O)H,

[0107] **- (CH2)2- OH,

[0108] **- (CH2)3- SO3Na,

[0109] **- (CH2)3- Si (OCH3)3,

[0110] **- (CH2)2- (CF2)7 - CF3,

[0111] **- CH2- COOH,

[0112] **- (CH2)9 - CH3,

[0113] **- CH2 - Ph, with Ph being benzyl group,

[0114] **- (CH2)2 - N(CH3)2 ; and

[0115] **- (CH2)2- NH2; in which the symbol represents a part at which each group R is connected to the sulfur atom in the moieties Ea and Eb.

[0116] The functional group R in any of the formulae (Ea1), (Ea2), (Eb1), (Eb2) may be selected from the group consisting of:

[0117] • group R210 of formula (210): **- (CH2)h - NRaB, with h being an integer from 1 to 5, with Rabeing H or a C1-C6 alkyl, preferably H or CH3, and in which the symbol "**" represents a part at which each group R210 is connected to the sulfur atom in the moieties Ea and Eb, with B representing a bioactive moiety which is covalently and / or ionically bound to the nitrogen atom in R and

[0118] B being derived from a compound B* selected from the group consisting of:

[0119] - antithrombotic agents or derivatives thereof, such as heparin,

[0120] - amino acids, such as proteinogenic (native) amino acids which are naturally encoded in the genome of organisms and / or non-proteinogenic amino acids including unnatural amino acids synthetically prepared from their native analogs via modifications such as amine alkylation, side chain substitution, structural bond extension cyclization, and isosteric replacements within the amino acid backbone; - nucleic acids (polymers made up of nucleotides), such as oligonucleotides (with typically 12-25 base pairs), RNAs (e.g., tRNA, mRNA, pre-mRNA, small nuclear RNA (snRNA), microRNA (miRNA), and small interfering RNA (siRNA)), DNA (e.g., singlestranded DNA, double-stranded DNA),

[0121] - glucuronic acid, glucuronic acid derivatives or glucuronic acid residues,

[0122] - hyaluronic acid or hyaluronic acid derivatives or hyaluronic acid residues,

[0123] - proteins, such as collagen, keratin, small peptides (generally therapeutic proteins that have less than 100 amino acids), enzymes, such as, but not limited to, lactase; glucanohydrolases (e.g., alpha-amylase and isoamylase); pectinases for pectin hydrolysis; enzymes for high-fructose corn syrup production; enzymes for debittering of fruit juices (e.g., for removing naringin (responsible for immediate bitterness) and / or limonin (responsible for "delayed bitterness"); esterases; lipases; acylases; enzymes that facilitate acidolysis reactions, ester synthesis or ester interchange reactions, transesterification reactions; enzymes having phospholipase or protease activity (such as pepsin);

[0124] - metal-chelating and / or protease inhibitor agents (such as ethylene glycol tetraacetic acid (EGTA) and ethylene diamine tetraacetic acid (EDTA));

[0125] - acidic lipids (such as prostaglandins), and

[0126] - any combination of two or more compounds B*;

[0127] • group R220 represented by formula (220): with h being an integer from 1 to 5, with Ra, Rb being independently H or a C1-C6 alkyl, preferably H or CH3, with Rs being independently a C1-C6 alkyl, preferably CH3, and X being a halide;

[0128] • group R230 represented by formula (230): with h being an integer from 1 to 5, with Ra, Rb being independently H or a C1-C6 alkyl, preferably H or CH3, and with Rvbeing a group of formula (CH2)x with x being 3 or 4; • group R240 represented by formula (240) : ** - (CH2)h - NRaZ with h being an integer from 1 to 5, and with Rabeing H or a C1-C6 alkyl, preferably H or CH3, in which Z is covalently and / or ionically bound to the nitrogen atom in the group R240 and is selected from the group consisting of o an alkyl carbonyl moiety Z3; o a carboxylic acid moiety Z4; o an aromatic sulfonate moiety Z5 ; o a sugar acid moiety Z6; o a zwitterionic moiety Z7; o a haloalky I carbonyl moiety Z8; o a hydroxyl moiety Z9; o a combination of an olefinic moiety with another moiety selected from moieties Z3 to Z9, such as a combination of an olefinic moiety and a carboxylic acid moiety Z4; and o any combination of two or more moieties Z3 to Z9 thereof; and

[0129] • any combination thereof.

[0130] The functional group R selected from groups R210, R220, R230, R240, is preferably formed by subsequent functionalization (2ndfunctionalization) of group R200 represented by formula (200) : **- (CH2)h - NRaRb with another functional compound to attach a new functional group to the nitrogen atom of group R200.

[0131] Functionalized recurring units (R*pf) of copolymer (Pf)

[0132] The functionalized recurring unit (R*pf) is of general formula (N):

[0133] [-Ar-SO2-Ar’-O-E-O-] (N), wherein

[0134] • Ar-SO2-Ar’ is a diaryl sulfone moiety derived from at least one dihalodiaryl sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group;

[0135] • E is a functionalized aliphatic moiety derived from at least one dihydroxy aliphatic allyl monomer (AA’), and

[0136] • E comprises at least one functionalized end moiety Ea represented by the formula (Ea1) and / or formula (Ea2), at least one functionalized divalent moiety Eb represented by the formula (Eb1) and / or formula (Eb2), or combination thereof, the formulae (Ea1), (Ea2), (Eb1), (Eb2) being as previously described: *— CHS(R) — CH2 — * (Eb2) in which R is a functional group, and in which the symbol represents a part at which the moieties Ea and Eb are connected to a carbon atom in the aliphatic moiety E of the recurring unit (R*pf) of formula (N).

[0137] The thio-ether bond -S-R contained in the functionalized recurring unit (R*pf) possesses several advantages. First, it is a stable non-hydrolysable linkage which is important for applications in membranes, especially for medical applications. Moreover, it is a highly biocompatible and bio-stable linkage and can therefore be used for hemodialysis applications; many biological active molecules contain a thio-ether moiety, e.g., biotin. Yet, this bond can be oxidized to form sulfoxide and sulfone linkages upon treatment with a suitable oxidizing agent like hydrogen peroxide. Further, thio-ethers can be easily alkylated with alkyl halides to form sulfonium salts; polymeric sulfonium salts can then be used for chemical transformations such as epoxidation. In addition, thio-ethers can be coordinated or bonded to heavy metals, therefore the copolymer of the present invention can act as polymeric ligand for metal removal.

[0138] The recurring units (R*pf) may be preferably represented by following formula (N1), formula (N2) and / or formula (N3),

[0139] (N3), in which • each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;

[0140] • each i is independently 0, 1 , 2, 3 or 4, preferably 0 or 1 , more preferably 0;

[0141] • the moieties Ea and Eb are previously described;;

[0142] • each of Ra, Rbis independently represented by -(CH2)a- , -CHRh-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)a- , -CHfCHs)-, -(CH2)a-CH(CH3)- or - CH(CH3)-CH2)a- , with a being 1 or 2;

[0143] • each of Rf, Rgis independently represented by -(CH2)a- , -(CHRh)p-

[0144] -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2 - with cz being 1 , 2 or 3, preferably 1 or 2;

[0145] • each of x1 , x2 is independently 0 or 1 , with the proviso that x1 +x2=1 or 2;

[0146] • each of y1 , y2 is independently 0 or 1 , with the proviso that y 1 +y2=1 or 2;

[0147] • each of z1 , z2 is independently 0 or 1 , with the proviso that z1 +z2=1 or 2;

[0148] • each Rcis independently represented by -(CH2)Z- or -(CH2)5-O-(CH2)E, with / being an integer from 1 to 6, with 5 being 0 , 1 or 2, with e being an integer from 1 to 6; preferably represented by -CH2- ,-(CH2)2- , -CH2-O-CH2-, -(CH2)2-O-(CH2)2-, -CH2-O-(CH2)2- or -(CH2)2-O-CH2-;

[0149] • each Rdis independently represented by a C1-C5 alkyl group, preferably -CH3 , -CH(CH3)2, -C(CH3)3, -C2H5 or -C3H7, more preferably -CH3, -C2H5 or -CH(CH3)2; and

[0150] • each Reis independently represented by -H, a C1-C5 alkyl group such as CH3, C2H5, C3H7, an alcohol group such as R1-OH, or an ether group -R1-O-R2 in which R1 is a C1-C6 alkylene and R2 is a C1-C5 alkyl group, preferably with R1 being -(CH2)a- , -(CHRh)p-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 3, preferably 1 or 2, with p being an integer from 1 to 3, preferably 1 or 2, with Rhbeing CH3 or C2H5, and with R2 being preferably being CH3 or C2H5.

[0151] The functionalized recurring units (R*pf) may more preferably be represented by following formula (N1 a) and / or formula (N1 b):

[0152] (N1 b).

[0153] The functional group R in formula (N1 a) and formula (N1 b) may be any group selected from groups R110, R120, R130, R140, R150, R160, R170, Riso, R190, R200, R210, R220, R230, and / or R240 described in the present application.

[0154] Recurring units (Rpf) of copolymer (Pf)

[0155] The recurring unit (Rpf) of the functionalized copolymer (Pf) is of general formula (M): [-Ar-SO2-Ar’-O-W-O-] (M), wherein

[0156] • Ar-SO2-Ar’ is a diaryl sulfone moiety derived from at least one dihalodiaryl sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group; and

[0157] • W is a moiety derived from at least one diol (BB) being selected from the group consisting of aromatic diols, saturated alicyclic diols and saturated acyclic diols.

[0158] The recurring unit (Rpf) of the functionalized copolymer (Pf) may be particularly represented by any of the following formulae (M’), (M”) and (M’”):

[0159] [-Ar-SO2-Ar’-O-W’-O-] (M’),

[0160] [-Ar-SO2-Ar’-O-W”-O-] (M”),

[0161] [-Ar-SO2-Ar’-O-W’”-O-] (M’”), wherein

[0162] • the moiety Ar-SO2-Ar’ is the same as defined for formula (M);

[0163] • W’ is an aromatic moiety derived from an aromatic diol (BB’);

[0164] • W” is a cycloaliphatic moiety derived from a saturated alicyclic diol (BB”); and

[0165] • W’” is an acyclic moiety derived from a saturated acyclic diol (BB’”).

[0166] When the recurring unit (Rpf) is represented by formula (M’) with an aromatic moiety W, the recurring unit (Rpf) may be represented by formula (M’*): wherein

[0167] • T is selected from the group consisting of a bond, -O-; -SO2-; -S-; -C(O)-; -C(CH3)2- C(CF3)2-; -C(=CCI2)-; -C(CH3)(CH2CH2COOH)-; -N=N-; -RaC=CRb-, where each Raand Rb, independently of one another, is a hydrogen, a C1-C12-alkyl group, a CICI 2-alkoxy group, or a C6-C18-aryl group; -(CH2)m- and -(CF2)m- with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and any combinations thereof; preferably each T being selected from the group consisting of a bond, -CH2-; -SO2-; and C(CH3)2-;

[0168] • each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and

[0169] • each i is independently 0, 1 , 2, 3 or 4, preferably i=0.

[0170] When the recurring unit (Rpf) of the functionalized copolymer (Pf) is represented by formula (M’) with an aromatic moiety W’, the recurring unit (Rpf) is preferably represented by any of following formulae (M’1), (M’2), (M’3), (M’4):

[0171] (M’4), wherein

[0172] • each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and

[0173] • each i is independently 0, 1 , 2, 3 or 4, preferably i=0.

[0174] When the recurring unit (Rpf) contains an aromatic moiety W’, the recurring unit (Rpf) is more preferably represented by formula (M’1) and / or (M’4), still more preferably represented by formula (M’1).

[0175] When i is not zero for at least one R’ in any of formulas (M’*), (M’1), (M’2), (M’3), (M’4), particularly i=1 , its corresponding R’ is preferably selected from the group consisting of alkali metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, and sulfonic acid (-SO3H).

[0176] Preferably in formulas (M’*), (M’1), (M’2), (M’3), (M’4), all i are 0, meaning that the phenyl rings are unsubstituted.

[0177] When the recurring unit (Rpf) of the functionalized copolymer (Pf) is represented by formula (M”) with an alicyclic moiety W”, the alicyclic moiety W” is preferably selected from following moieties (W”1) to (W”11): wherein each sign * in the formulae (W’1) to (W”11) denotes where W” is bonded to an oxygen atom of the -O-W”-O- moiety of formula (M”); and wherein each Q’, being the same or different in formula (W”11), is an acyclic moiety.

[0178] The acyclic moiety Q’ in formula (W”11) may be derived from an acyclic diol selected from alkylene glycols and / or poly(alkylene glycol)s, preferably selected from the group consisting of ethylene glycol; propylene glycol [HO-CH2-CH(CH3)-OH]; 1 ,3-propanediol; 1 ,4-butanediol; 1 ,5-pentanediol; 1 ,6-hexanediol; 1 ,8-octanediol; 1 ,10-decanediol; 2-methyl- 1 ,3-propanediol; 2,2-dimethylpropane-1 ,3-diol; 2,2,4-trimethyl-1 ,3-pentanediol; 2-ethyl-2- butyl-1 ,3-propanediol; poly(ethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.

[0179] Q’ in formula (W”11) may be represented by formula (VI): -[Rk-O-]z-Rk-, in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH2-CH2-CH2], 2,2- dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-1 ,3-propylene [CH2-C(C2H5)(C4Hg)- CH2], 2,2,4-trimethyl-1 ,3-pentylene [CH(C(CH3)2)-C(CH3)2-CH2], and any combination thereof; and z is 0 or an integer from 1 to 500, preferably an integer from 2 to 200, more preferably an integer from 2 to 100, yet more preferably an integer from 2 to 50.

[0180] Q’ in formula (W”11) is preferably represented by any one of following formulae (VI’),

[0181] (VI”), (VI’”) and (VI””):

[0182] -[CH2-CH2-O]Z-CH2-CH2- (VI ),

[0183] -[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (VI”),

[0184] -[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (VI ”),

[0185] -[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (VI ”), in which z is 0 or an integer from 1 to 500, preferably an integer from 2 to 200, more preferably an integer from 2 to 100, yet more preferably an integer from 2 to 50.

[0186] When the recurring unit (Rpf) of the functionalized copolymer (Pf) is represented by formula (M”) with an alicyclic moiety W”, the recurring unit (Rpf) may be represented by any of following formulae (M”1), (M”2), (M”3) and / or (M”4), more preferably represented by formula (M”1), , wherein

[0187] • each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and

[0188] • each i is independently 0, 1 , 2, 3 or 4, preferably i=0. When i is not zero for at least one R’ in any of the formulae (M”1), (M”2), (M”3), (M”4), particularly i=1 , its corresponding R’ is preferably selected from the group consisting of alkali metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, and sulfonic acid (-SO3H).

[0189] Preferably in any of the formulae (M”1), (M”2), (M”3), (M”4), all i are 0, meaning that the phenyl rings are unsubstituted.

[0190] When the recurring unit (Rpf) of the functionalized copolymer (Pf) is represented by formula (M’”) with an acyclic moiety W”, the recurring unit (Rpf) is preferably represented by following formulae (M’”1) in which W’” is represented by — (Rk — O)z— Rk — : wherein

[0191] • each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;

[0192] • each i is independently 0, 1 , 2, 3 or 4, preferably i=0;

[0193] • Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH2-CH2-CH2], 2,2- dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-1 ,3-propylene [CH2- C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-1 ,3-pentylene [CH(C(CH3)2)-C(CH3)2-CH2], and any combination thereof; and

[0194] • z is 0 or an integer from 1 to 500.

[0195] W’” in formula (M’”1) is preferably represented by any one of following formulae

[0196] (V’), (V”), (V’”) and (V””):

[0197] -[CH2-CH2-O]Z-CH2-CH2- (V ),

[0198] -[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (V”),

[0199] -[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (V ”),

[0200] -[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (V””), in which z is 0 or an integer from 1 to 500. Preferably, in formula (M’”1), z is equal to 0. In such an instance, W’” is represented by any one of following formulae (V’*), (V”*), (V’”*) and (V””*), preferably represented by formula (V’*):

[0201] -CH2-CH2- (V *),

[0202] -CH2-CH(CH3)- (V”*),

[0203] -CH2-CH2-CH2-CH2- (V ’*),

[0204] -CH2-C(CH3)2-CH2- (V””*).

[0205] When i is not zero for at least one R’ in formula (M’”1), particularly i=1 , its corresponding R’ is preferably selected from the group consisting of alkali metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, and sulfonic acid (-SO3H).

[0206] Preferably in formula (M””1), all i are 0, meaning that the phenyl rings are unsubstituted.

[0207] When the recurring unit (Rpf) contains an alicyclic moiety W”, the recurring unit (Rpf) is more preferably represented by following formula (M””1 a):

[0208] (M’”1 a), wherein R’ and i are the same as defined for formula (M’”1).

[0209] Preferably in formula (M”’1 a), all i are 0.

[0210] More particularly, the recurring units (Rpf) of the functionalized copolymer (Pf) is preferably represented by the formula (M’1), (M’2), (M’3), (M”1) and / or (M’”1), more preferably represented by formula (M’1), (M”1) and / or (M”’1a). In any of these formulae, the i are preferably 0.

[0211] Most preferably, the recurring units (Rpf) of the functionalized copolymer (Pf) are represented by:

[0212] - formula (M’1 a), or

[0213] - formula (M’2a), or

[0214] - formula (M’3a), or

[0215] - a combination of formula (M’1 a) and formula (M”1 a), or

[0216] - a combination of formula (M’2a) and formula (M”1 a), or

[0217] - a combination of formula (M’3a) and formula (M”1 a), wherein the formulae (M’1 a), (M’2a), (M’3a) and (M”1a) are as follows:

[0218] One of the advantages of the copolymer (Pf) in which its recurring units consist essentially of

[0219] - at least one functionalized recurring unit (R*pf) of formula (N) and

[0220] - at least one recurring unit (Rpf) of formula (M) selected from formulae (M’1),(M’4), (M”1), (M”2), (M”3), (M”4), and / or (M’”1), preferably selected from formulae (M’1 a) and / or (M”1 a), is that such a copolymer (Pf) is free of bisphenol A, preferably free of bisphenol A, 2,2’-diallyl bisphenol A, bisphenol S, and 2,2’-diallyl bisphenol S.

[0221] The copolymer (Pf) according to the invention is advantageously transparent and amorphous. The amorphous copolymer (Pf) may have a heat of fusion of less than about 5 J / g, preferably less than about 3 J / g, said heat of fusion being measured using differential scanning calorimetry (DSC).

[0222] The glass transition temperature (Tg) of the copolymer (Pf) according to the invention is preferably measured by Differential Scanning Calorimetry (DSC). The Tg value is provided using the second heat curve unless otherwise noted. A particular suitable DSC method to measure Tg is detailed in the examples below.

[0223] The decomposition temperature of the copolymer (Pf) according to the invention is preferably measured by thermogravimetric analysis (TGA). A particular suitable TGA method to measure the decomposition temperature is detailed in the examples below.

[0224] The copolymer (Pf) advantageously has a weight average molecular weight (Mw) above 10000 g / mol or at least 12000 g / mol or at least 14000 g / mol. Upper limit for the number average molecular weight (Mw) of the copolymer (Pf) is not particularly critical and will be selected by the person skilled in the art in view of intended field of use. In general, the copolymer (Pf) may have a weight average molecular weight (Mw) equal to or less than 200000 g / mol, preferably equal to or less than 180000 g / mol.

