Unsaturated poly(aryl ether sulfone) copolymer

Abstract

An unsaturated poly(arylethersulfone) (PAES) copolymer comprising C=C bonds on its main polymeric chain and / or on side chains, made from condensation of an aliphatic allyl monomer (AA) comprising at least one C=C bond and being selected from dihydroxy monomers (AA') and / or dihalogenated monomers (AA"), at least one diol (BB) selected from aromatic diols (BB'), alicyclic diols (BB") and / or acyclic diols (BB'"), and a dihalodiaryl sulfone monomer (CC). Monomer (AA') may be a α,ω-dihydroxy C4-C10 alkene and / or a C7-C15 allyl ether, preferably trimethylolpropane allyl ether. Monomer (AA") may be a α,ω-dichloro C4-C10 alkene. Diol (BB) may be an aromatic diol (BB') preferably having low-endocrine activity, an alicyclic diol (BB") preferably being bio-based, and / or an acyclic diol (BB'") preferably being a C2-C6 alkylene glycol. Monomer (CC) comprises dihalodiphenylsulfone, preferably dichlorodiphenylsulfone. The C=C bonds in the PAES copolymer are useful to efficiently further functionalize the PAES or to form a crosslinked material.

Description

[0001] Unsaturated poly(aryl ether sulfone) copolymer

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to U.S. application No. 63 / 690615 filed on September 4, 2024, the entire content of this application being incorporated herein by reference for all purposes.

[0004] TECHNICAL FIELD

[0005] The present invention pertains to an allyl-functionalized poly(aryl ether sulfone) (PAES) copolymer and a process for manufacturing the PAES copolymer. The PAES copolymer comprises allyl groups comprising carboncarbon double bonds which are reactive and is therefore useful to efficiently modify or crosslink the PAES copolymer.

[0006] BACKGROUND

[0007] 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.

[0008] These PAES resins are made by polycondensation reactions typically using dichlorodiphenyl sulfone (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 NMP, DMAc, DMSO, and hence are extensively used to make hollow fiber or flat sheet membranes mainly for filtration and also for biological fluid such as blood purification (hemo-dialysis) processes along with separating complex biological mixtures such as proteins, enzymes and amino acids etc.

[0009] They are also used for water filtration and other food contact applications.

[0010] 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. 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 side-chain 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 etc. These side-chain olefinic groups were introduced in the PAES polymer by using olefinic bisphenols such as daBPA (2,2’ -diallyl bisphenol A) or daBPS (2,2’-diallyl bisphenol S) as co-diols in addition to the commonly-used aromatic diol: bisphenol A, 4-4’-biphenol or bisphenol S.

[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] While the side-chain functionalizable PAES described in WO 2020 / 187684A1, WO 2023 / 118302A1, and WO 2023 / 139134A1 by Solvay Specialty Polymers USA (SYENSQO group) contain reactive allyl / vinyl side chains, their manufacture uses two aromatic bisphenol monomers: BPA, BPS or BP with an olefinic 2,2’-diallyl bisphenol.

[0013] 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 (EP A) 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.

[0014] Hence there is an urgent need to identify non-bisphenolic and / or allyl comonomers 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.

[0015] SUMMARY The present invention relates to an unsaturated PAES copolymer with reactive allyl moieties comprising carbon-carbon double bonds (C=C) which can be used as a universal PAES scaffold to permit functionalization with a variety of functional groups depending on the intended use of the PAES copolymer or which can be crosslinked. The reactive allyl groups may be on the main PAES polymeric chain and / or on side chains.

[0016] The various aspects of the present invention are set out in the appended set of claims.

[0017] A first aspect of the invention relates to a polyarylethersulfone (“PAES”) copolymer defined in any one of claims 1-14.

[0018] A second aspect of the invention relates to a process defined in any one of claims 15-16 for manufacturing the PAES copolymer.