[0225] Unless explicitly stated otherwise, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer (Pf) are estimated by gelpermeation chromatography (GPC), also known as size exclusion chromatography (SEC), preferably calibrated with polystyrene standards, and performed using a mobile phase. The mobile phase may be selected from any solvent for the copolymer (Pf) described herein, preferably NMP. A particular suitable GPC method is detailed in the examples below. The molecular weight distribution (MWD) of the copolymer (Pf) may be characterized by a polydispersity index (PDI) expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

[0226] The copolymer (Pf) contains advantageously less than 10 ppm, preferably less than 5 ppm of Bisphenol A (BPA), more preferably less than 1 ppm of BPA, said ppm being based on total weight of the copolymer (Pf).

[0227] The copolymer (Pf) contains advantageously less than 10 ppm, preferably less than 5 ppm Bisphenol S (BPS), more preferably less than 1 ppm of BPS, said ppm being based on total weight of the copolymer (Pf) .

[0228] The copolymer (Pf) preferably is substantially free (e.g., less than 1 ppm) of BPA and of BPS.

[0229] The copolymer (Pf) more preferably is substantially free (e.g., less than 1 ppm) of BPA, diallyl BPA, BPS and diallyl BPS.

[0230] The BPS content in the copolymer (Pf) may be measured by liquid chromatography analysis of a solution of the copolymer (Pf) in DMF after precipitation of the polymer by acetonitrile.

[0231] The BPA content in the copolymer (Pf) may be measured by gas chromatography analysis of a solution of the copolymer (Pf) in DMF or trichloromethane.

[0232] Processes for making functionalized copolymer (Pf)

[0233] The copolymer (Pf) can be prepared from an unsaturated copolymer (Pu) containing C=C bonds in the main chain and / or pendant groups as a polymer scaffold by using various chemical processes, notably by free radical-thermal reaction, by free radical-UV reaction, by base-catalyzed reaction or by nucleophilic-catalyzed reaction to attach functional groups. The unsaturated copolymer (Pu) will be described later in the text.

[0234] A copolymer (Pf) may also be prepared using a secondary functionalization from a first-functionalized copolymer (Pf1) containing reactive amino groups in the main chain and / or pendant groups. The functionalized copolymer (Pf) thus may be made by : process A: carrying out a first functionalization from the unsaturated copolymer (Pu) as polymeric scaffold, or process B: carrying out a second functionalization process from a first- functionalized copolymer (Pf1) containing reactive amino groups (preferably groups R200 described herein), the copolymer (Pf1) being itself obtained from the process A.

[0235] Process A

[0236] The process for making the functionalized copolymer (Pf) comprises reacting in a solvent an unsaturated copolymer (Pu) with a compound of formula (J): HS - R , in which the functional group R may be any group selected from groups R110, R120, R130, R140, R150, R160, R170, R180, R190, and / or R200 previously described in the present application.

[0237] The compound of formula (J): HS - R may be selected from:

[0238] • compound J110 represented by formula : HS-(CH2)a-COCH3 with a being an integer from 0 to 10,

[0239] • compound J120 represented by formula : HS-C(O)Rmwith Rm being a C1-C6 alkyl or H, preferably H,

[0240] • compound J130 represented by formula : HS- (CH2)b - OH with b being an integer from 1 to 5,

[0241] • compound J140 represented by formula : HS- (CH2)d - SOs' NT with d being an integer from 1 to 5, and with M+being H+or an alkali metal cation, preferably H+, Na+, K+or Li+,

[0242] • compound J150 represented by formula : HS- (CH2)e - Si (OCHsh with e being an integer from 1 to 5,

[0243] • compound J160 represented by formula : HS- (CH2)f - (CF2)g - CF3 with f being an integer from 1 to 5 and with g being an integer from 1 to 10,

[0244] • compound J170 represented by formula : HS- (CH2)h - COOH with h being an integer from 1 to 5,

[0245] • compound Jiso represented by formula : HS- (CH2)k- CH3 with k being an integer from 5 to 30,

[0246] • compound J190 represented by formula : HS- (CH2)I - Ar1with I being an integer from 1 to 10 and with Ar1comprising one or two aromatic or heteroaromatic rings, or

[0247] • compound J200 represented by formula : HS- (CH2)h - NRaRb with h being an integer from 1 to 5, and with Raand Rb being independently H or a C1-C6 alkyl, preferably H or CH3. The compound (J) of formula HS-R used to react the copolymer (Pu) in the process (A) is such that R is independently selected from the group consisting of:

[0248] **- (CH2)2- COCH3,

[0249] **- C(H)O,

[0250] **- (CH2)2- OH,

[0251] **- (CH2)3- SO3Na,

[0252] **- (CH2)3- Si (OCH3)3,

[0253] **- (CH2)2 - (CF2)7 - CF3,

[0254] **- CH2- COOH,

[0255] **- (CH2)9 - CH3,

[0256] **- CH2 - Ph, with Ph being benzyl group,

[0257] **- (CH2)2 - N(CH3)2 ; and

[0258] **- (CH2)2- NH2.

[0259] The reaction with the compound (J) of formula HS - R to prepare the copolymer (Pf) in the process A is preferably carried out in a solvent. When the reaction to prepare copolymer (Pf) is carried out in a solvent, the solvent is for example a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N dimethylacetamide (DMAC), 1 ,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole and sulfolane. The solvent may also be chloroform or dichloromethane (DCM). The reaction to prepare copolymer (Pf) is preferably carried out in sulfolane or NMP.

[0260] The reaction temperature to prepare the copolymer (Pf) in the process A varies between 10°C and 300°C, preferably between room temperature and 200°C, or more preferably between 35°C and 100°C.

[0261] The reaction to prepare the copolymer (Pf) in the process A may be carried out in the presence of a base, for example selected from the group consisting of potassium carbonate (K2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), cesium carbonate (CS2CO3) and sodium tert-butoxide. The base may also be selected from the group consisting of N-Ethyl-N- (propan-2-yl)propan-2-amine (Hunig base), triethylamine (TEA), and pyridine.

[0262] The reaction to prepare the copolymer (Pf) in the process A may be carried out in the presence of:

[0263] - at least one free radical initiator, preferably 2,2'-Azobis(2-methylpropionitrile) (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN); and / or

[0264] - at least one catalyst, preferably selected from peroxides (which include hydroperoxides). The amount of copolymer (Pf) at the end of the reaction is at least 10 wt.% based on the total weight of the copolymer (PO) and the solvent, for example at least 15 wt.%, or at least 20 wt.%, or at least 30 wt.%.

[0265] In preferred embodiments, the reaction to prepare the copolymer (Pf) in the process A is carried out using at least one of following features i) to iv): i) the presence of at least one free radical initiator selected from 2,2'-Azobis(2- methylpropionitrile) (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN); ii) the presence of at least one catalyst selected from peroxides; iii) the presence of a base selected from the group consisting of N-Ethyl-N-(propan-2- yl)propan-2-amine (Hunig base), triethylamine (TEA) and pyridine; iv) the exposure to UV light at a wavelength ranging from 300 nm to 600 nm, preferably from 350 nm to 450 nm., more preferably at 365 nm.

[0266] At the end of the reaction, the copolymer (Pf) may be separated from solids to obtain a solution, such as by filtration. The solution can be used “as is” for reacting the copolymer (Pf) with yet another functional compound, or alternatively, the copolymer (Pf) can be recovered from the solvent, for example by coagulation or devolatilization of the solvent. Process B

[0267] Another process for making a functionalized copolymer (Pf) comprises

[0268] • a 1stfunctionalization step (A): carrying out the process A which comprises reacting in a solvent an unsaturated copolymer (Pu) with a compound J200 of formula : HS-(CH2)h - NRaRb, previously described in the present application, so as to form a first-functionalized copolymer (Pf1) containing the amine functional groups R200 of formula (200): -(CH2)h - NRaRb ; and

[0269] • a 2nd(subsequent) functionalization step (B): performing a secondary functionalization on the copolymer (Pf1) by reacting the amine functional group R200 of the copolymer (Pf1) with another functional compound so as to form a second functionalized copolymer (Pf2) containing functional groups R selected from groups R210, R220, R230, and / or R240 previously described.

[0270] The first-functionalized copolymer (Pf1) containing the amine groups R200 of formula (200): -(CH2)h - NRaRb may be termed “aminated copolymer (Pf1 )”.

[0271] The 2ndfunctionalization step (B) carried out with another functional compound in the process B attaches a new functionality to the nitrogen atom of group R200.

[0272] The aminated copolymer (Pf1) may be in the form of powder, granules or pellets, or beads or “soft” pellets before being used for the preparation of functionalized copolymer (Pf2) or for making an article. In such case of making an article, the functionalized copolymer (Pf2) can be made from the aminated copolymer (Pf1) by contacting the aminated copolymer (Pf1) with at least one functional compound Z* , either at the same time or after the article is formed.

[0273] At the end of the 1stfunctionalization step (A) and prior to carrying out the 2ndfunctionalization step (B), the reaction solution containing the aminated copolymer (Pf1) may be used “as is” for reacting the aminated copolymer (Pf1) with the other functional compound. Alternatively, the aminated copolymer (Pf1) can be recovered in solid form from the solvent, for example by coagulation or devolatilization of the solvent used during the 1stfunctionalization step (A), and then the solidified aminated copolymer (Pf1) is subjected after its re-dissolution to the 2ndfunctionalization step (B) with another functionalization compound.

[0274] The aminated copolymer (Pf1) may be dried to remove moisture / solvent before being used for the preparation of the functionalized copolymer (Pf2).

[0275] The aminated copolymer (Pf1) obtained in step (A) may be dehydrated before coupling in step (B). In such an instance, the process B may thus include the following preliminary steps:

[0276] - first dissolving the aminated copolymer (Pf1) in a mixture of the organic solvent, optionally an acid quencher or scavenger such as tributylamine, and a co-solvent; and

[0277] - subjecting the solution to azeotropic dehydration by heating it to a temperature of 130- 170°C, preferably of 140-160°C, more preferably of 145-155°C, still more preferably of 150 °C±2 °C, and removing most of the co-solvent by distillation. The co-solvent which forms an azeotrope with water includes aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like. The co-solvent is preferably toluene or chlorobenzene. The azeotrope forming co-solvent and the organic solvent are used typically in a co-solvent / solvent weight ratio of from about 1 :100 to about 1 :1 or from about 1 :30 to about 1 :1 , preferably from about 1 :10 to about 1 :1 , more preferably from about 1 :5 to about 1 :1. The azeotrope-forming co-solvent, for example, chlorobenzene or toluene, is removed from the polymer solution, typically by distillation, after the water is removed leaving the aminated copolymer (Pf1) dissolved in the solvent.

[0278] At the end of the 2ndfunctionalization step (B), the second copolymer (Pf2) may be recovered in solid form from the copolymer (Pf2) solution, for example by coagulation or devolatilization of the solvent used during the 2ndfunctionalization step (B).

[0279] The 2ndfunctionalization step (B) can be carried out in following step (B2) using the bioactive compound B* or step (B2’) using a functional compound Z*.

[0280] Step (B2)

[0281] The step (B2) in the process B may comprise contacting the aminated copolymer (Pfi) having amine groups R200 of formula (200) - in which Rb is H, with the bioactive compound B*, optionally in the presence of a coupling agent, in an acidic aqueous solvent, preferably of pH from 3 to 6, or from 4.2 to 5, or from 4.4 to 4.8, to form a second functionalized copolymer (Pf2), whereby amine groups R200 of formula: -(CH2)h-NRaH are converted to groups R210 of formula (210): - (CH2)h -NRaB in the second functionalized copolymer (Pf2), with h and Rain group R210 being the same as in group R200,

[0282] B in group R210 representing a bioactive moiety which is covalently and / or ionically bound to the nitrogen atom in the group R210, and

[0283] B being derived from the bioactive compound B* previously described in relation to group R210.

[0284] The binding of the bioactive compound B* to the aminated copolymer (Pf1) to make the copolymer (Pf2) may be ionic and / or covalent in step (B2).

[0285] The description, including the examples, concerning the conditions for binding the bioactive compound B* to an aminated polyarylethersulfone, such as the acidic aqueous solvent (e.g., comprising an organic acid with a pKa from 2.5 to 5, preferably citric acid), the coupling agent (preferably selected from N-(3-Dimethylaminopropyl)-N'- ethylcarbodiimide hydrochloride (EDC) and / or N-Hydroxy succinimide (NHS)), suitable reaction temperature (e.g., from 15 to 60 °C) and suitable reaction time (e.g., from 10 to 120 min), can be found in WO 2022 / 171683A1 by Solvay Specialty Polymers, USA (SYENSQO group).

[0286] In this process B, the aminated copolymer (Pf1) is modified into the copolymer (Pf2), so that the binding of the bioactive compound B* to the amine groups R200 confers a functionalization to the copolymer (Pf2) for a specific property associated with a biological medium or body fluid with which the bioactive compound-immobilized copolymer (Pf2) will come into contact. On the other end, the aminated copolymer (Pf1) with amine groups R200 does not have such property. This specific property of the copolymer (Pf2) may include hemocompatibility. Hemocompatibility can be measured for example by activated partial thromboplastin time (aPTT) for coagulation of blood plasma.

[0287] Step (B2’)

[0288] The step (B2’) in the process B comprises contacting the first functionalized (aminated) copolymer (Pf1) containing amine groups R200 of formula: - (CH2)h - NRaRb, with a functional compound Z*, optionally in the presence of a coupling agent, in an organic solvent, to make a second functionalized copolymer (Pf2’), in which the group R200 in the aminated copolymer (Pf1) is converted:

[0289] • to the group R220 represented by the formula (220) with a functional compound Z1* being an haloalkane of formula XRS; to the group R230 represented by the formula (230) with a functional compound Z2* being a cyclic sulfonate ester of formula RvOsS, preferably selected from 1 ,3-propane sultone or 1 , 4, butane sultone; or

[0290] • to the group R240 represented by the formula (240): “ - (CH2)h - NRaZ , in which h, Raare the same as in the group R200, and Z, being covalently and / or ionically bound to the nitrogen atom in the group R240, is selected from the group consisting of

[0291] • an alkyl carbonyl moiety Z3;

[0292] • a carboxylic acid moiety Z4;

[0293] • an aromatic sulfonate moiety Z5 ;

[0294] • a sugar acid moiety Z6;

[0295] • a zwitterionic moiety Z7;

[0296] • a haloalky I carbonyl moiety Z8;

[0297] • a hydroxyl moiety Z9; and

[0298] • a combination of olefinic and carboxylic acid moieties Z10, with a functional compound Z* respectively selected from the group consisting of

[0299] - an alkanoyl halide [compound Z3*];

[0300] - a carboxylic acid anhydride [compound Z4* ];

[0301] - an aromatic sulfonic acid or sulfonate salt [compound Z5*];

[0302] - a sugar acid or salt thereof [compound Z6*];

[0303] - a betaine (meth)acrylate zwitterionic compound [compound Z7*];

[0304] - a haloacetyl halide [compound Z8*];

[0305] - a linear or cyclic alcohol or polyol [compound Z9*]; and

[0306] - maleic anhydride [compound Z10*].

[0307] In instances where it is desired to retain, in the functionalized copolymer (Pf2), some amine groups originating from the aminated copolymer (Pf1), it may be advantageous to use a sub-stoichiometric molar amount of the functional compound Z* relative to the molar amount of available R200 groups (preferably containing the following reactive moieties: -(CH2)h-NH2 or -(CH2)h-N(CH3)2) in the recurring units (R*pf). In that way, in addition to having at least one functionality derived from a functional compound Z* selected from compounds Z*1 to Z*10, the resulting functionalized copolymer (Pf2) further has an amine functionality by the presence of the unreacted -NRaRb moieties (preferably being -NH2 or -N(CHs)2 moieties) in the unreacted recurring units (R*pu).

[0308] The attachment of the functional compound Z* to the aminated copolymer (Pf1) to make the functionalized PAES copolymer (Pf) may be ionic and / or covalent, but preferably covalent. The description, including the examples, concerning the conditions for binding the functional compound Z* to an aminated polyarylethersulfone, such as the choice of organic solvent, the coupling agent if used, suitable reaction temperature (e.g., from 40 °C to 95 °C) and suitable reaction time (e.g., from 5 to 60 min), can be found in EP4421109A1 by Solvay Specialty Polymers, USA (Syensqo group).

[0309] Functional compound Z*

[0310] It should be understood that a sole functional compound Z* or two or more functional compounds Z* may be used in the making of the functionalized copolymer (Pf2).

[0311] The functional compounds Z* which are described in EP4421109A1 by Solvay Specialty Polymers, USA (SYENSQO group) are particularly suitable to be used in step (B2’), in particular those used in the examples.

[0312] Preferably, the functional compound Z* used in step (B2’) may be selected from compounds Z1* to Z10*.

[0313] • A haloalkane [compound Z1*]: A non-limiting suitable functional compound Z1* may be a methyl halide or C2+linear haloalkane with a straight-chain structure. Z1* may be of formula: X(CnH2n+i) in which n is an integer of from 1 to 10, or from 3 to 10, or from 4 to 10, or from 5 to 9, preferably n being 6, and in which X is an halide selected from Br, Cl, or I. Alternatively, the functional compound Z1* may be a cyclic haloalkane of the formula: X- (CyH2y-2)n-CH3 or X-(CyH2y-i)n with y being an integer from 3 to 10, preferably y being 5 or 6; n’ being an integer of from 1 to 5, preferably n’ being 1 or 2; and X being an halide selected from Br, Cl, or I, preferably X being Cl. A preferred functional compound Z1* is methyl halide or a hexyl halide of formula: X(CeHi3), in which the halide X is Br, Cl, or I, preferably X being chloride.

[0314] • A C3 alkyl or C4 alkyl sultone [compound Z2*]: a non-limiting suitable functional compound Z2* may be a cyclic sulfonate ester of formula RvOsS, (also known as alkyl sultone] with Rvbeing a group of formula (CH2)x with x being 3 or 4, preferably selected from 1 ,3-propane sultone or 1 , 4, butane sultone.

[0315] • An alkanoyl halide [compound Z3*]: a non-limiting suitable functional compound Z3* may be an acyl halide with a straight-chain structure of formula: X-C(O)-(CH2)n-CH3 in which n is an integer of from 2 to 11 , or from 3 to 10, or from 4 to 10, or from 5 to 9, or preferably n = 6, or with a cyclic structure of formula: X-C(O)-(CyH2y-2)n -CH3 or X-C(O)- (CyH2y-i)n , with y being an integer from 3 to 12, preferably y being 5 or 6; n’ being an integer of from 1 to 5, or preferably n’ being 1 or 2, X being an halide selected from Br, Cl, or I, preferably X being Cl. Preferred functional compound Z3* may be of formula: X- C(O)-(CH2)6-CH3or X-C(O)-(CeH4)-CH3, with X being a halide selected from Br, Cl, or I, preferably X being Cl. The more preferred functional compound Z3* is octanoyl chloride. • A carboxylic acid anhydride [compound Z4*]: a non-limiting suitable functional compound Z4* may be a carboxylic acid anhydride, such as succinic anhydride, or a nitrilotricarboxylic acid such as 2,2’,2”-nitrilotriacetic acid (or triglycollamic acid). In some embodiments, the functional compound Z4* may exclude 2,2’,2”-nitri lotriacetic acid.

[0316] • An aromatic sulfonic acid or sulfonate salt [compound Z5*]: a non-limiting suitable functional compound Z5* may be a carboxy aryl sulfonic acid or sulfonate, such as of formula: C(O)-Ar2-SO3M with M being H or an alkali metal, preferably H or Na or Li, and Ar2being an aromatic ring which may be unsubstituted (meaning of formula -CeFL-) or substituted by one to four C1-C5 alkyl groups. Preferred functional compound Z5* may be 3-carboxybenzene sulfonic acid or sulfonate of formula: C(O)-CeH4-SO3M, with M being H or an alkali metal salt, preferably H or Na.

[0317] • A sugar acid or salt thereof [compound Z6*]: a non-limiting suitable functional compound Z6* may be at least one uronic or alduronic acid (e.g., glucuronic acid, galacturonic acid, mannuronic acid, alluronic acid, iduronic acid, guluronic acid), gluconic acid (stereoisomer of 2,3,4,5,6-pentahydroxy hexanoic acid), glyceric acid, N- glycolylneuraminic acid, hexenuronic acid, isosaccharinic acid, lactobionic acid, threonic acid, xylonic acid, lyxonic acid, or any alkali metal salt of these acids, such as glucuronate sodium salt, or any polymers made from one or more of these sugar acids. When the sugar acid compound Z6* is a polymer or copolymer made from these sugar acids, the compound Z6* may be a poly(urionic acid) or poly(alduronic acid), in particular may be alginic acid which is a polysaccharide made from mannuronic acid and guluronic acid, or its corresponding alginate salt.

[0318] • A betaine (meth)acrylate zwitterionic compound [compound Z7*]: a non-limiting suitable functional compound Z7* is at least one betaine (meth)acrylate, particularly a betaine sulfo(meth)acrylate and / or betaine carboxy(meth)acrylate, preferably in the form of alkali metal salt, more preferably in the form of sodium salt. A preferred functional compound Z7* is [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (DM APS).

[0319] • A haloacetyl halide [compound Z8*]: a non-limiting suitable functional compound Z8* is chloroacetyl chloride.

[0320] • A linear or cyclic alcohol or polyol [compound Z9*]: a non-limiting suitable functional compound Z9* is an alcohol or polyol. Particularly, the functional compound Z9* may contain both epoxide and alcohol groups such as glycidol, 7-oxabicyclo[4.1 .0]heptan- 2-ol, or 2-oxiraneethanol; or

[0321] • A non-limiting suitable functional compound Z10* is maleic anhydride.

[0322] Unsaturated copolymer (Pu) The unsaturated copolymer (Pu) comprises at least 60 mol%, based on the total amount of moles of recurring units in the unsaturated copolymer (Pu), of:

[0323] - at least one recurring unit (Rpu) of formula (M):

[0324] [-Ar-SO2-Ar’-O-W-O-] (M),

[0325] - at least one unsaturated recurring unit (R*pu) of formula (P):

[0326] [-Ar-SO2-Ar’-O-E’-O-] (P), wherein

[0327] • Ar-SO2-Ar’ is a diaryl sulfone moiety derived from at least one dihalodiaryl sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group;

[0328] • W is a moiety derived from at least one diol (BB) being selected from the group consisting of aromatic diols, saturated alicyclic diols and saturated acyclic diols;

[0329] • E’ is an unsaturated aliphatic moiety derived from at least one dihydroxy aliphatic allyl monomer (AA’); and

[0330] • E’ comprises at least one unsaturated end moiety E’a represented by formula (E’a1), at least one unsaturated divalent moiety E’b represented by formula (E’b1), or combination thereof,

[0331] • the formulae (E’a1), (E’b1) being as follows:

[0332] *— CH = CH2(E’a1)

[0333] *— CH = CH — * (E’b1) in which the symbol represents a part at which the moieties E’a and E’b are connected to a carbon atom in the unsaturated aliphatic moiety E’ of the recurring unit (R*pu) of formula (P).

[0334] The copolymer (Pu) may particularly comprise collectively at least 70 mol.%, or at least 80 mol.%, or at least 90 mol.%, or at least 95 mol.%, or at least 98 mol.% of recurring units (Rpu) and (R*PU), based on the total number of moles of recurring units in the copolymer (Pu). The recurring units of the copolymer (Pu) preferably consist essentially of recurring units (Rpu) and (R*pu).

[0335] The unsaturated copolymer (Pu) may particularly comprise collectively at least 60 mol.%, or at least 70 mol.%, or at least 80 mol.%, or at least 90 mol.%, or at least 95 mol.%, or at least 99 mol.%, based on the total amount of moles of recurring units in the functionalized copolymer (Pf), of :

[0336] - unsaturated recurring unit (R*pu) of formula (P) and recurring unit (Rpu) of formula (M’);

[0337] - unsaturated recurring unit (R*pu) of formula (P) and recurring unit (Rpu) of formula (M”);

[0338] - unsaturated recurring unit (R*pu) of formula (P) and recurring unit (Rpu) of formula (M’”);

[0339] - unsaturated recurring unit (R*pu) of formula (P), recurring unit (Rpu) of formula (M’) and recurring unit (Rpu) of formula (M”); - unsaturated recurring unit (R*pu) of formula (P), recurring unit (Rpu) of formula (M’) and recurring unit (Rpu) of formula (M’”);

[0340] - unsaturated recurring unit (R*pu) of formula (P), recurring unit (Rpu) of formula (M”) and recurring unit (Rpu) of formula (M’”); wherein the formula (P) and its unsaturated aliphatic moiety E’ are the same as previously described; wherein the formulae (M’), (M”) and (M’”) are as follows :

[0341] [-Ar-SO2-Ar’-O-W’-O-] (M’),

[0342] [-Ar-SO2-Ar’-O-W”-O-] (M”),

[0343] [-Ar-SO2-Ar’-O-W’”-O-] (M’”), in which

[0344] • Ar-SO2-Ar’ is a diaryl sulfone moiety derived from a dihalodiaryl sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group;

[0345] • W’ is an aromatic moiety derived from an aromatic diol (BB’);

[0346] • W” is a cycloaliphatic moiety derived from a saturated alicyclic diol (BB”); and

[0347] • W’” is an acyclic moiety derived from a saturated acyclic diol (BB’”).

[0348] In the unsaturated copolymer (Pu), E’ in unsaturated recurring unit (R*pu) of formula (P) is preferably derived from trimethylolpropane allyl ether (TMPAE), 1 ,4-butenediol, or both, more preferably derived from TMPAE; W’ in recurring unit (Rpu) of formula (M’) is preferably derived from 4,4’biphenol, TMBPF, or both, more preferably derived from 4,4’biphenol; W” in recurring unit (Rpu) of formula (M”) is preferably derived from a biobased alicyclic diol, more preferably derived from isosorbide; and W’” in recurring unit (Rpu) of formula (M’”) is preferably derived from C2-Cs alkylene glycols, more preferably derived from ethylene glycol..

[0349] The recurring units (R*pu) and (Rpu) in the copolymer (Pu) are such that the molar ratio r1 of the recurring units (R*pu) to the recurring units (Rpu) is:

[0350] • at most 45:55, preferably at most 40:60, more preferably at most 35:65, still more preferably at most 30:70, and

[0351] • at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88.

[0352] Unsaturated recurring units (R*pu) of copolymer (Pu)

[0353] The unsaturated recurring units (R*pu) preferably may be represented by following formula (P1), formula (P2) and / or formula (P3):

[0354] (P3), in which

[0355] • each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;

[0356] • each i is independently 0, 1 , 2, 3 or 4, preferably 0 or 1 , more preferably 0;

[0357] • each of Ra, Rbis independently represented by -(CH2)a- , -CHRh- -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with p being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)a- , -CHfCHs)-, -(CH2)a-CH(CH3)- or - CH(CH3)-CH2)a- , with a being 1 or 2;

[0358] • each of Rf, Rgis independently represented by -(CH2)a- , -(CHRh)p-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)«- with cz being an integer from 1 to 3, or preferably 1 or 2;

[0359] • each of x1 , x2 is independently 0 or 1 , with the proviso that x1+x2=1 or 2; • each of y1 , y2 is independently 0 or 1 , with the proviso that y1+y2=1 or 2;

[0360] • each of z1 , z2 is independently 0 or 1 , with the proviso that z1+z2=1 or 2;

[0361] • each Rcis independently represented by -(CH2)Z- or -(CH2)s-O-(CH2)E, with / being an integer from 1 to 6, with 5 being 0 , 1 or 2, with e being an integer from 1 to 6; preferably represented by -CH2- ,-(CH2)2- , -CH2-O-CH2-,

[0362] -(CH2)2-O-(CH2)2- -CH2-O-(CH2)2- or -(CH2)2-O-CH2-;

[0363] • each Rdis independently represented by a C1-C5 alkyl group, preferably -CH3 , -CH(CH3)2, -C(CH3>3, -C2H5 or -C3H7, more preferably -CH3, -C2H5 or -CH(CH3)2; and

[0364] • each Reis independently represented by -H, a C1-C5 alkyl group such as CH3, C2H5, C3H7, an alcohol group such as R1-OH, or an ether group -R1-O-R2 in which R1 is a C1-C6 alkylene and R2 is a C1-C5 alkyl group, preferably with R1 being -(CH2)a- , -(CHRh)p-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being 1 , 2 or 3, preferably 1 or 2, with being 1 , 2 or 3,, preferably 1 or 2, with Rhbeing CH3 or C2H5, and with R2 being preferably being CH3 or C2H5.

[0365] The unsaturated recurring units (R*pu) may be more preferably represented by following formula (P1 a) or (P3a), still more preferably represented by formula (P1 a):

[0366] (P3a).

[0367] Recurring units (Rpu) of copolymer (Pu)

[0368] The recurring unit (Rpu) of the unsaturated copolymer (Pu) and the recurring unit (Rpf) of the functionalized copolymer (Pf) are the same.

[0369] The recurring unit (Rpu) of the copolymer (Pu) is of general formula (M), particularly represented by any of the following formulae (M’), (M”) and (M’”), preferably represented by any of following formulas (M’1), (M’2), (M’3), (M’4), (M”1), (M”2), (M”3) and / or (M’”1), more preferably represented by formula (M’1), (M’2), (M’3), (M”1) and / or (M’”1 a), yet more preferably represented by formula (M’1), (M”1) and / or (M’”1 a), such formulae being described in relation to the recurring unit (Rpf) of the copolymer (Pf). Preferably in any of these formulae, i=0, meaning that the divalent arylene groups are unsubstituted.

[0370] Most preferably, the recurring units (Rpu) of the copolymer (Pu) are represented by:

[0371] - formula (M’1 a), or

[0372] - formula (M’2a), or

[0373] - formula (M’3a), or

[0374] - a combination of formula (M’1 a) and formula (M”1 a), or

[0375] - a combination of formula (M’2a) and formula (M”1 a), or

[0376] - a combination of formula (M’3a) and formula (M”1 a).

[0377] Processes for making unsaturated copolymer (Pu)

[0378] The unsaturated copolymer (Pu) is made by condensation of

[0379] - at least one dihydroxy allyl monomer (AA’) comprising at least one C=C bond and at least two hydroxyl groups, said at least one dihydroxy allyl monomer (AA’) preferably having from 4 to 15 carbon atoms and;

[0380] - at least one diol (BB) selected from the group consisting of aromatic diols (BB’), saturated alicyclic diols (BB”), saturated acyclic diols (BB’”), and any combination thereof, in particular any combination of at least one aromatic diol (BB’) and at least one saturated alicyclic diol (BB”), or any combination of at least one aromatic diol (BB’) and at least one saturated acyclic diol (BB’”), or any combination of at least one aromatic diol (BB’), at least one saturated alicyclic diol (BB”) and at least one saturated acyclic diol (BB’”); and

[0381] - at least one dihalodiary I sulfone monomer (CC).

[0382] The at least one diol (BB) represents at least 25 mol% based on all dihydroxy monomers used during condensation.

[0383] The at least one dihalodiaryl sulfone monomer (CC) represents at least 50 mol% and up to 100 mol%, said mol % being based on all dihalogenated monomers used during condensation.

[0384] When using an endocrine-safe aromatic diol (BB’) - meaning which does not have high estrogenic activity, the copolymer (Pu) which incorporates the dihydroxy allyl monomer (AA’) may further exhibit low or reduced estrogenic activity compared to PAES polymers made from bisphenol A, or from bisphenol S, and / or from any olefinic derivatives thereof such as dially l-bisphenol A or dially l-bisphenol S, and therefore such a copolymer (Pu) would present lower risk for human health.

[0385] The copolymer (Pu) can also be effectively prepared using a less-expensive dichlorodiphenylsulfone monomer (DCDPS), thereby providing a more cost effective production, despite the fact that the aliphatic dihydroxy allyl monomers (AA’) may have poorer reactivity with DCDPS, when compared to the very reactive difluorodiphenylsulfone monomer (DFDPS). Preferred unsaturated copolymers (Pu) may be made by condensation of a dihalodiphenylsulfone (CC) with

[0386] - at least one dihydroxy aliphatic allyl diol (AA’) selected from the group consisting of olefinic C4-C10 diols (AA’1) and dihydroxy allyl C7-C15 ethers (AA’2), preferably selected from dihydroxybutene (DHB) and / or TMPAE and

[0387] - at least one diol (BB) which is endocrine safe, particularly being selected from 4,4’- biphenol and / or tetramethyl Bisphenol F (TMBPF) as aromatic diol (BB’), and / or 1 , 4:3,6- dianhydrohexitols and / or 1 ,4:3,6-dianhydrohexitols with acyclic aliphatic end groups as alicyclic diol (BB”), and / or C2-C6 alkylene glycols as acyclic diol (B’”); the at least one diol (BB) preferably being selected from 4,4’-biphenol, isosorbide, and / or ethylene glycol ; the at least one diol (BB) more preferably selected from 4,4’-biphenol and / or isosorbide.

[0388] The molar ratio r1 of the at least one dihydroxy aliphatic allyl monomer (AA’) to the diol (BB) is:

[0389] - at most 45:55, preferably at most 40:60, more preferably at most 35:65, still more preferably at most 30:70, and

[0390] - at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88.

[0391] Preferred molar ratios r1 of the at least one dihydroxy aliphatic allyl monomer (AA’) to the diol (BB) may be from 5:95 to 45:55, from 7:93 to 40:60, from 10:90 to 35:65, or from 12:88 to 30:70.

[0392] The copolymer (Pu) made by condensation may not include one or more units derived from a benzonitrile compound selected from dihalogenated benzonitriles and / or dihydroxy benzonitriles, such as 2,6-dichlorobenzonitrile, 3,4-dichlorobenzonitrile,2,6- dihydroxybenzonitrile, 2,5-dihydroxybenzonitrile, 3,4-dihydroxybenzonitrile.

[0393] The copolymer (Pu) made by condensation may not include one or more units derived from a naphthyridine diol selected from quinoxaline diols (also called benzopyrazine diols), quinazoline diols, cinnoline diols and / or phthalazine diols.

[0394] Presence of C=C bonds in copolymer (Pu)

[0395] The copolymer (Pu) has reactive allyl groups comprising C=C bonds on its main polymeric chain and / or on side chains. The reactive allyl moieties comprising C=C bonds in the copolymer (Pu) originate from the at least one hydroxy aliphatic monomer (AA’).

[0396] When at least one dihydroxy aliphatic allyl monomer (AA’) comprises an olefinic diol (AA’1), at least some of the C=C bonds in the copolymer (Pu) are on the main polymeric chain of copolymer (Pu).

[0397] When at least one dihydroxy aliphatic allyl monomer (AA’) comprises an allyl ether (AA’2), at least some of the C=C bonds in the copolymer (Pu) are on side chains, preferably the furthest away from the junction of the side chain with the main polymeric chain of copolymer (Pu).

[0398] Olefin Content in copolymer (Pu)

[0399] The copolymer (Pu) may have an olefin content, based on the total weight of the copolymer (Pu), of at least 2 wt.%, or at least 3 wt.%, or at least 4 wt.%, or at least 5 wt.%, or at least 6 wt.%, or at least 7 wt.%, or at least 8 wt.%, and / or at most 40 wt.%, or at most 35 wt.%, or at most 30 wt.%, or at most 28 wt.%. Preferably, the copolymer (Pu) has an olefin content, based on the total weight of the copolymer (Pu), of from 2 wt.% to 40 wt.%, or from 3 wt.% to 35 wt.%, or from 4 wt.% to 30 wt.%, or from 5 wt.% to 30 wt.%, or from 5 wt.% to 28 wt.%.

[0400] The olefin content in the copolymer (Pu) is preferably measured by1H-NMR. A particular suitable method for measuring the olefin content is detailed in the examples section below.

[0401] Dihydroxy aliphatic allyl monomer (AA’)

[0402] The at least one dihydroxy monomer (AA’) preferably has from 4 to 15 carbon atoms and comprises at least one unsaturated C=C bond.

[0403] The at least one dihydroxy monomer (AA’) preferably contains only one C=C bond or two C=C bonds.

[0404] The at least one dihydroxy monomer (AA’) may represent at least 4 mol%, preferably at least 6 mol%, or at least 8 mol%, or at least 10 mol%, or at least 12 mol%, and less than 50 mol%, or at most 40 mol%, preferably at most 35 mol%, or at most 32 mol%, or at most 30 mol%, said mol% being based on the total number of moles of all dihydroxy monomers used during condensation. Preferably the at least one dihydroxy monomer (AA’) represents from 6 mol% to 45 mol%, preferably from 8 mol% to 40 mol%, or from 10 mol% to 35 mol%, or from 12 mol% to 32 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0405] The at least one dihydroxy monomer (AA’) may be of general formula (A’): HO-E’- OH, in which E’ is an aliphatic allyl moiety.

[0406] Preferably, the at least one dihydroxy monomer (AA’) is acyclic and the aliphatic allyl moiety E’ is acyclic.

[0407] The at least one dihydroxy monomer (AA’) is selected from olefinic diols (AA’i) and / or allyl ethers (AA’2), preferably selected from the group consisting of olefinic C4-C10 diols (AA’i) and allyl C7-C15 ethers (AA’2). Suitable olefinic diols (AA’i) and allyl ethers (AA’2) are described as follows.

[0408] Olefinic diol (AA’i) A suitable olefinic diol (AA’i), preferably acyclic, comprises from 4 to 15 carbon atoms, preferably from 4 to 14 carbon atoms, more preferably from 4 to 12 carbon atoms, still more preferably from 4 to 10 carbon atoms.

[0409] The olefinic diol (AA’i) preferably has at least two hydroxyl groups, one of these hydroxyl groups being at the alpha (a) position or omega (w) position. A preferred olefinic diol (AA’i) is a a, w-di hydroxy C4-C15 or C4-C14 or C4-C12 or C4-C10 alkene.

[0410] The C=C bond in the olefinic diol (AA’i) is preferably not at the alpha (a) position (also termed primary position), nor omega (w) position.

[0411] The olefinic diol (AA’i) preferably contains only one C=C bond. Preferably, the olefinic diol (AA’i) is selected from the group consisting of 1 ,4-butenediol; 1 ,5-pentenediol; 1 ,6-hexenediol; 1 ,7-heptenediol; 1 ,8-octenediol; 1 ,9-nonenediol; 1 ,10-decenediol; 2,2,4- trimethyl-1 ,3-pentenediol; and any combination thereof; preferably selected from 1 ,4- butenediol; 1 ,5-pentenediol; 1 ,6-hexenediol; 1 ,7-heptenediol; 1 ,8-octenediol; 1 ,9- nonenediol; 1 ,10-decenediol; or any combination thereof. Most preferably, the olefinic diol (AA’i) is 1 ,4-dihydroxy-2-butene.

[0412] Allyl ether (AA’2)

[0413] A suitable allyl ether (AA’2), preferably acyclic, comprises from 4 to 15 carbon atoms, preferably from 5 to 14 carbon atoms, more preferably from 6 to 13 carbon atoms, still more preferably from 7 to 13 carbon atoms.

[0414] The allyl ether (AA’2) has at least two hydroxyl groups, which are preferably spaced by at least 3 carbon atoms.

[0415] The allyl ether (AA’2) preferably contains only one C=C bond.

[0416] The allyl ether (AA’2) may be of formula HO-E’-OH, in which E’ is a moiety comprising at least one C3+ olefinic pendant group R2’ optionally containing at least one ether -O- bond and another pendant group R2” containing at least one ether -O- bond when R2’ does not. For example, R2’ may be a C3+ olefinic pendant group, preferably having the C=C bond in the alpha position, and R2” may be a C2+ ether pendant group with at least one ether -O- bond. Alternatively, R2’ may be a C3+ olefinic pendant group comprising at least one ether -O- bond, preferably having the C=C bond in the alpha position, and R2” may be a pendant group being a hydroxyl group or a C1+ alkyl or alcohol group.

[0417] The allyl ether (AA’2) may be of any of the two following formulae:

[0418] Rc-CH=CH-RdRC-CH=CH2

[0419] HO — (Ra)y1— C — (Rb)y2— OH HO — (Ra)y1— C — (Rb)y2— OH

[0420] Re Rewherein • each of Ra, Rbis independently represented by -(CH2)a- , -CHRh-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)a- , -CHfCHs)-, -(CH2)a-CH(CH3)- or - CH(CH3)-CH2)a- , with a being 1 or 2;

[0421] • each of Rf, Rgis independently represented by -(CH2)a- , -(CHRh)p-

[0422] -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2 - with cz being 1 ,2, or 3, preferably 1 or 2;

[0423] • each of x1 , x2 is independently 0 or 1 , with the proviso that x1 +x2=1 or 2;

[0424] • each of y1 , y2 is independently 0 or 1 , with the proviso that y 1 +y2=1 or 2;

[0425] • each of z1 , z2 is independently 0 or 1 , with the proviso that z1 +z2=1 or 2;

[0426] • each Rcis independently represented by -(CH2)X- or -(CH2)8-O-(CH2)e, with / being an integer from 1 to 6, with 5 being 0 , 1 or 2, with e being an integer from 1 to 6; preferably represented by -CH2- ,-(CH2)2- , -CH2-O-CH2-, -(CH2)2-O-(CH2)2-, -CH2-O-(CH2)2- or -(CH2)2-O-CH2-;

[0427] • each Rdis independently represented by a C1-C5 alkyl group, preferably -CH3 , -CH(CH3)2, -C(CH3)3, -C2H5 or -C3H7, more preferably -CH3, -C2H5 or -CH(CH3)2; and

[0428] • each Reis independently represented by -H, a C1-C5 alkyl group such as CH3, C2H5, C3H7, an alcohol group such as R1-OH, an ether group -R1-0-R2 in which R1 is a C1-C6 alkylene and R2 is a C1-C5 alkyl group, preferably with R1 being -(CH2)a- , -(CHRh)p- -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 3, preferably 1 or 2, with p being an integer from 1 to 3, preferably 1 or 2, with Rhbeing CH3 or C2H5, and with R2 being preferably being CH3 or C2H5.

[0429] Preferably, the allyl ether (AA’2) is selected from the group consisting of those of formulae (A1) to (A43) in TABLE 1.

[0430] More preferably, the allyl ether (AA’2) is trimethylolpropane allyl ether (TMPAE) of formula (A1) : H2C=CHCH2OCH2C(C2H5)(CH2OH)2.

[0431] Table 1 : Suitable allyl ethers (AA’2)

[0432] Diol (BB)

[0433] The at least one diol (BB) may represent at least 25 mol%, preferably at least 30 mol%, or at least 35 mol%, or at least 40 mol%, or at least 45 mol%, or at least 50 mol%, or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, and less than 100 mol%, or at most 99 mol%, or at most 98 mol%, or at most 97 mol%, or at most 96 mol%, or at most 95 mol%, or at most 92 mol%, or at most 90 mol%, or at most 85 mol%, said mol% being based on the total number of moles of all dihydroxy monomers used during condensation. Particularly when used in the condensation, the at least one diol (BB) may represent from 50 mol% to less than 100 mol%, preferably from 55 mol% to 95 mol%, more preferably from 60 mol% to 90 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0434] The at least one diol (BB) may be selected from the group consisting of aromatic diols (BB’), saturated alicyclic diols (BB”), saturated acyclic diols (BB’”), and any combination thereof. In particular any combination of at least one aromatic diol (BB’) and at least one saturated alicyclic diol (BB”), any combination of at least one aromatic diol (BB’) and at least one saturated acyclic diol (BB’”), or any combination of at least one aromatic diol (BB’) at least one saturated alicyclic diol (BB”) and at least one saturated acyclic diol (BB’”) are envisioned.

[0435] In particular, the at least one diol (BB) may be selected from at least one aromatic diol (BB’), at least one saturated alicyclic diol (BB”), or any combination thereof.

[0436] Alternatively, the at least one diol (BB) may be selected from at least one aromatic diol (BB’), at least one saturated acyclic diol (BB’”), or any combination thereof.

[0437] It should be understood that in the context of the present disclosure, the terms “diol” and “dihydroxy monomer” can be used interchangeably and each means a compound having at least two hydroxyl groups. This means that, in the context of the present invention, a dihydroxy allyl monomer (AA’) or diol (BB) also encompasses any aliphatic allyl monomer or diol with more than two hydroxyl groups. For instance, an aliphatic allyl diol (AA’*) which has 3 to 6 hydroxyl groups, particularly 3 or 4 hydroxyl groups, may be envisioned to use in the dihydroxy allyl monomer (AA’) or as the dihydroxy allyl monomer (AA’). For example, the dihydroxy allyl monomer (AA’) may include, or may be, an allyl ether triol (AA’2), such as 1 ,3-propanediol,2(hydroxymethyl)-2-[(2-propen-1-yloxy)methyl]- (ACI) or 1 ,3-propanediol,2-(hydroxymethyl)-2-[(7-octen-1-yloxy)methyl]- (ACI). For another example, the diol (BB) may comprise an aromatic triol (BB’) having three OH groups and optionally at least one alicyclic diol (BB”) or at least one acyclic diol (BB’”) having only 2 OH groups.

[0438] The diol (BB) may be of general formula (B): HO-W-OH, in which W is an aromatic, saturated cycloaliphatic or saturated acyclic moiety.

[0439] Aromatic diol (BB’)

[0440] The at least one diol (BB) may comprise at least one aromatic diol (BB’), or substantially all of the diol (BB) may be at least one aromatic diol (BB’).

[0441] Alternatively, the at least one diol (BB) may exclude any aromatic diol (BB’).

[0442] When used in the condensation, the at least one aromatic diol (BB’) may represent, based on the total number of moles of all dihydroxy monomers used during condensation, at least 25 mol%, preferably at least 30 mol%, or at least 35 mol%, or at least 40 mol%, or at least 45 mol%, or at least 50 mol%, or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, and less than 100 mol%, or at most 99 mol%, or at most 98 mol%, or at most 97 mol%, or at most 96 mol%, or at most 95 mol%, or at most 92 mol%, or at most 90 mol%, or at most 85 mol%.

[0443] Particularly when used in the condensation, the at least one aromatic diol (BB’) may represent from 50 mol% to less than 100 mol%, preferably from 55 mol% to 95 mol%, more preferably from 60 mol% to 90 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0444] It should be understood that the at least one aromatic diol (BB’) contains at least two hydroxyl groups. This means that, in the context of the present invention, the aromatic diol (BB’) also encompasses any aromatic compound (BB’*) with more than two hydroxyl groups. An aromatic compound (BB’*) which has 3 to 6 hydroxyl groups, particularly 3 or 4 hydroxyl groups, may be envisioned to use in the aromatic diol (BB’), or as a sole aromatic diol (BB’), to make the sulfone recurring unit (Rc’) by reacting with the at least one dihalodiaryl sulfone monomer (CC). For example, the aromatic diol (BB’) may include, or may be, an aromatic triol, such as 1 ,1 ,1-tris-(4-hydroxyphenyl)-ethane.

[0445] The at least one aromatic diol (BB’) may be of general formula (B’): HO-W’-OH, in which W’ is an aromatic moiety comprising at least one aromatic ring.

[0446] The at least one aromatic diol (BB’) or the aromatic moiety W’ may contain only one aromatic ring or may have at least two aromatic rings. Preferably, the at least one aromatic diol (BB’) or aromatic moiety W’ may contain two or more aromatic rings.

[0447] The two or more aromatic rings in the at least one aromatic diol (BB’) or aromatic moiety W’ may be fused together by sharing two or more neighboring ring carbon atoms.

[0448] Preferably, the two or more aromatic rings in the at least one aromatic diol (BB’) or in aromatic moiety W’ may be connected by a single bond or a linking group such as - C(CH3)2-, -SO2-, or an alkylene group -(CH2)p- with p>1 , preferably p=1.

[0449] At least one aromatic ring in the aromatic diol (BB’) or aromatic moiety W’ may have at least one heteroatom, such as at least one oxygen atom and / or at least one nitrogen atom.

[0450] Preferably though, each aromatic ring in the aromatic diol (BB’) or aromatic moiety W’ does not have any nitrogen atom. For example, the aromatic diol (BB’) or aromatic moiety W’ does not contain any nitrogen-containing ring selected from pyridine, pyridazine, pyrimidine, pyrazine, quinolone, isoquinoline, cinnoline, phthalazine, and quinazoline,

[0451] More preferably, none of the aromatic rings in the aromatic diol (BB’) or aromatic moiety W’ has any heteroatom. In such instance, the backbone of each aromatic ring in the aromatic diol (BB’) or aromatic moiety W’ is made only of interconnected carbon atoms.

[0452] In particular, the aromatic diol (BB’) should not comprise naphthyridine diols selected from quinoxaline diols (also called benzopyrazine diols), quinazoline diols, cinnoline diols, and phthalazine diols. Examples of quinoxaline diols may be 2,6-dihydroxy quinoxaline or 2,3-dihydroxy quinoxaline. As used herein, a ‘quinoxaline” diol is a hetero-bicyclic naphthyridine containing two fused six-membered aromatic rings : a benzene ring and a pyrazine ring. Isomeric structures of quinoxalane are quinazoline, cinnoline, and phthalazine. Preferably, no aromatic ring in the aromatic diol (BB’) or aromatic moiety W’ should have a nitrile -C=N pendant group.

[0453] In particular, the aromatic diol (BB’) should not comprise dihydroxy benzonitriles, such as 2,6-dihydroxybenzonitrile, 2,5-dihydroxybenzonitrile, 3,4-dihydroxybenzonitrile, etc.

[0454] As non-limiting examples of suitable aromatic diols (BB’) are selected from the group consisting of bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4’- biphenol, diallyl biphenol, bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, hydroquinone, resorcinol, aromatic triols such as 1 ,1 ,1-tris-(4-hydroxyphenyl)-ethane, and any combination of two or more thereof.

[0455] Particularly, the aromatic diol (BB’) may exclude any diol selected from the group consisting of bisphenol A; 2,2’-diallyl Bisphenol A; bisphenol S; bisphenol S derivatives chosen from 2,2’-diallyl bisphenol S, 4,4’-bis(4-hydroxyphenoxy) diphenyl sulfone, 4,4’- bis(4-(4-(4-hydroxyphenylsulfonyl)phenoxy)phenoxy) diphenyl sulfone; bisphenol F, and 2,2’-dially I bisphenol F.

[0456] Yet more particularly, the aromatic diol (BB’) may exclude any diol selected from the group consisting of bisphenol A, 2,2’-dially I bisphenol A, bisphenol S, 2,2’-dially I bisphenol S, bisphenol F, and 2,2’-diallyl bisphenol F.

[0457] Preferably, the aromatic diol (BB’) is selected from the group consisting of 4,4’- biphenol, a diallyl biphenol, tetramethyl bisphenol F, and any combination thereof.

[0458] More preferably, the aromatic diol (BB’) is selected from the group consisting of 4,4’- biphenol, tetramethyl bisphenol F, and any combination thereof.

[0459] Still more preferably, the aromatic diol (BB’) consists of 4,4’-biphenol and optionally diallyl biphenol and / or tetramethyl bisphenol F.

[0460] Most preferably, the aromatic diol (BB’) is 4,4’-biphenol.

[0461] Alicyclic diol (BB”)

[0462] The at least one diol (BB) may comprise at least one saturated alicyclic diol (BB”), or substantially all of the diol (BB) may be at least one saturated alicyclic diol (BB”).

[0463] Alternatively, the at least one diol (BB) may exclude any alicyclic diol (BB”).

[0464] The alicyclic diol (BB”) is saturated, meaning that it does not contain C=C bonds.

[0465] When used during condensation, the at least one alicyclic diol (BB”) may represent, based on the total number of moles of all dihydroxy monomers used in the condensation, at least 2 mol%, preferably at least 4 mol%, or at least 6 mol%, or at least 8 mol%, or at least 10 mol%, and less than 100 mol%, or at most 99 mol%, or at most 98 mol%, or at most 97 mol%, or at most 96 mol%, or at most 95 mol%, or at most 92 mol%, or at most 90 mol%, or at most 85 mol%, or at most 80 mol%, or at most 75 mol%, or at most 70 mol%, or at most 65 mol%, or at most 60 mol%, or at most 55 mol%, or at most 50 mol%, or at most 45 mol%, or at most 40 mol%, preferably at most 35 mol%, or at most 30 mol%, or at most 25 mol%, or at most 20 mol%, or at most 19 mol%, or at most 18 mol%, or at most 17 mol%, or at most 16 mol%, or at most 15 mol%.

[0466] Particularly when used during condensation, the at least one alicyclic diol (BB”) may represent from 50 mol% to less than 100 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0467] With the dihydroxy monomer (AA’) used during condensation, the alicyclic diol (BB”) may represent at most 90 mol%, preferably at most 85 mol%, or at most 80 mol%, or at most 75 mol%, or at most 70 mol%, or at most 65 mol%, or at most 60 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0468] Particularly when used during condensation, the alicyclic diol (BB”) may represent from 2 mol% to 45 mol%, preferably from 4 mol% to 40 mol%, or from 6 mol% to 35 mol%, or from 8 mol% to 35 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0469] When used in combination with an aromatic diol (BB’) during condensation, in such instance the at least one alicyclic diol (BB”) may represent at most 40 mol%, preferably at most 35 mol%, or at most 30 mol%, or at most 25 mol%, or at most 20 mol%, or at most 19 mol%, or at most 18 mol%, or at most 17 mol%, or at most 16 mol%, or at most 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0470] Preferably, when used in combination with an aromatic diol (BB’) during condensation, the at least one alicyclic diol (BB”) represents from 2 mol% to 40 mol% or from 4 mol% to 35 mol%, preferably from 6 mol% to 30 mol%, or from 8 mol% to 30 mol%, or from 10 mol% to 25 mol%, or from 10 mol% to 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0471] The alicyclic diol (BB”) may be of general formula (B”): HO-W”-OH, in which W” is a cycloaliphatic moiety comprises at least one non-aromatic ring. The moiety W” does not contain any aromatic ring.

[0472] When the at least one alicyclic diol (BB”) or cycloaliphatic moiety W” contains two or more non-aromatic rings, at least two of the non-aromatic rings in the alicyclic diol (BB”) or cycloaliphatic moiety W” may be fused together by sharing two or more neighboring ring carbon atoms, or may be connected by a single bond or a linking group such as - C(CHS)2- , -SO2-, or an alkylene group -(CH2)p- with p>1 , preferably p=1 .

[0473] At least one non-aromatic ring in the alicyclic diol (BB”) or cycloaliphatic moiety W” may comprise at least one heteroatom, such as at least one oxygen atom, at least one sulfur atom, and / or at least one nitrogen atom. Alternatively, non-aromatic ring(s) in the alicyclic diol (BB”) or cycloaliphatic moiety W’ may not comprise any heteroatoms, meaning that the backbone of such non-aromatic ring is made only of interconnected carbon atoms.

[0474] When used during condensation, the at least one alicyclic diol (BB”) may be particularly selected from the group consisting of those diols complying with formulae (D1) to (D11) and any combination thereof : wherein each Q’, being the same or different in formula (D11), is an acyclic moiety.

[0475] The acyclic moiety Q’ in formula (D11) is the same as defined for the alicyclic moiety (W”11). The alicyclic diol (BB”), when used, is preferably a bio-based diol, such as selected from 2,3-di-O-alkylene-1-threitols; 1 ,4:3,6-dianhydrohexitols and / or 1 , 4:3,6- dianhydrohexitols with acyclic aliphatic end groups.

[0476] The alicyclic diol (BB”) is more preferably selected from the group consisting of 1 ,4:3,6-dianhydrohexitols such as isosorbide (of formula D1), isomannide (of formula D2), isoidide (of formula D3); 2,3-di-O-alkylene-1-threitols such as 2,3-O-isopropylidene-l- threitol (of formula D4) and / or 2,3-di-O-methylene-1-threitol; and / or 1 , 4:3,6- dianhydrohexitols with acyclic aliphatic end groups such as isosorbide with acyclic aliphatic end groups (of formula D11).

[0477] Yet more preferably, the at least one alicyclic diol (BB”) is selected from the group consisting of isosorbide (of formula D1) and 2,3-O-isopropylidene-l-threitol of formula D4).

[0478] Most preferably, the at least one alicyclic diol (BB”) is isosorbide (of formula D1).

[0479] Acyclic diol (BB’”)

[0480] The at least one diol (BB) may comprise at least one acyclic diol (BB’”).

[0481] Alternatively, the at least one diol (BB) may exclude any acyclic diol (BB’”).

[0482] The acyclic diol (BB”) is saturated, meaning that it does not contain C=C bond

[0483] When used during condensation, the at least one acyclic diol (BB’”) may represent, based on the total number of moles of all dihydroxy monomers used during condensation, at least 2 mol%, preferably at least 4 mol%, or at least 6 mol%, or at least 8 mol%, or at least 10 mol%, or or at least 12 mol%, and less than 100 mol%, or at most 99 mol%, or at most 98 mol%, or at most 97 mol%, or at most 96 mol%, or at most 95 mol%, or at most 92 mol%, or at most 90 mol%, or at most 85 mol%, or at most 80 mol%, or at most 75 mol%, or at most 70 mol%, or at most 65 mol%, or at most 60 mol%, or at most 55 mol%, or at most 50 mol%, or at most 45 mol%, or at most 40 mol%, preferably at most 35 mol%, or at most 30 mol%, or at most 25 mol%, or at most 20 mol%, or at most 19 mol%, or at most 18 mol%, or at most 17 mol%, or at most 16 mol%, or at most 15 mol%.

[0484] Particularly when used during condensation, the acyclic diol (BB’”) may represent from 2 mol% to 45 mol%, preferably from 4 mol% to 40 mol%, or from 6 mol% to 35 mol%, or from 8 mol% to 35 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0485] Preferably, when used in combination with an aromatic diol (BB’) during condensation, the at least one acyclic diol (BB’”) represents from 2 mol% to 40 mol% or from 4 mol% to 35 mol%, preferably from 6 mol% to 30 mol%, or from 8 mol% to 30 mol%, or from 10 mol% to 25 mol%, or from 10 mol% to 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0486] With the dihydroxy monomer (AA’) used during condensation, the acyclic diol (BB’”) may represent at most 90 mol%, preferably at most 85 mol%, or at most 80 mol%, or at most 75 mol%, or at most 70 mol%, or at most 65 mol%, or at most 60 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0487] When an aromatic diol (BB’) is used during condensation, in such instance the at least one acyclic diol (BB’”) may represent at most 40 mol%, preferably at most 35 mol%, or at most 30 mol%, or at most 25 mol%, or at most 20 mol%, or at most 19 mol%, or at most 18 mol%, or at most 17 mol%, or at most 16 mol%, or at most 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0488] Preferably, when used in combination with an aromatic diol (BB’) during condensation, the acyclic diol (BB’”) represents from 4 mol% to 35 mol%, preferably from 6 mol% to 30 mol%, or from 8 mol% to 30 mol%, or from 10 mol% to 25 mol%, or from 10 mol% to 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0489] The acyclic diol (BB’”) may be a linear or branched aliphatic diol.

[0490] In addition to the oxygen atoms of the two hydroxyl groups, the acyclic diol (BB’”) may comprise one or more heteroatoms (i.e., non-carbon atoms, for example atoms of oxygen, nitrogen and / or sulfur) connected to at least one carbon atom.

[0491] Alternatively, the acyclic diol (BB’”) may have a backbone made only of connected carbon atoms.

[0492] Non-limiting examples of acyclic diols ((BB’”) may be selected from alkylene glycols and / or poly(alkylene glycol)s, preferably selected from the group consisting of ethylene glycol; propylene glycol [HO-CH2-CH(CH3)-OH]; tetraethylene glycol; 1 ,3-propanediol; 1 ,4- butanediol; 1 ,5-pentanediol; 1 ,6-hexanediol; 1 ,8-octanediol; 1 ,10-decanediol; 2-methyl-1 ,3- propanediol; 2,2-dimethylpropane-1 ,3-diol (also known as neopentyl glycol); 2,2,4- trimethyl-1 ,3-pentanediol; 2-ethyl-2-butyl-1 ,3-propanediol; poly(ethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.

[0493] Non-limiting examples of acyclic diols (BB’”) which are linear aliphatic diols are ethylene glycol, poly(ethylene glycol), tetraethylene glycol, poly(tetramethylene oxide), 1 ,3- propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,8-octanediol and / or 1 ,10- decanediol. Non-limiting examples of acyclic diols (BB’”) which are branched aliphatic diols are 2-methyl-1 ,3-propanediol, 2,2-dimethylpropane-1 ,3-diol, 2,2,4-trimethyl-1 ,3- pentanediol, 2-ethyl-2-butyl-1 ,3-propanediol, propylene glycol, and / or polypropylene glycol). A preferred acyclic diol (BB’”) may include at least one alkylene glycol selected from C2-C6 alkylene glycols, or more preferably from C2-C5 alkylene glycols, or still more preferably from C2-C4 alkylene glycols. A more preferred acyclic diol (BB’) may comprise or consist of an alkylene glycol selected from the group consisting of ethylene glycol; 1 ,3- propanediol; 1 ,4-butanediol; 1 ,5-pentanediol; 1 ,6-hexanediol; 2-methyl-1 ,3-propanediol; neopentyl glycol; 2,2,4-trimethyl-1 ,3-pentanediol, and any combination of two or more thereof. A still more preferred acyclic diol (BB’) includes ethylene glycol. The most preferred acyclic diol (BB’”) is ethylene glycol.

[0494] The at least one acyclic diol (BB’”) may be of general formula (B’”): HO-W”’-OH, in which W’” is an acyclic moiety, meaning an aliphatic moiety without ring structure.

[0495] The acyclic moiety W” may be represented by formula (V): -[Rk-O-]z-Rk- (V), in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH2-CH2-CH2], 2,2- dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-1 ,3-propylene [CH2-C(C2H5)(C4Hg)- CH2], 2,2,4-trimethyl-1 ,3-pentylene [CH(C(CH3)2)-C(CH3)2-CH2], and any combination thereof; and z is 0 or an integer from 1 to 500.

[0496] The acyclic moiety W’” is preferably represented by any one of following formulae

[0497] (V’), (V”), (V’”) and (V””):

[0498] -[CH2-CH2-O]Z-CH2-CH2- (V ),

[0499] -[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (V”),

[0500] -[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (V ”),

[0501] -[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (V ””), in which z is 0 or an integer from 1 to 500.

[0502] When the acyclic moiety W’” is derived from a poly(alkylene glycol), z is an integer from 1 to 500, preferably an integer from 2 to 200, more preferably an integer from 2 to 100. Although not preferred, when W’” is represented by any one of the formulae (V), (V’), (V”), (V’”) and (V””) is a poly(alkylene glycol), z in any of these formulae may be selected such that the average molecular weight (Mn) of the formula (B’”): HO-W’”-OH is less than 30,000 g / mol, preferably less than 10,000 g / mol, or less than 5,000 g / mol, or less than 3,000 g / mol, or less than 1 ,000 g / mol.

[0503] Preferably, when W’” is represented by any one of following formulae (V’), (V”), (V’”) and (V””), z is equal to 0. In such an instance, the acyclic diol (BB’”) is represented by any one of following formulae (V’d), (V”d), (V’”d) and (V””d), preferably represented by formula

[0504] (V’d):

[0505] HO-CH2-CH2-OH (V’d),

[0506] HO-CH2-CH(CH3)-OH (V”d),

[0507] HO-CH2-CH2-CH2-CH2-OH (V’”d),

[0508] HO-CH2-C(CH3)2-CH2-OH (V””d).

[0509] Dihalodiaryl sulfone monomer (CC)

[0510] The at least one dihalodiaryl sulfone monomer (CC) may represent at least 50 mol%, preferably at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, based on the total number of moles of all dihalogenated monomers used during condensation.

[0511] The at least one dihalodiaryl sulfone monomer (CC) may represent at most 100 mol%, or at most 99 mol%, or at most 98 mol%, or at most 97 mol%, or at most 96 mol%, or at most 95 mol%, or at most 92 mol%, or at most 90 mol%, or at most 85 mol%, based on the total number of moles of all dihalogenated monomers used during condensation.

[0512] Preferably, the at least one dihalodiaryl sulfone monomer (CC) represents from 50 mol% to 100 mol%, preferably from 60 mol% to 100 mol%, more preferably from 65 mol% to 100 mol%, based on the total number of moles of all dihalogenated monomers used during condensation.

[0513] The at least one dihalodiaryl sulfone monomer (CC) may represent substantially the sole dihalogenated monomer used during condensation.

[0514] The at least one dihalodiaryl sulfone monomer (CC) may be of general formula (C): X-Ar-SO2-Ar’-X’, in which the -Ar-SO2-Ar’- is a diaryl sulfone moiety, in which: each of X, X in formula (C), independent from each other, is Cl or F; preferably both X,X’ are Cl; and each of Ar, Ar in formula (C), independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group.

[0515] Each of Ar, Ar may be of formula (IV): wherein each R in any of Ar, Ar’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and each i is independently 0, 1 , 2, 3 or 4.

[0516] In addition, when i in any of Ar, Ar’ is 1 , 2, 3 or 4, each R corresponding to such an i is preferably independently selected from the group consisting of alkali metal or alkaline earth metal sulfonates, alkyl sulfonates, and sulfonic acid (-SO3H).

[0517] More preferably, each i in Ar, Ar’ is 0, and none of the aromatic rings in Ar, Ar’ is substituted by R. That is to say, Ar, and Ar’ in formula (C) are unsubstituted arylene groups.

[0518] The dihalodiaryl sulfone monomer (CC) may be selected from the group consisting of: 4,4’-dichlorodiphenyl sulfone (DCDPS), monosulfonated 4,4’-dichlorodiphenyl sulfone (msDCDPS), disulfonated 4,4’-dichlorodiphenyl sulfone (dsDCDPS), 4,4’-difluorodiphenyl sulfone (DFDPS), monosulfonated 4,4’-difluorodiphenyl sulfone (msDFDPS), disulfonated 4,4’-difluorodiphenyl sulfone (dsDFDPS), and any combination thereof.

[0519] Preferably, the dihalodiaryl sulfone monomer (CC) is selected from the group consisting of: DFDPS, DCDPS, disodium bis(4-chloro-3-sulfophenyl)sulfone (dsDCDPS), and any combination thereof.

[0520] In particular, the dichlorodiphenylsulfone (DCDPS) of formula (C*): CI-Ar-SO2-Ar’-CI, in which Ar and Ar’ are both unsubstituted arylene groups, may represent at least 50 mol%, preferably at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mol%, or up to 100 mol% based on the total number of moles of the dihalodiaryl sulfone monomer (CC) used during condensation.

[0521] Most preferably, the dihalodiaryl sulfone monomer (CC) is DCDPS.

[0522] Process for making the copolymer (Pu)

[0523] The process for making the copolymer (Pu) comprises reacting in a reaction medium comprising a polar aprotic solvent, a base and a monomers mixture comprising:

[0524] - the at least one dihydroxy aliphatic allyl monomer (AA’),

[0525] - the at least one diol (BB) selected from aromatic diols (BB’), alicyclic diols (BB”), acyclic diols (BB’”), or any combination thereof, in particular any combination of at least one aromatic diol (BB’) and at least one alicyclic diol (BB”), or any combination of at least one aromatic diol (BB’) and at least one acyclic diol (BB’”), or any combination of at least one aromatic diol (BB’), at least one alicyclic diol (BB”) and at least one acyclic diol (BB’”); and

[0526] - the at least one dihalodiaryl sulfone monomer (CC), under condensation conditions effective to form the copolymer (Pu) having reactive allyl groups comprising C=C on its main polymeric chain and / or on side chains.

[0527] Monomer (AA’), monomer (BB) such as monomers (BB’), (BB”), and / or (BB’”), and monomer (CC) are described above.

[0528] Generally, monomers (AA’), (BB), (CC) are employed as starting compounds, which means that the condensation reaction generally does not start from prepolymers of monomers (AA’), (BB), (CC).

[0529] The at least one diol (BB) may represent at least 25 mol% based on all dihydroxy monomers present in the reaction mixture during condensation.

[0530] The dihalodiaryl sulfone monomer (CC) represents at least 50 mol% and up to 100 mol% based on all dihalogenated monomers present in the reaction mixture during condensation.

[0531] The reaction medium preferably does not include : - a naphthyridine diol selected from quinoxaline diols (also called benzopyrazine diols), quinazoline diols, cinnoline diols, and phthalazine diols, particularly 2,6-dihydroxy quinoxaline or 2, 3-d i hydroxy quinoxaline; and / or

[0532] - a benzonitrile compound selected from dihalogenated benzonitriles and / or dihydroxy benzonitriles, such as 2,6-dichlorobenzonitrile, 3,4-dichlorobenzonitrile,2,6- dihydroxybenzonitrile, 2,5-dihydroxybenzonitrile, 3,4-dihydroxybenzonitrile, etc.

[0533] The reaction is preferably conducted in one stage. This means that the reaction between dihydroxy monomers and dihalogenated monomers takes place in a single reactor vessel without isolation of intermediate products.

[0534] Alternatively, the reaction can also be conducted in two or more stages, for example:

[0535] - by pre-mixing the dihydroxy monomers and dihalogenated monomers with the polar aprotic solvent in a reactor vessel and then adding the base to that pre-mixture, or

[0536] - by pre-mixing the base with the polar aprotic solvent in a reactor vessel and then adding the dihydroxy monomers and dihalogenated monomers later to that pre-mixture.

[0537] The reaction medium in which the condensation reaction is carried out has a total weight % monomer concentration [hereinafter “total wt% monomers”] based on the total weight of all monomers and the polar aprotic solvent, of:

[0538] - at least 30 wt%, preferably at least 35 wt%, more preferably at least 38 wt%, and / or

[0539] - at most 60 wt%, preferably at most 55 wt%, more preferably at most 50 wt%.

[0540] The reaction medium comprises a base.

[0541] The molar amount of the base, relative to the molar amount of all dihydroxy monomers used during condensation which may be referred to as the molar ratio ‘Tbase” is:

[0542] - at least 1.00, or at least 1.04, or at least 1.10, or at least 1.15, or at least 1.2, or at least 1 .25, or at least 1 .30 ; and / or

[0543] - at most 3.0, or at most 2.8, or at most 2.75, or at most 2.5, or at most 2.4.

[0544] The base preferably comprises an anhydrous alkali metal carbonate.

[0545] The anhydrous alkali metal carbonate may be selected from the group consisting of sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate. The anhydrous alkali metal carbonate is preferably selected from sodium carbonate and / or potassium carbonate, is more preferably potassium carbonate.

[0546] The average particle size (D50) of the alkali metal carbonate may be at least 10 microns and at most 400 microns, preferably at least 15 microns and at most 200 microns, more preferably at least 20 microns and at most 100 microns. Even more preferably, the alkali metal carbonate’s average particle size (D50) of at least 20 microns and at most 50 microns is used.

[0547] The base used during condensation (in the reaction medium) is preferably anhydrous. As used herein, the term “anhydrous” refers to a substance containing less than 2 wt% moisture, preferably less than 1 wt% moisture, more preferably less than 0.5 wt% moisture, most preferably less than 0.25 wt% moisture as measured by Karl-Fisher titration or by loss on drying test.

[0548] The dihydroxy and dihalogenated monomers and the base are dissolved and / or dispersed in a polar aprotic solvent.

[0549] The polar aprotic solvent employed is one generally known in the art and widely used for the manufacture of aromatic sulfone polymers. The polar aprotic solvent is preferably selected from the group consisting of 1 ,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1 ,1 -dioxide (commonly called tetramethylene sulfone or sulfolane), N-Methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N-dimethylacetamide (DMAc), N,N'- dimethylpropyleneurea (DMPU), N,N’-dimethylformamide (DMF), N-methylcaprolactame, N-ethylcaprolactame, tetrahydrothiophene-1 -monoxide, and any mixture of two or more thereof. The polar aprotic solvent is more preferably selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N- di methylformamide (DMF), N,N’-dimethylacetamide (DMAc), 1 ,3-dimethyl-2- imidazolidinone (DMI), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), sulfolane, and any combination thereof. The polar aprotic solvent is yet more preferably selected from sulfolane, DMAc, or NMP.

[0550] For the purpose of the present invention, the term “additional solvent” or “co-solvent” is understood to denote a solvent different from the reactants and the products of the condensation reaction.

[0551] If desired, an additional solvent can be used together with the polar aprotic solvent which forms an azeotrope with water, whereby water that can originate from at least one raw material and / or can be formed as a byproduct during the polymerization (for example when an alkali metal carbonate base is used) may be removed by azeotropic distillation continuously throughout the condensation polymerization. In general, the reaction medium may be maintained in substantially anhydrous conditions during the condensation polymerization by removing water continuously from the reaction mass. Water can be removed by distillation or with the azeotrope-forming solvent as an azeotrope, as described above.

[0552] The additional solvent that forms an azeotrope with water will generally be selected to be inert with respect to the monomers and polar aprotic solvent. Suitable azeotropeforming solvents for use in such condensation polymerization processes include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, and the like, preferably chlorobenzene.

[0553] The azeotrope-forming solvent and the polar aprotic solvent are typically employed in a weight ratio of from about 1 : 20 to about 1 : 1 , preferably from about 1 : 10 to about 1 : 1 , more preferably from about 1 : 5 to about 1 : 3.

[0554] The condensation reaction though is preferably carried out without an azeotropeforming co-solvent.

[0555] The reaction medium, containing the following ingredients: the dihydroxy and dihalogenated monomers, the base, and the polar aprotic solvent, is formed by :

[0556] 1 / mixing all of these ingredients together, or

[0557] 2 / pre-mixing some of the ingredients together to obtain a pre-mixture and then adding the missing ingredient(s) to the pre-mixture.

[0558] The molar ratio r3 of the hydroxyl groups and halogen groups (preferably chlorine) in the reaction medium can vary, depending on factors such as control of the end group types and contents or control of reaction speed and PAES’s molecular weight. It is generally preferred that the molar ratio r3 of the hydroxyl groups from the dihydroxy monomer(s) and the halogen groups from the dihalogenated monomer(s) which are reactive towards each other is controlled or adjusted.

[0559] For the purpose of the present invention, the expression “substantially equimolar” used with reference to the overall amount of hydroxyl groups from dihydroxy monomer(s) and halogen groups from dihalo monomer(s) during polycondensation is to be understood that the molar ratio r3 between the overall amount of hydroxyl groups from all dihydroxy monomers [i.e., the dihydroxy aliphatic allyl monomer (AA’) and the diol(s) (BB) such as aromatic diol (BB’), alicyclic diol (BB”) and / or acyclic diol (BB’” and the overall amount of halogen groups from the dihalodiaryl sulfone monomer (CC) is from 0.95 to 1.05, preferably from 0.98 to 1.02, more preferably from 0.99 to 1.01 , yet more preferably from 0.993 to 1 .008, still more preferably from 0.995 to 1 .005.

[0560] While the molar ratio of the hydroxyl groups and halogen groups is preferably substantially equimolar with respect to obtaining high molecular weights (Mw> 30 kDa), alternatively the molar amount of the halogen groups (preferably chlorine) can be higher than that of the hydroxyl groups or vice versa. For instance, to increase the number of phenolic OH end groups, the molar ratio of halogen (chlorine) end groups to phenolic OH end groups is adjusted by using a molar excess of the starting dihydroxy monomer (AA’) and diol (BB) [aromatic diol (BB’), alicyclic diol (BB”) and / or acyclic diol (BB’”)] compared to the starting dihalodiaryl sulfone monomer (CC). For example, the molar ratio r3 of OH groups to halogen (chlorine) groups in the monomers may be from 1.005 to 1.2, especially from 1.007 to 1.15, most preferably from 1.01 to 1.1. When it is desired to have less reactive end groups in the copolymer (Pu), it may be preferred to increase the number of halogen (chlorine) end groups, in particular phenyl chlorine, and the molar ratio of halogen (chlorine) end groups to phenolic OH end groups is adjusted by using a molar excess of the starting dihalodiaryl sulfone monomer (CC) compared to the starting dihydroxy monomer (AA’), aromatic diol (BB’), and optional alicyclic diol (BB”), whereby an excess of chlorine end groups is preferable. In such instance, the molar ratio (1 / r3) of halogen (chlorine) groups to OH groups may be from 1.005 to 1 .2, especially from 1 .007 to 1 .15, most preferably from 1 .01 to 1 .1.

[0561] The reaction medium to prepare the copolymer (Pu) is kept at a temperature suitable for condensation to occur. Such a suitable temperature for the reaction medium may be:

[0562] - more than 150 °C, preferably at least 155 °C, more preferably at least 160 °C, yet more preferably at least 165 °C, still more preferably at least 170 °C, and

[0563] - less than 230 °C, preferably at most 225 °C, more preferably at most 220 °C, yet more preferably at most 215 °C, still more preferably at most 210 °C.

[0564] Preferred temperature of the reaction medium may be from about 165°C to about 225°C, preferably from about 170 °C to about 220 °C, more preferably from about 180 °C to about 215 °C, when NMP and / or sulfolane is used as solvent.

[0565] The process to manufacture the copolymer (Pu) is such that the reaction conversion is at least 90%, preferably at least 95%.

[0566] The time for reaction to prepare the copolymer (Pu) may be from about 3 hours to 24 hours, or from about 4 hours to 20 hours, or from 5 hours to 18 hours.

[0567] Typically, if the condensation reaction is conducted at atmospheric pressure, the boiling temperature of the solvent selected usually limits the temperature of the reaction. The condensation reaction may be conveniently carried out in an inert atmosphere, e. g., nitrogen, at atmospheric pressure, although higher or lower pressures may also be used. Recovery of copolymer (Pu) in solid form

[0568] The copolymer (Pu) can be recovered by methods well known and widely employed in the art such as, for example, coagulation, solvent evaporation, and the like.

[0569] The resulting copolymer (Pu) may be isolated by devolatilization of the reaction medium after separation of salts with or without first adding additional solvent(s) to fully dissolve any polymer and cause the precipitation of the metal halide (preferably KCI). The additional solvent may be different than the polar aprotic solvent used in the reaction, but preferably it is the same.

[0570] Alternatively, the copolymer (Pu) may be isolated by precipitation and / or coagulation by contacting the reaction medium, optionally after salt removal by filtration, with a nonsolvent for the copolymer (Pu) such as a C1-C5 alcohol, water, or any mixture thereof. The preci pitate / coag ulate may be rinsed and / or washed with demineralized water or a Ci- Cs alcohol prior to drying at a temperature ranging from at least 70 °C to about 170 °C. While a vacuum may be applied during drying, drying is generally performed at ambient pressure.

[0571] The resulting copolymer (Pu) solid may be further processed by extruding and pelletizing. The pelletized product may subsequently be subjected to further melt processing such as injection molding and / or sheet extrusion. The conditions for molding, extruding, and thermoforming the resulting copolymer (Pu) are well known in the art.

[0572] The copolymer (Pu) features all the benefits of the currently sold polyarylethersulfones while also unexpectedly featuring a reduced content in potential endocrine disruptors especially when an endocrine-safe aromatic diol (BB’), such as 4,4’- biphenol or TMBPF, is used, potentially a higher renewable content especially when a biosourced alicyclic diol (BB”), such as diols of any of formulae (D1) to (D4), is used in making such a copolymer (Pu).

[0573] Use of the copolymer (Pf)

[0574] Another aspect of the present invention provides the use of the copolymer (Pf) for preparing an article (or a part thereof) as described herein.

[0575] This aspect may comprise using the copolymer (Pf) in forming the article or a part thereof. The methods for making such an article are provided herein.

[0576] Among applications of use, mention can be made of healthcare applications, in particular medical and dental applications, wherein shaped articles comprising, or made from, the copolymer (Pf) can advantageously be used for replacing metal, glass and other traditional materials in single-use and reusable instruments and devices.

[0577] Article

[0578] Another aspect of the present invention provides an article (preferably a shaped article) comprising, or made from, the copolymer (Pf) according to the present invention.

[0579] The article may be selected from the group consisting of medical devices; implants; membranes; beads; coatings; melt processed films, monofilaments and fibers; solution processed films (porous and non-porous films, including solution casted membranes, and membranes from solution spinning); solution processed monofilaments; melt process monofilaments and fibers; hollow fibers and solid fibers; coatings; printed objects, and injection and compression molded objects.

[0580] The shaped article may be transparent or colored.

[0581] The copolymer (Pf) can be incorporated into articles having a polymeric surface. The article can have a polymeric surface, at least a portion of which comes into direct contact with an aqueous stream, biological medium, body fluid and / or food product in its intended application setting. The polymeric surface may be an external or internal surface of the article. A person of ordinary skill in the art will know which surface is intended to contact such liquid. For example, a medical implant has at least one external surface intended to come into direct contact with a body fluid.

[0582] A surface of the article may comprise or may be made from the copolymer (Pf). For example, the copolymer (Pf) may form a portion of such a surface, or the copolymer (Pf) may form all, or substantially all, of the article.

[0583] In another example, a surface of the article may comprise a coating or film comprising the copolymer (Pf), disposed on an underlying substrate. In such instances, the underlying substrate may be a structural component having a composition distinct from the copolymer (Pf). The film or coating may have an average thickness of from about 25 pm to about 1 mm.

[0584] For example, the copolymer (Pf) may be included in at least a portion of a surface of a stent (e.g., a coating) onto a surface of a tubular substrate for the stent, when the stent is intended for such surface to come in contact with a body fluid. Alternatively, the copolymer (Pf) can form all, or substantially all, of the stent. A stent is generally a tube inserted into the lumen of an anatomic vessel or duct to keep the passageway open. Particularly, the shaped article may be selected from medical devices or implants, particularly selected from implantable cardioverter defibrillators, artificial hip joints, artificial knee joints, heart pacemakers, breast implants, spinal fusion hardware (including, but not limited to, artificial discs), intra-uterine devices, artificial knees, stents (including, but not limited to, coronary stents), stent grafts, bypass grafts, ear tubes, prostheses, artificial heart valves, implantable tubes (including, but not limited to, catheters), filtration membranes (including, but not limited to, hemodialysis membranes), surgical instruments (including, but not limited to, forceps, clamps, retractors, distractors, scalpels, surgical scissors, dilators, specula, suction tips, staplers, injection needles, drills, fiber optic instruments; preferably coronary stents, artificial heart valves, or heart pacemakers.

[0585] Particularly preferred, the shaped article is a membrane, or a part thereof. Among membranes, the copolymer (Pf) according to the present invention is particularly suitable for manufacturing membranes intended for contact with an aqueous stream, a biological medium, body fluid or food product. The shaped article may be selected from membranes for bioprocessing and medical nitrations (such as hemodialysis membranes), membranes for food and beverage processing, membranes for water purification, membranes for wastewater treatment and membranes for industrial process separations involving biological medium.

[0586] Membranes can be in the form of a flat sheet or in the form of tubes.

[0587] Tubular membranes are classified based on their dimensions in tubular membranes having a diameter greater than 3 mm; capillary membranes, having a diameter comprised between 0.5 mm and 3 mm; and hollow fibers having a diameter of less than 0.5 mm. Capillary membranes are otherwise referred to as hollow fibers.

[0588] From an architectural perspective, membranes may be provided under the form of flat structures (e.g. films or sheets), corrugated structures (such as corrugated sheets), tubular structures, or hollow fibers; as per the pore size is concerned, full range of membranes (non-porous and porous, including for microfiltration, ultrafiltration, nanofiltration, and reverse osmosis) can be advantageously manufactured; pore distribution can be isotropic or anisotropic.

[0589] According to the present invention, a membrane is typically a microporous membrane which can be characterized by its average pore diameter and porosity, i.e., the fraction of the total membrane that is porous.

[0590] The membrane may have a gravimetric porosity (%) of 20 to 90 % and comprises pores, wherein at least 90 % by volume of the said pores has an average pore diameter of less than 5 pm. Gravimetric porosity of the membrane is defined as the volume of the pores divided by the total volume of the membrane.

[0591] Membranes having a uniform structure throughout their thickness are generally known as symmetrical membranes; membranes having pores which are not homogeneously distributed throughout their thickness are generally known as asymmetric membranes. Asymmetric membranes are characterized by a thin selective layer (0.1-1 pm thick) and a highly porous thick layer (100-200 pm thick) which acts as a support and has little effect on the separation characteristics of the membrane.

[0592] Hollow fibers are particularly advantageous in applications where compact modules with high surface areas are required.

[0593] The shaped article may be, as above mentioned, under the form of films or sheets. These shaped articles are particularly useful as specialized optical films or sheets, and / or suitable for packaging.

[0594] For hemodialysis membranes, the copolymer (Pf) containing groups R210 with attached heparin may be particularly advantageous.

[0595] The shaped article may be in the form of beads or membrane intended for us as chromatography polymeric stationary material. The chromatography polymeric stationary material may be used in affinity chromatography (which may include metal affinity chromatography), in hydrophobic interaction chromatography and / or in ion exchange chromatography. For chromatography applications, the copolymer (Pf) containing functional groups selected from groups R220 to R240 may be particularly advantageous. Further description concerning chromatography polymeric stationary material can be found in EP4421109A1 by Solvay Specialty Polymers, USA (Syensqo group). The article may further comprise at least one polymer distinct from the functionalized copolymer (Pf) described herein. For example the article may further comprise at least one polymer selected from the group consisting of the aminated copolymer (Pf1), the unsaturated copolymer (Pu), another sulfone polymer, e.g., polysulfone (PSU), polyethersulfone (PESU), poly(biphenyl ether sulfone) (PPSU), a polyphenylene sulfide (PPS), a poly(aryl ether ketone) (PAEK), e.g. a poly(ether ether ketone) (PEEK), a poly(ether ketone ketone) (PEKK), a poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer), a polylactide (PLA), a polyetherimide (PEI), a polycarbonate (PC), a polyphenylene oxide (PPO), polyvinylpyrrolidone (PVP) and / or polyethylene glycol (PEG), said PEG preferably having a molecular weight of at least 200 g / mol.

[0596] The article may comprise the functionalized copolymer (Pf) of the present invention in an amount of at least 1 wt. %, or at least 2 wt. %, or at least 3 wt. %, or at least 4 wt. %, or at least 5 wt. %, or at least 6 wt. %, or at least 7 wt. %, or at least 8 wt. %, based on the total weight of the polymers in the article, and / or may comprise the functionalized copolymer (Pf) of the present invention in an amount of more than 50 wt. %, for example more than 55 wt. %, or more than 60 wt. %, or more than 65 wt. %, or more than 70 wt. %, or more than 75 wt. %, or more than 80 wt. %, or more than 85 wt. %, or more than 90 wt. %, or more than 92 wt. %, or more than 95 wt. %, based on the total weight of the polymers in the article.

[0597] According to an embodiment, the chromatography polymeric stationary material may comprise the functionalized copolymer (Pf) and optionally another sulfone polymer distinct from the functionalized PAES copolymer (Pf), e.g., the aminated copolymer (Pf1), the copolymer (Pu), PSU, PESU, PPSU described herein, in an amount ranging from 1 to 99 wt. %, for example from 2 to 98 wt. %, or from 3 to 97 wt. % or from 4 to 96 wt. %, based on the total weight of polymers in the chromatography polymeric stationary material.

[0598] The article may further comprise at least one non-polymeric ingredient such as a solvent, a filler, a lubricant, a mold release, an antistatic agent, a flame retardant, an antifogging agent, a matting agent, a pigment, a dye, and / or an optical brightener.

[0599] Method for preparing the article

[0600] Another aspect of the present invention provides a method for preparing the article (or a part thereof) comprising the copolymer (Pf). Such method may be carried out in different ways. For example, the method may comprise performing one of the following: method (I) : using the copolymer (Pf) in forming the article or part thereof; or method (Ila) : contacting the copolymer (Pu) with a functional compound to make the copolymer (Pf) while at the same time forming the article or part thereof; or method (lib) : contacting the aminated copolymer (Pf1) with a compound Z* or bioactive compound B* to make the copolymer (P12) while at the same time forming the article or part thereof; method (Illa) : contacting a pre-formed article or part thereof comprising the copolymer (Pu) with a functional compound to make the copolymer (Pf), method (lllb) : contacting a pre-formed article or part thereof comprising the copolymer (Pf1) with a compound Z* or bioactive compound B* to make the copolymer (Pf), wherein the copolymer (Pu) in method (Ila) or method (Illa) comprises recurring units (R*pu) of formula (P), and recurring units (Rpu) of formula (M), as described herein; wherein the copolymer (Pf1) in method (lib) or method (lllb) comprises recurring units (R*pf) of formula (N) containing amine groups R200, and recurring units (Rpf) of formula (M), as described herein.

[0601] When the article is a membrane or a part thereof, the method preferably includes a phase inversion occurring in a liquid phase (e.g., precipitation bath) to form the membrane or part thereof.

[0602] In method (I), the article may be formed from a copolymer (Pf) solution.

[0603] The methods (Ila) and (lib) may be called in-situ method, while methods (Illa) and (lllb) may be called ex-situ method.

[0604] Yet an alternate method (IV) for preparing the article may be used to attach one or more functional compounds Z* or bioactive compounds B* in two (consecutive) steps:

[0605] 1 / attachment of at least one amine compound J200 onto copolymer (Pu) to make the aminated copolymer (Pf1) before or while forming the article; and

[0606] 2 / attachment of at least a functional compound Z* or bioactive compound B* onto the copolymer (Pf1) to form a copolymer (Pf2).

[0607] The beads according to the present invention can be manufactured using any of the conventionally known bead preparation methods, for example, by a solution casting method.

[0608] The membrane according to the present invention can be manufactured using any of the conventionally known membrane preparation methods, for example, by a solution casting or solution spinning method.

[0609] The membrane according to the present invention may be prepared by a phase inversion method occurring in a liquid phase, said method comprising the following steps:

[0610] (i) preparing a polymer solution comprising the copolymer (Pf) described herein and a polar solvent,

[0611] (ii) processing said polymer solution into a film; and

[0612] (iii) contacting said film with a non-solvent bath. Various embodiments of the method for making the article described herein (e.g., methods (I), (Ila), (lib), (Illa), (II lb), (IV)) are equally applicable to make the membrane.

[0613] The disclosure will now be illustrated with working examples, which are intended to illustrate the working of disclosure and not intended to take restrictively to imply any limitations on the scope of the present disclosure.

[0614] EXAMPLES

[0615] The invention will be now described in more details with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.

[0616] RAW MATERIALS

[0617] DCDPS (4,4’-dichlorodiphenyl sulfone) from Solvay Speciality Polymers (SYENSQO group) BPS (4,4’-dihydroxydiphenyl sulfone, also known as bisphenol S), available from Nicca BPA (Bisphenol A) from Covestro

[0618] BP (4,4’-biphenol) from SI Group, Inc.

[0619] TMPAE (trimethyloylpropane allyl ether), ISOSO (isosorbide, also known as 1 , 4:3,6- dianhydro-D-glucitol), chlorobenzene, DMSO (dimethylsulfoxide), thioglycolic acid, Sodium 3-mercapto-1 -propanesulfonate, Cysteamine. HCI, NMP (N-Methyl-2- pyrrolidone), AIBN (2,2'-Azobis(2-methylpropionitrile), ADVN (2,2'-azobis(2,4- dimethylvaleronitrile), 2-dimethylamino ethanethiol hydrochloride, lodomethane from Sigma-Aldrich, US.

[0620] K2CO3 (Potassium Carbonate) from Armand products

[0621] Sulfolane from Chevron Phillips.

[0622] TEST METHODS

[0623] GPC Method 1 for measuring Molecular weight (Mn, Mw) of unsaturated Sulfone Polymers (Pu)

[0624] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5pl mixed D columns with guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254 nm was used to obtain the chromatogram. A flow rate of 1 .5 ml / min and an injection volume of 20 pL of a 0.2 w / v% solution in the mobile phase were selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (Peak molecular weight range: 371 ,000 to 580 g / mol). The number average molecular weight Mn and weight average molecular weight Mw were reported.

[0625] GPC Method 2 for measuring Molecular weight (Mn, Mw) of functionalized copolymers (Pf)

[0626] Viscotek GPC Max (Autosampler, pump, and degasser) with a TDA302 triple detector array comprised of RALS (Right Angle Light Scattering), Rl (Refractive Index) and Viscosity detectors were used. Samples were prepared as ~2 mg / mL in DMAc / LiBr. Samples were run in NMP with 0.2 w / w% LiBr at 65°C at 1.0 mL / min through a set of 3 columns: a guard column (CLM1019 - with a 20k Da exclusion limit), a high Mw column (CLM1013 exclusion of 10MM Daltons relative to Poly Styrene) and a low Mw column (CLM1011 - exclusion limit of 20k Daltons relative to PS). Calibration was done with a single, mono-disperse polystyrene standard of ~100k Da. Light Scattering, Rl, and Viscosity detectors were calibrated based on a set of input data supplied with the standards. Samples were prepared as about 2 mg / mL in NMP / LiBr. Viscotek's OMNISec v4.6.1 Software was used for data analysis.

[0627] Thermal gravimetric analysis (TGA)

[0628] TGA experiments were carried out using a TA Instrument TGA Q500. TGA measurements were obtained by heating the sample at a heating rate of 10°C / min from 20°C to 800°C under nitrogen.

[0629] 1H NMR (Proton Nuclear Magnetic Resonance)

[0630] 1H NMR spectra were measured using a 400 MHz Bruker spectrometer with TCE or DMSO as the deuterated solvent. All spectra are reference to residual proton in the solvent.

[0631] Differential Scanning Calorimetry (DSC)

[0632] DSC was used to determine glass transition temperatures (Tg). DSC experiments were carried out using a TA Instrument Q100. DSC curves were recorded by heating, cooling, re-heating, and then re-cooling the sample between 25°C and 320°C at a heating and cooling rate of 20°C / min. All DSC measurements were taken under a nitrogen purge. The reported Tg values were provided using the second heat curve unless otherwise noted.

[0633] Amine content estimation

[0634] A sample of 0.2 to 0.3g of polymer was dissolved in 55 mL of methylene chloride with stirring. 15 mL of glacial acetic acid was added. The sample was then titrated potentionmetrically with 0.1 N perchloric acid in acetic acid using a Metrohm Titrando 809 Titrator with a Metrohm Solvotrode electrode. Perchloric acid titrant reacts with basic groups in the sample and produces an endpoint in the potential curve when all base has been neutralized. Two blanks and one control sample were tested prior to testing samples. Two replicates were run for each sample. The results were reported only after duplicate analyses agree within 5% for base concentration values above 100 peq / g or were within 10 peq / g for values below 100 peq / g.

[0635] Calculation of base concentration:

[0636] [Sample Base, peq / g] = ( / V perchloric acid) X (Vperchloric acid—blank) X 1000 / PVsample in which • Nperchioric acid = number of moles of perchloric acid (N);

[0637] • Vperchioric acid = volume (ml) of perchloric acid;

[0638] • Vbiank = volume (ml) of blank; and

[0639] • Wsampie = weight (g) of the sample.

[0640] The blank value was determined from the volume of titrant needed to achieve the same mV electrode potential as the sample titration endpoint potential.

[0641] Sodium content Analysis

[0642] The sodium concentration was measured by using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy) with scandium as an internal standard. About 2 g of polymer samples were ashed in a platinum crucible. The ash was dissolved in hydrochloric acid, diluted, and transferred to a volumetric flask. Samples were analyzed using ICP-AES following established instrument setup and calibration procedures by spectroscopic measurement of Na at 589.587 nm.

[0643] Calculations and reporting: Sodium concentration was calculated using the ICP-AES software or manually with the formula : A = B*CID wherein A was the concentration in mg / kg, B was the element concentration in the solution (mg / L), C was the solution volume analyzed (mL), and D was the sample weight (g).

[0644] Results were reported with their standard deviations to ensure accuracy, both in ppm on a weight basis.

[0645] Acid content Analysis

[0646] A representative portion of the polymer sample was weighed and dissolved in chlorobenzene:sulfolane 50:50, and pyridine, then was diluted with methylene chloride. The sample was spiked with a known concentration of spiking solution containing HCI, acetic acid and p-cumylphenol, dissolved in pyridine The end groups were titrated, using a potentiometric titrator, with tetrabutylammonium hydroxide in toluene / methanol. Three equivalence points were found during titration related to the strong acid, phenolic hydroxyl polymer end group, and the sulfonic hydroxyl polymer end group. Each end group was calculated based on the consumption of base used.

[0647] CALCULATIONS

[0648] Strong acid or base = [((VS1-VB1)N*1000) / ((W1-W2)S] in microequivalents / g of polymer Sulfone Hydroxyl = [((VS2-VS1)-(VB2-VB1))N*1000) / ((W1-W2)S] in microequivalents / g of polymer

[0649] Phenolic hydroxyl = [(VS3-VS2)-(VB3-VB2)]N*1000)Z ((W1-W2)S] in microequivalents / g of polymer wherein:

[0650] N = normality of the tetrabutylammoniumhydroxide solution;

[0651] W1 = for solutions, weight in grams of syringe plus polymer solution; W2 = for solutions, weight in grams of empty syringe after transferring the polymer solution;

[0652] W1 = for solid samples, weight of sample on tared weighing paper;

[0653] W2 = for solid samples, weight of residual sample remaining on weighing paper after transfer;

[0654] VB1 ,VB2,VB3 = amount of titrant in mL required to reach the first, second, and third equivalence points when spiking solution is titrated;

[0655] VS1 ,VS2,VS3 = amount of titrant in mL required to reach the first, second, and third equivalence points when sample solution is titrated; and

[0656] S = % solids of the sample (100% for solids)

[0657] Example 1 : Synthesis of unsaturated PPSU copolymer (Pu-A) by polycondensation of DCDPS (monomer CC) with 30 mol% TMPAE (as monomer AA’) and 70 mol% BP (as monomer BB’)

[0658] A batch of the unsaturated PPSU copolymer (Pu-A) was prepared according to following Scheme 1 , in which n represents the 70 mol% molar fraction of recurring unit (RPU) of formula (M’1 a) [being formula (M’1) with both i=0] and m represents the 30 mol% molar fraction of recurring unit (R*pu) of formula (P1 a) in the illustrated structure of the PPSU copolymer (Pu-A).

[0659] C2H5

[0660] HO-CH2-C-CH2OH

[0661] CH2o

[0662] CH2

[0663] CH Sulfolane II CH2K2CO3

[0664] 210 °C

[0665] Trimethylolpropane allyl ether

[0666] Scheme 1

[0667] The polymerization took place in a 2-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (287.16g, 1 mol), BP (130.34 g, 0.7 mol) and TMPAE (52.26 g, 0.3 mol) were added to the vessel first, followed by the addition of potassium carbonate (156.17g) and sulfolane (484 g). The reaction mixture was heated from room temperature to 210 °C using a 10°C / min heating ramp. The temperature of the reaction mixture was maintained at 210 °C for around eight hours, depending upon the viscosity of the solution. The reaction was terminated by passing excess methyl chloride gas through the reaction mixture for about 30 minutes and stopping the heat. The reaction mixture was filtered, and the copolymer in the filtrate was coagulated into methanol. The coagulated copolymer (Pu-A) was then washed with methanol and water and again with methanol and dried at 110°C.

[0668] The characterization (Mw, Mn, PDI measured by GPC Method 1 , Tg by DSC, TGA) of the unsaturated PPSU copolymer (Pu-A) is shown in Table 2.

[0669] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 5.22-5.87 ppm which indicated the incorporation of the TMPAE monomer in the polymer. The TMPAE content was estimated to be around 27 mol%.

[0670] The % olefin content (by1H NMR) of unsaturated PPSU copolymer (Pu-A) was 27 mol%.

[0671] Example 2: Synthesis of unsaturated PPSU-co-isosorbide-co-TMPAE copolymer (Pu-B) by polycondensation of DCDPS (monomer CC) with 12.5 mol% TMPAE (as monomer AA’), 12.5 mol% ISOSO (as monomer BB”), and 75 mol% BP (as monomer BB’)

[0672] A batch of PPSU-co-isosorbide-co-TMPAE copolymer (Pu-B) was prepared according to following Scheme 2, in which in the illustrated structure of the copolymer (Pu- B), n represents the 75 mol% molar fraction of first recurring unit (Rpu) of formula (M’1 a) [being formula (M’1) with both i=0]; m represents the 12.5 mol% molar fraction of recurring unit (R*pu) of formula (P1 a), and p represents the 12.5 mol% molar fraction of second recurring unit (Rpu) of (M”1 a) [being formula (M”1) with both i=0].

[0673] Scheme 2 The polymerization took place in a 2-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (287.16g, 1 mol), BP (139. 65 g, 0.75 mol), ISOSO (18.26 g, 0.125 mol) and TMPAE (21 .78 g, 0.125 mol) were added to the vessel first, followed by the addition of potassium carbonate (152.75 g, 1.13 mol), sulfolane (477 g) and chlorobenzene (160 g). The reaction mixture was heated from room temperature to 210 °C using a 10°C / min heating ramp, during which most of the chlorobenzene was distilled out of the reaction mixture. The temperature of the reaction mixture was maintained for around eight hours at 210 °C, depending upon the viscosity of the solution. The reaction was terminated by introducing methyl chloride gas and stopping the heat. The reaction mixture was filtered, and the copolymer in the filtrate was coagulated into methanol. The coagulated copolymer was then washed with methanol and water and again with methanol and dried at 110°C.

[0674] The characterization (Mw, Mn, PDI measured by GPC Method 1 , Tg by DSC, TGA) of the unsaturated copolymer (Pu-B) is shown in Table 2.

[0675] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 5.22-5.87 ppm which indicated the incorporation of the TMPAE monomer in the polymer. The TMPAE content was estimated to be around 11 mol%. The isosorbide content in the copolymer was estimated to be around 20.09 mol%.

[0676] The % olefin content (by1H NMR) of unsaturated copolymer (Pu-B) was 11 mol%.

[0677] Example 3: Synthesis of unsaturated PESU copolymer (Pu-C) by polycondensation of DCDPS (as monomer CC) with 18 mol% TMPAE (as monomer AA’) and 82 mol% BPS (as monomer BB’)

[0678] A batch of unsaturated PESU copolymer (Pu-C) was prepared according to following Scheme 3, in which in the illustrated structure of the copolymer (Pu-C), n represents the 82 mol% molar fraction of recurring unit (Rpu) of formula (M’2a) [being formula (M’2) with both i=0], and m represents the 18 mol% molar fraction of recurring unit (R*pu) of formula (P1 a).

[0679] The polymerization took place in a glass reactor vessel (2 L) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The monomers DCDPS (288.88 g, 1 mol), BPS (205.22 g, 0.82 mol), and TMPAE (31.36 g, 0.18 mol) were added to the vessel first, followed by the addition of potassium carbonate (140.96 g, 1.02), and sulfolane (551 g). The reaction mixture was heated from room temperature to 210 °C using a 150°C / mi heating ramp. The temperature of the reaction mixture was maintained for about six hours, depending upon the viscosity of the solution. The reaction was stopped by passing excess methyl chloride to endcap the copolymer (meaning reacting the -OH endgroups to form methoxy end groups). After endcapping, the reaction mixture was cooled and then filtered to remove the salts. Then the copolymer from the filtrate was coagulated into methanol. The coagulated copolymer was washed with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0680] Scheme 3

[0681] The characterization (Mw, Mn, PDI measured by GPC Method 1 , Tg by DSC, TGA) of the unsaturated copolymer (Pu-C) is shown in Table 2.

[0682] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 5.22-5.82 ppm which indicated the incorporation of 16.5 mol% TMPAE monomer in the (Pu-C) copolymer. The % olefin content (by1H NMR) of unsaturated copolymer (Pu-C) was 16.5 mol%.

[0683] Example 4: Synthesis of an acid functionalized PPSU copolymer (Pf-A)

[0684] A batch of an acid functionalized PPSU copolymer (Pf-A) was prepared starting from unsaturated copolymer (Pu-A) according to following Scheme 4, in which in the illustrated acid functionalized PPSU copolymer (Pf-A), n represents the 70 mol% molar fraction of recurring unit (Rpf) and m represents the 30 mol% molar fraction of acid functionalized recurring unit (R*pf).

[0685] In a 500 mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 300 g of the reaction solution for unsaturated copolymer (Pu-A) obtained in Example 1 was added along with thioglycolic acid (7.46 g) and heated to 80 °C with constant stirring. Once the temperature of 80 °C was reached, AIBN (2.2 g) was added all at once and the reaction was allowed to continue at least for 24 hours. After 24 hours, the heating was stopped, and the copolymer was recovered by coagulating the reaction mixture in methanol. The coagulated copolymer was washed with water twice and with methanol twice. The copolymer was then dried at 110 °C for 12 hours under vacuum. The characterization (Mw, Mn, PDI measured by GPC Method 2, Tg by DSC, TGA) of the copolymer (Pf-A) is shown in Table 3. The acid content of the copolymer (Pf-A) was 136 microeq / g. No olefinic signals could be detected by1H NMR indicating complete conversion of the olefin groups

[0686] Carboxylic acid functionalization CH2

[0687] CH2CH2SCH2COOH

[0688] Scheme 4

[0689] Example 5: Synthesis of an amine functionalized PPSU copolymer (Pf-B) (30%)

[0690] A batch of an amine functionalized PPSU copolymer (Pf-B) was prepared starting from unsaturated copolymer (Pu-A) according to following Scheme 5, in which in the illustrated amine functionalized PPSU copolymer (Pf-B), n represents the 70 mol% molar fraction of recurring unit (Rpf) and m represents the 30 mol% molar fraction of amine functionalized recurring unit (R*pf).

[0691] In a 500 mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 200 g of the reaction solution obtained for unsaturated copolymer (Pu- A) in Example 1 was added along with Cysteamine. HCI (60.04 g) and heated to 50 °C with constant stirring. Once the temperature of 50 °C was reached, ADVN (18.75 g) was added all at once, and the reaction was allowed to continue at least for 24 hours. After 24 hours, the heating was stopped, and the polymer was recovered by coagulating the reaction mixture in water. The coagulated solid polymer was washed with water five times and with methanol twice. The polymer was then dried at 110 °C for 12 hours under vacuum.

[0692] The characterization (Mw, Mn, PDI measured by GPC Method 2, Tg by DSC, TGA) of the copolymer (Pf-B) is shown in Table 3. The amine content of the copolymer (Pf-B) was 448 microEq / g. No olefinic signals could be detected by1H NMR indicating complete conversion of the olefin groups. i

[0693] Amine functionalization CH2

[0694] CH2CH2SCH2CH2NH2

[0695] Scheme 5

[0696] Example 6: Synthesis of a sulfonate functionalized PESU copolymer (Pf-C)

[0697] A batch of a sulfonate functionalized PESU copolymer (Pf-C) was prepared starting from unsaturated copolymer (Pu-C) according to following Scheme 6, in which in the illustrated structure of the sulfonate functionalized copolymer (Pf-C), n represents the 82 mol% molar fraction of recurring unit (Rpf), and m represents the 18 mol% molar fraction of functionalized recurring unit (R*pf).

[0698] Scheme 6 In a 500 mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 60 g of the unsaturated PESU copolymer (Pu-C) made in Example 3 was added along with DMSO (140 g) and heated to 85 °C with constant stirring. Once the temperature of 85 °C was reached, Sodium 3-mercapto-1 -propanesulfonate (12.29 g) was added and stirred till a homogenous solution was obtained. Then AIBN (1.88 g) was added in a single portion, and the reaction was allowed to continue at least for 24 hours. After 24 hours, the heating was stopped, and the polymer was recovered by coagulating the reaction mixture in methanol. The coagulated copolymer was washed with water twice and with methanol twice. The copolymer was then dried at 110 °C for 12 hours under vacuum.

[0699] The characterization (Mw, Mn, PDI measured by GPC Method 2, Tg by DSC, TGA) of the copolymer (Pf-C) is shown in Table 3. The sodium (Na) content of the copolymer (Pf-C) was 7657 ppm Na. No olefinic signals could be detected by1H NMR indicating complete conversion of the olefin groups.

[0700] Example 7: Synthesis of a sulfonate functionalized PPSU-co-lsosorbide-co-TMPAE copolymer (Pf-D)

[0701] A batch of a sulfonate functionalized PPSU-co-lsosorbide-co-TMPAE copolymer (Pf-D) was prepared starting from unsaturated copolymer (Pu-B) according to following Scheme 7, in which in the illustrated sulfonate functionalized PPSU copolymer (Pf-D), n represents the 75 mol% molar fraction of first recurring unit (Rpf); m represents the 12.5 mol% molar fraction of sulfonate functionalized recurring unit (R*pf), and p represents the

[0702] 12.5 mol% molar fraction of second recurring unit (Rpf).

[0703] Scheme 7 In a 500 mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 40 g of the unsaturated copolymer (Pu-B) made in Example 2 was added along with DMSO (93 g) and heated to 85 °C with constant stirring. Once the temperature was reached, Sodium 3-mercapto-1 -propanesulfonate (6.68 g) was added and stirred till a homogenous solution was obtained. Then AIBN (1.02 g) was added in a single portion, and the reaction was allowed to continue at least for 24 hours. After 24 hours, the heating was stopped, and the copolymer was recovered by coagulating the reaction mixture in methanol. The coagulated copolymer was washed with water twice and with methanol twice. The copolymer was then dried at 110 °C for 12 hours under vacuum.

[0704] The characterization (Mw, Mn, PDI measured by GPC Method 2, Tg by DSC, TGA) of the copolymer (Pf-D) is shown in Table 4. The sodium (Na) content of the copolymer (Pf-D) was 5825 ppm Na. No olefinic signals could be detected by1H NMR indicating complete conversion of the olefin groups.

[0705] Example 8: Synthesis of a dimethyl amino functionalized PESU-co-TMPAE copolymer (Pf-E)

[0706] A batch of a sulfonate functionalized PESU-co-lsosorbide-co-TMPAE copolymer (Pf-E) was prepared starting from unsaturated copolymer (Pu-C) according to following Scheme 8, in which in the illustrated structure of the functionalized copolymer (Pf-E), n represents the 82 mol% molar fraction of recurring unit (Rpf) and m represents the 18 mol% molar fraction of dimethyl amino functionalized recurring unit (R*pf).

[0707] Scheme 8

[0708] In a 500 mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 100 g of the unsaturated copolymer (Pu-C) obtained in Example 3 was added along with NMP (100 g) and heated to 75 °C with constant stirring. Once the temperature of 75 °C was reached, 2-dimethylamino ethanethiol hydrochloride (16.57 g) was added and stirred till a homogenous solution was obtained. Then AIBN (3.2 g) was added in a single portion, and the reaction was allowed to continue at least for 24 hours. After 24 hours, the heating was stopped, and the polymer was recovered by coagulating the reaction mixture in methanol. The coagulated copolymer was washed with water twice and with methanol twice. The polymer was then dried at 110 °C for 12 hours under vacuum.

[0709] The characterization (Mw, Mn, PDI measured by GPC Method 2, Tg by DSC, TGA) of the copolymer (Pf-E) is shown in Table 4. No olefinic signals could be detected by1H NMR indicating complete conversion of the olefin groups. The functionalization was qualitatively detected by1H NMR, however the quantification was not possible due to overlapping signals

[0710] Example 9: Synthesis of a quaternary ammonium iodide functionalized PESU-co- TMPAE copolymer (Pf-F)

[0711] A batch of a quaternary ammonium iodide functionalized PESU-co-TMPAE copolymer (Pf-F) was prepared starting from dimethyl amino functionalized copolymer (Pf- E) according to following Scheme 9, in which in the illustrated structure of the functionalized copolymer (Pf-F), n represents the 82 mol% molar fraction of recurring unit (Rpf) and m represents the 18 mol% molar fraction of quaternary ammonium iodide functionalized recurring unit (R*pf).

[0712] Scheme 9 In a 100 mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 20 g of the dimethyl amino functionalized PESU-co-TMPAE copolymer (Pf-E) obtained in Example 8 was added along with DMF (50 g) and heated to 60 °C with constant stirring. Once the temperature of 60 °C was reached, iodomethane (50 g) was added and stirred till a homogenous solution was obtained, the reaction was allowed to continue at least for 24 hours. After 24 hours, the heating was stopped, and the polymer was recovered by coagulating the reaction mixture in methanol. The coagulated polymer was washed with water twice and with methanol twice. The polymer was then dried at 110 °C for 12 hours under vacuum.

[0713] The characterization (Mw, Mn, PDI measured by GPC Method 2, Tg by DSC, TGA) of the copolymer (Pf-F) is shown in Table 5. The content of trimethylamino groups in copolymer (Pf-F) was 10.4 mol%.

[0714] Example 10: Synthesis of a sulfobetaine functionalized PESU-co-TMPAE polymer (Pf-G)

[0715] A batch of a sulfobetaine functionalized PESU-co-TMPAE copolymer (Pf-G) was prepared starting from dimethyl amino functionalized copolymer (Pf-E) according to following Scheme 10, in which in the illustrated structure of the functionalized copolymer (Pf-F), n represents the 82 mol% molar fraction of recurring unit (Rpf) and m represents the

[0716] 18 mol% molar fraction of sulfobetaine functionalized recurring unit (R*pf).

[0717] Scheme 10 ln a 100 mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer, 20 g of the dimethyl amino functionalized PESU-co-TMPAE copolymer (Pf-E) obtained in Example 8 was added along with DMF (300 g) and heated to 60 °C with constant stirring. Once the temperature of 60 °C was reached, 1 ,3-propane sultone (1.9 g) was added and stirred till a homogenous solution was obtained, the reaction was allowed to continue at least for 24 hours. After 24 hours, the heating was stopped, and the polymer was recovered by coagulating the reaction mixture in methanol. The coagulated copolymer was washed with water twice and with methanol twice. The copolymer was then dried at 110 °C for 12 hours under vacuum.

[0718] The characterization (Mw, Mn, PDI measured by GPC Method 2, Tg by DSC, TGA) of the copolymer (Pf-G) is shown in Table 5.

[0719] 1H NMR: The copolymer product was analyzed by1H NMR, the incorporation of the (- CH2CH2CH2SO3 ) was confirmed by the presence of a triplet at ~4.2 ppm and the presence of a multiplet at ~1 .9 ppm, however the exact quantification was not possible due to overlapping signals

[0720] TABLE 2 summarizes the main characteristics of the unsaturated copolymers (Pu- A) to (Pu-C). TABLES 3, 4 and 5 summarize the main characteristics of the functionalized copolymers (Pf-A) to (Pf-F).

[0721] TABLE 2 - unsaturated copolymers TABLE 3 - primary functionalization of unsaturated copolymers

[0722] TABLE 4 - primary functionalization of unsaturated copolymers

[0723] TABLE 5 - secondary functionalization of amine functionalized copolymers

[0724] The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of systems and methods are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention. What is claimed is:

Claims

C L A I M SClaim 1. A functionalized copolymer (Pf) comprising at least 60 mol%, based on the total amount of moles of recurring units in the copolymer (Pf), of- at least one recurring unit (Rpf) of formula (M)[-Ar-SO2-Ar’-O-W-O-] (M),- at least one recurring unit (R*pf) of formula (N):[-Ar-SO2-Ar’-O-E-O-] (N), wherein• Ar-SO2-Ar’ is a diaryl sulfone moiety derived from at least one dihalodiary I sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group;• W is a moiety derived from at least one diol (BB) being selected from the group consisting of aromatic diols, saturated alicyclic diols and saturated acyclic diols;• E is a functionalized aliphatic moiety derived from at least one dihydroxy aliphatic allyl monomer (AA’), and• E comprises at least one functionalized end moiety Ea represented by following formula (Ea1) and / or formula (Ea2), at least one functionalized divalent moiety Eb represented by following formula (Eb1) and / or formula (Eb2), or combination thereof,• the formulae (Ea1), (Ea2), (Eb1), (Eb2) being as follows:in which R is a functional group, and in which the symbol represents a part at which the moieties Ea and Eb are connected to a carbon atom in the functionalized aliphatic moiety E of the recurring unit (R*pf) of formula (N).Claim 2. The functionalized copolymer (Pf) of claim 1 , wherein the functional group R in any of the formulae (Ea1), (Ea2), (Eb1), (Eb2) is selected from the group consisting of:• group R110 represented by formula (110) : **- (CH2)a- COCH3 with a being an integer from 0 to 10,• group R120 represented by formula (120) : **- C(O)Rmwith Rm being a C1-C6 alkyl or H, preferably H,• group R130 represented by formula (130) : **- (CH2)b - OH with b being an integer from 1 to 5,• group R140 represented by formula (140) : **- (CH2)d - SOs- M+with d being an integer from 1 to 5, and with M+being H+or an alkali metal cation, preferably H+, Na+, K+or Li+,• group R150 represented by formula (150) : **- (CH2)e - Si (OCH3)3 with e being an integer from 1 to 5,• group R160 represented by formula (160) : **- (CH2)f - (CF2)g - CF3 with f being an integer from 1 to 5 and with g being an integer from 1 to 10,• group R170 represented by formula (170) : (CH2)h - COOH with h being an integer from 1 to 5,• group R180 represented by formula (180) : **- (CH2)k- CH3 with k being an integer from 5 to 30,• group R190 represented by formula (190) : **- (CH2)I - Ar1with I being an integer from 1 to 10 and with Ar1comprising one or two aromatic or heteroaromatic rings;• group R200 represented by formula (200) : **- (CH2)h - NRa b with h being an integer from 1 to 5, and with Raand Rb being independently H or a C1- C6 alkyl, preferably H or CH3; and• any combination thereof.Claim 3. The functionalized copolymer (Pf) of claim 1 , wherein the functional group R in any of the formulae (Ea1), (Ea2), (Eb1), (Eb2) is selected from:• group R210 of formula (210) : **- (CH2)h - NRaB, with h being an integer from 1 to 5, with Rabeing H or a C1-C6 alkyl, preferably H or CH3, and with B representing a bioactive moiety which is covalently and / or ionically bound to the nitrogen atom in R and B being derived from a compound B* selected from the group consisting of:- antithrombotic agents or derivatives thereof, such as heparin,- amino acids, such as proteinogenic (native) amino acids which are naturally encoded in the genome of organisms and / or non-proteinogenic amino acids including unnatural amino acids synthetically prepared from their native analogs via modifications such as amine alkylation, side chain substitution, structural bond extension cyclization, and isosteric replacements within the amino acid backbone;- nucleic acids (polymers made up of nucleotides), such as oligonucleotides (with typically 12-25 base pairs), RNAs (e.g., tRNA, mRNA, pre-mRNA, small nuclear RNA (snRNA), microRNA (miRNA), and small interfering RNA (siRNA), DNA (e.g., singlestranded DNA, double-stranded DNA),- glucuronic acid, glucuronic acid derivatives or glucuronic acid residues,- hyaluronic acid or hyaluronic acid derivatives or hyaluronic acid residues,- proteins, such as collagen, keratin, small peptides (generally therapeutic proteins that have less than 100 amino acids), or enzymes,- metal-chelating and / or protease inhibitor agents such as ethylene glycol tetraacetic acid (EGTA) or ethylene diamine tetraacetic acid (EDTA);- acidic lipids, such as prostaglandins, and- any combinations of two or more compounds thereof;• group R220 represented by formula (220):with h being an integer from 1 to 5, with Ra, Rb being independently H or a C1-C6 alkyl, preferably H or CH3, with Rs being independently a C1-C6 alkyl, preferably CH3, and X being a halide;• group R230 represented by formula (230):with h being an integer from 1 to 5, with Ra, Rb being independently H or a C1-C6 alkyl, preferably H or CH3, and with Rvbeing a group of formula (CH2)x with x being 3 or 4; and / or• group R240 represented by formula (240): ** - (CH2)h - NRaZ with h being an integer from 1 to 5, and Ra being H or a C1-C6 alkyl, preferably H or CH3, in which Z, being covalently and / or ionically bound to the nitrogen atom in the group R240, is selected from the group consisting of: an alkyl carbonyl moiety Z3;a carboxylic acid moiety Z4; an aromatic sulfonate moiety Z5 ; a sugar acid moiety Z6; a zwitterionic moiety Z7; a haloalkyl carbonyl moiety Z8; a hydroxyl moiety Z9; a combination of an olefinic moiety with another moiety selected from Z3 to Z9 [ moiety Z10], such as a combination of olefinic moiety and carboxylic acid moiety Z4; and any combination of moieties Z3 to Z9; or• any combination of two or more of these groups.Claim 4. The functionalized copolymer (Pf) of any one of claims 1 to 3, comprising at least 60 mol%, based on the total amount of moles of recurring units in the functionalized copolymer (Pf), of :- recurring unit (R*pf) of the formula (N) and recurring unit (Rpf) of formula (M’); or- recurring unit (R*pf) of the formula (N) and recurring unit (Rpf) of formula (M”);- recurring unit (R*pf) of the formula (N) and recurring unit (Rpf) of formula (M’”);- recurring unit (R*pf) of the formula (N), recurring unit (Rpf) of formula (M’) and recurring unit (Rpf) of formula (M”);- recurring unit (R*pf) of the formula (N), recurring unit (Rpf) of formula (M’) and recurring unit (Rpf) of formula (M’”);- recurring unit (R*pf) of the formula (N), recurring unit (Rpf) of formula (M”) and recurring unit (Rpf) of formula (M’”); wherein the formulae (M’), (M”) and (M’”) are as follows :[-Ar-SO2-Ar’-O-W’-O-] (M’),[-Ar-SO2-Ar’-O-W”-O-] (M”),[-Ar-SO2-Ar’-O-W’”-O-] (M’”), wherein • Ar-SO2-Ar’ and E are the same as defined in claim 1 ;W’ is an aromatic moiety derived from at least one aromatic diol (BB’);W” is a cycloaliphatic moiety derived from at least one alicyclic diol (BB”); and W’” is an acyclic moiety derived from at least one acyclic diol (BB’”).Claim 5. The functionalized copolymer (Pf) of any one of claims 1 to 4, wherein the recurring units (R*pf) are represented by formula (N1), formula (N2) and / or formula (N3),(N3), in which• each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;• each i is independently 0, 1 , 2, 3 or 4, preferably 0 or 1 , more preferably 0;• the moieties Ea and Eb are defined in claim 1 ;• each of Ra, Rbis independently represented by -(CH2)a- , -CHRh- -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)a- , -CHfCHs)-, -(CH2)a-CH(CH3)- or- CH(CH3)-CH2)a- , with a being 1 or 2;• each of Rf, Rgis independently represented by -(CH2)a- , -(CHRh)p-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6,preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)«- with cz being an integer from 1 to 3, or preferably 1 or 2;• each of x1 , x2 is independently 0 or 1 , with the proviso that x1+x2=1 or 2;• each of y1 , y2 is independently 0 or 1 , with the proviso that y1+y2=1 or 2;• each of z1 , z2 is independently 0 or 1 , with the proviso that z1+z2=1 or 2;• each Rcis independently represented by -(CH2)Z- or -(CH2)8-O-(CH2)e-, with / being an integer from 1 to 6, with 5 being 0 , 1 or 2, with e being an integer from 1 to 6; preferably represented by -CH2- ,-(CH2>2- , -CH2-O-CH2-, -(CH2)2-O-(CH2)2- -CH2-O-(CH2)2- or -(CH2)2-O-CH2-;• each Rdis independently represented by a C1-C5 alkyl group, preferably -CH3 , -CH(CH3)2, -C(CH3>3, -C2H5 or -C3H7, more preferably -CH3, -C2H5 or -CH(CH3)2; and• each Reis independently represented by -H, a C1-C5 alkyl group, an alcohol group, or an ether group -R1-O-R2 in which R1 is a C1-C6 alkylene and R2 is a C1-C5 alkyl group, preferably with R1 being -(CH2)a- , -(CHRh)p-, -(CH2)a- (CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 3, preferably 1 or 2, with p being an integer from 1 to 3, preferably 1 or 2, with Rhbeing CH3 or C2H5, and with R2 being preferably being CH3 or C2H5.Claim 6. The functionalized copolymer (Pf) of any one of claims 1 to 5, wherein the recurring units (R*pf) are represented by following formula (N1 a) and / or formula (N1 b):(N1 b), in which R is the functional group.Claim 7. The functionalized copolymer (Pf) of any one of claims 1 to 6, wherein the recurring units (Rpf) are represented by any of following formulas (M’1), (M’2), (M’3), (M’4), (M”1), (M”2), (M”3) and / or (M’”1):(M”’1 a), preferably represented by formula (M’1), (M’2), (M’3), (M”1) and / or (M”’1 a), more preferably represented by formula (M’1), (M”1) and / or (M”’1 a), wherein• each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;• each i is independently 0, 1 , 2, 3 or 4, preferably i=0.Claim 8. The functionalized copolymer (Pf) of any one of claims 1 to 7, wherein the recurring units (R*pf) and (Rpf) are such that the molar ratio r1 of the recurring units (R*pf) to the recurring units (Rpf) is:• at most 45:55, preferably at most 40:60, more preferably at most 35:65, still more preferably at most 30:70, and• at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88.Claim 9. A process for making the functionalized copolymer (Pf) of any one of claims 1 to8, comprising: reacting in a solvent an unsaturated copolymer (Pu) comprising at least 60 mol%, based on the total amount of moles of recurring units in the unsaturated copolymer (Pu), of:- at least one recurring unit (Rpu) of formula (M):[-Ar-SO2-Ar’-O-W-O-] (M),- at least one recurring unit (R*pu) of formula (P):[-Ar-SO2-Ar’-O-E’-O-] (P), wherein• Ar-SO2-Ar’ is a diaryl sulfone moiety derived from at least one dihalodiary I sulfone monomer (CC), in which each of Ar, Ar’, independent from each other, is an unsubstituted or substituted divalent arylene group, preferably an unsubstituted divalent arylene group;• W is a moiety derived from at least one diol (BB) being selected from the group consisting of aromatic diols, saturated alicyclic diols and saturated acyclic diols;• E’ is an unsaturated aliphatic moiety derived from at least one dihydroxy aliphatic allyl monomer (AA’); and• E’ comprises at least one unsaturated end moiety E’a represented by formula (E’a1), at least one unsaturated divalent moiety E’b represented by formula (E’b1), or combination thereof,• the formulae (E’a1), (E’b1) being as follows:*— CH = CH2(E’a1)*— CH = CH — * (E’b1) in which the symbol represents a part at which the moieties E’a and E’b are connected to a carbon atom in the unsaturated aliphatic moiety E’ of the recurring unit (R*pu) of formula (P), with a compound of formula (I): R - SH , wherein R is selected from the group consisting of:• group R110 represented by formula : **- (CH2)a - COCH3 with a being an integer from 0 to 10,• group R120 represented by formula : **- C(O)Rmwith Rm being a C1-C6 alkyl or H, preferably H,• group R130 represented by formula : **- (CH2)b - OH with b being an integer from 1 to 5,• group R140 represented by formula : **- (CH2)d - SOs- M+with d being an integer from 1 to 5, and with M+being H+or an alkali metal cation, preferably H+, Na+, K+or Li+,. group R150 represented by formula : **- (CH2)e - Si (OCH3)3 with e being an integer from 1 to 5,• group R160 represented by formula : **- (CH2)f - (CF2)g - CF3 with f being an integer from 1 to 5 and with g being an integer from 1 to 10,• group R170 represented by formula : **- (CH2)h - COOH with h being an integer from 1 to 5,. group R180 represented by formula : **- (CH2)k- CH3, with k being an integer from 5 to 30,. group R190 represented by formula : **- (CH2)I - Ar1with I being an integer from 1 to 10 and with Ar1comprising one or two aromatic or heteroaromatic rings;• group R200 represented by formula : **- (CH2)h - NRaRb with h being an integer from 1 to 5, and with Raand Rb being independently H or a C1-C6 alkyl, preferably H or CH3; and• any combination thereof, wherein the symbol represents a part at which the group R is connected to the sulfur atom in the compound (I).Claim 10. The process of claim 9, wherein the recurring unit (R*pu) is represented by(P3), in which• each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;• each i is independently 0, 1 , 2, 3 or 4, preferably 0 or 1 , more preferably 0;• each of Ra, Rbis independently represented by -(CH2)a- , -CHRh- -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)a- , -CHfCHs)-, -(CH2)a-CH(CH3)- or -CH(CH3)-CH2)a- , with a being 1 or 2;• each of Rf, Rgis independently represented by -(CH2)a- , -(CHRh)p-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 6, preferably from 1 to 3, more preferably 1 or 2, with being an integer from 1 to 3, preferably 1 or 2, and with Rhbeing an C1-C5 alkyl, preferably CH3 or C2H5; preferably represented by -(CH2)«- with cz being an integer from 1 to 3, or preferably 1 or 2;• each of x1 , x2 is independently 0 or 1 , with the proviso that x1+x2=1 or 2;• each of y1 , y2 is independently 0 or 1 , with the proviso that y1+y2=1 or 2;• each of z1 , z2 is independently 0 or 1 , with the proviso that z1+z2=1 or 2;• each Rcis independently represented by -(CH2)Z- or -(CH2)s-O-(CH2)e-, with / being an integer from 1 to 6, with 5 being 0 , 1 or 2, with e being an integer from 1 to 6; preferably represented by -CH2- ,-(CH2)2- , -CH2-O-CH2-, -(CH2)2-O-(CH2)2- -CH2-O-(CH2)2- or -(CH2)2-O-CH2-;• each Rdis independently represented by a C1-C5 alkyl group, preferably -CH3 , -CH(CH3)2, -C(CH3>3, -C2H5 or -C3H7, more preferably -CH3, -C2H5 or -CH(CH3)2; and• each Reis independently represented by -H, a C1-C5 alkyl group, an alcohol group such as R1-OH, or an ether group -R1-O-R2 in which R1 is a C1-C6 alkylene and R2 is a C1-C5 alkyl group, preferably with R1 being -(CH2)a- , -(CHRh)p-, -(CH2)a-(CHRh)p- or -(CHRh)p-(CH2)a- , with a being an integer from 1 to 3, preferably 1 or 2, with p being an integer from 1 to 3, preferably 1 or 2, with Rhbeing CH3 or C2H5, and with R2 being preferably being CH3 or C2H5.Claim 11. The process of claim 9 or claim 10, wherein the recurring unit (R*pu) is represented by following formula (P1 a) or (P3a), still more preferably represented by formula (P1 a):(P3a).Claim 12. The process of any one of claims 9 to 11 , wherein the recurring units (Rpu) are represented by any of following formulas (M’1), (M’2), (M’3), (M’4), (M”1), (M”2), (M”3) and / or (M’”1), preferably represented by formula (M’1), (M’2), (M’3), (M”1) and / or (M’”1), more preferably represented by formula (M’1), (M”1) and / or (M’”1):(M’4),(M’”1), wherein• each R’ is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;• each i is independently 0, 1 , 2, 3 or 4; and• n is an integer being from 2 to 15.Claim 13. The process of any one of claims 9 to 12, wherein the process is being carried out using at least one of following features i) to iv): i) the presence of at least one free radical initiator selected from 2,2'-Azobis(2- methylpropionitrile) (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN); ii) the presence of at least one catalyst selected from peroxides; iii) the presence of a base selected from the group consisting of N-Ethyl-N-(propan-2- yl)propan-2-amine (Hunig base), triethylamine (TEA) and pyridine;iv) the exposure to UV light at a wavelength ranging from 300 nm to 600 nm, preferably from 350 nm to 450 nm., more preferably at 365 nm.Claim 14. The process of any one of claims 9 to 13, wherein, for a first functionalization step (A), the process uses a compound J200 of formula:HS- (CH2)h - NRaRb , with h being an integer from 1 to 5, with Rabeing H or CH3, and with Rb being H or CH3, to react with C=C bonds in the unsaturated copolymer (Pu) so as to form an aminated copolymer (Pfi) containing amine functional groups R200 of formula (200): -(CH2)h - NRaRb ; and for a second functionalization step (B), the process comprises reacting the aminated copolymer (Pf1) containing the amine functional group R200 with another functional compound so as to form a second-functionalized copolymer (Pf2), said second functionalization step (B) being carrying out in following step (B2) or step (B2’): step (B2): contacting the aminated copolymer (Pfi) having the amine groups R200 of formula (200) with Rb being H with a bioactive compound B*, optionally in the presence of a coupling agent, in an acidic aqueous solvent, preferably of pH from 3 to 6, or from 4.2 to 5, or from 4.4 to 4.8, to bind the bioactive compound B* whereby the amine group R200 of formula: - (CH2)h - NRaH is converted to a group R210 of formula (210): **- (CH2)h - NRaB , so as to form a second functionalized copolymer (Pf2) having the group R210, with h and Ra in group R210 being the same as in amine group R200, and with B being derived from the bioactive compound B*,B in group R210 representing a bioactive moiety which is covalently and / or ionically bound to the nitrogen atom in the group R210, the bioactive compound B* being selected from the group consisting of:- antithrombotic agents or derivatives thereof, such as heparin,- amino acids, such as proteinogenic (native) amino acids which are naturally encoded in the genome of organisms and / or non-proteinogenic amino acids including unnatural amino acids synthetically prepared from their native analogs via modifications such as amine alkylation, side chain substitution, structural bond extension cyclization, and isosteric replacements within the amino acid backbone;- nucleic acids (polymers made up of nucleotides), such as oligonucleotides (with typically 12-25 base pairs), RNAs (e.g., tRNA, mRNA, pre-mRNA, small nuclearRNA (snRNA), microRNA (miRNA), and small interfering RNA (siRNA), DNA (e.g., single-stranded DNA, double-stranded DNA),- glucuronic acid, glucuronic acid derivatives or glucuronic acid residues,- hyaluronic acid or hyaluronic acid derivatives or hyaluronic acid residues,- proteins, such as collagen, keratin, small peptides (generally therapeutic proteins that have less than 100 amino acids), or enzymes,- metal-chelating and / or protease inhibitor agents such as ethylene glycol tetraacetic acid (EGTA) or ethylene diamine tetraacetic acid (EDTA);- acidic lipids, such as prostaglandins, and- any combinations of two or more compounds thereof; or step (B2’): contacting the first functionalized copolymer (Pf1) having the amine groups R200 of formula (200): - (CH2)h - NRaRb with a functional compound Z*, optionally in the presence of a coupling agent, in an organic solvent, to couple the functional compound Z* to make a second functionalized copolymer (Pf2’), in which the amine group R200 in the first functionalized copolymer (Pf1) is converted:• to a group R220 represented by formula (220):with h being an integer from 1 to 5, with Ra , Rb being independently H or a C1-C6 alkyl, preferably H or CH3, with Rs being independently a C1-C6 alkyl, preferably CH3, and X being a halide; with a functional compound Z1* being an haloalkane of formula XRS;• to a group R230 represented by formula (230):with h being an integer from 1 to 5, with Ra, b being independently H or a C1-C6 alkyl, preferably H or CH3, and with Rvbeing a group of formula (CH2)x with x being 3 or 4, with a functional compound Z2* being a cyclic sulfonate ester of formula RvOsS, preferably selected from 1 ,3-propane sultone or 1 , 4, butane sultone; or• to a group R240 represented by formula (240): ** - (CH2)h - NRaZ in which h, Ra are the same as in the group R200 ; Z, being covalently and / or ionically bound to the nitrogen atom in the group R240, is selected from the group consisting of:• an alkyl carbonyl moiety Z3;• a carboxylic acid moiety Z4;• an aromatic sulfonate moiety Z5 ;• a sugar acid moiety Z6;• a zwitterionic moiety Z7;• a haloalky I carbonyl moiety Z8;• a hydroxyl moiety Z9; and• a combination of olefinic and carboxylic acid moieties Z10, with a functional compound Z* respectively selected from the group consisting of- an alkanoyl halide [compound Z3*];- a carboxylic acid anhydride [compound Z4* ];- an aromatic sulfonic acid or sulfonate salt [compound Z5*];- a sugar acid or salt thereof [compound Z6*];- a betaine (meth)acrylate zwitterionic compound [compound Z7*];- a haloacetyl halide [compound Z8*];- a linear or cyclic alcohol or polyol [compound Z9*]; and- maleic anhydride [compound Z10*].Claim 15. The process of any one of claims 9 to 14, wherein the unsaturated copolymer (Pu) is prepared by condensation of:• at least one dihalodiaryl sulfone monomer (CC) of formula (C) :X-Ar-SC -Ar’-X’, in which each of X, X’ is independent from each other, is a halide, preferably Cl or F;• at least one diol (BB) being of formula : HO-W-OH and being selected from the group consisting of aromatic diols, saturated alicyclic diols, and saturated acyclic diols; and• at least one dihydroxy aliphatic allyl monomer (AA’) being of formula : HO-E’-OH, in which Ar, Ar’, W and E’ are the same as in claim 9.Claim 16. Use of the functionalized copolymer (Pf) of any one of claims 1 to 8, in the preparation of an article being selected from the group consisting of medical devices, implants, membranes, beads, coatings, melt processed films, solution processed films, melt process monofilaments and fibers, solution processed monofilaments, hollow fibers and solid fibers, coatings, printed objects, and injection and compression molded objects, preferably membranes being selected from membranes for bioprocessing, membranes for biological fluid nitrations (such as hemodialysis membranes), membranes for food and beverage processing, membranes for water purification, membranes for waste water treatment and membranes for industrial process separations involving aqueous media.

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