[0019] A third aspect of the invention relates to the use defined in claim 17 of the PAES copolymer as a polymeric scaffold comprising reactive allyl groups (or unsaturated groups) in its main polymeric chain and / or side chains to permit functionalization of the PAES copolymer by reaction of at least some of the reactive allyl groups (or unsaturated groups) with at least one functional group.

[0020] A fourth aspect of the invention relates to a crosslinkable composition comprising the PAES copolymer and optionally a free radical initiator and its use defined in claim 18 to make a crosslinked material.

[0021] 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.

[0022] DETAILED DESCRIPTION

[0023] Definitions

[0024] In the present descriptive specification, some terms are intended to have the following meanings for sake of clarity.

[0025] As used herein, the terminology “aliphatic allyl monomer (AA)” may be simplified as “allyl monomer (AA)”; the terminology “dihydroxy aliphatic allyl monomer (AA”)” may be simplified as “dihydroxy monomer (AA”)”; and the terminology “dihalogenated aliphatic allyl monomer (AA”)” can be simplified as “dihalo monomer (AA”)”.

[0026] As used herein, 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. As used herein, 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.

[0027] For the purpose of the present invention, 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 (or alicyclic moiety) does not comprise any heteroatoms in the ring, the backbone of the cycle of the cycloaliphatic (or alicyclic) moiety is made only of interconnected carbon atoms.

[0028] Similarly, for the purpose of the present invention, 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.

[0029] The term “heteroatom” means a non-carbon atom, for example an atom of oxygen, nitrogen and / or sulfur.

[0030] The term “acyclic” defines a structure which does not have any ring. For the purpose of the present invention, an 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, an 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. An allyl aliphatic monomer or moiety is unsaturated.

[0031] As used herein, the term “aromatic” or “aryl” defines a structure (such as a diol or moiety) which contains at least one aromatic ring which denotes a cyclic moiety having a number of n electrons equal to 4n+2, wherein n is 1 or any positive integer.

[0032] Any reference to general formulae of recurring units of the polymer (PAES) is intended to include each specific formula falling within the respective general formula, unless indicated otherwise.

[0033] The indeterminate article "a" in expressions like "a monomer" etc... is intended to mean "one or more", or "at least one" unless indicated otherwise.

[0034] The use of brackets "( )" before and after names, symbols or numbers identifying formulae or parts of formulae, e.g., polymer (PAES), recurring unit (Ra), 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.

[0035] The term "halogen" includes an element selected from the group consisting of fluorine, chlorine, bromine and iodine, unless indicated otherwise.

[0036] The term "method" is to be regarded as a synonym of "process" and vice versa.

[0037] 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.

[0038] As used herein, the terms “dihalogenated monomer”, “dihalo monomer” or “dihalodiaryl sulfone compound” refer to a compound comprising two halogen groups.

[0039] As used herein, the term “total weight % monomers” is defined as the weight of the monomers based on the total weights of monomers and solvent initially present during condensation (in the reaction medium).

[0040] In the present disclosure, the term “recurring unit” designates the smallest unit of a PAES polymer which is repeating in the main chain and which is composed of a condensation of a diol monomer and a dihalodiaryl sulfone monomer. The term “recurring unit” is synonymous to the terms “repeating unit” and “structural unit”.

[0041] As used herein, the term “homopolymer” encompasses a polymer which only has one type of recurring unit. Meaning, a homopolymer is obtained from the condensation of only one diol monomer and only one dihalodiaryl monomer.

[0042] As used herein, the term “copolymer” encompasses a polymer which may have two or more different types of recurring units. The PAES copolymer may be obtained from polycondensation of at least two dihydroxy monomers and at least one dihalodiaryl sulfone monomer, or from polycondensation of at least one dihydroxy monomer, at least one dihalodiaryl sulfone monomer and at least one other dihalogenated monomer.

[0043] As used herein, the abbreviation “BP A” means Bisphenol A or 4,4'- isopropylidenediphenol; the abbreviation “BPS” or “DHDPS” means Bisphenol S or 4,4’ -dihydroxy diphenyl sulfone; the abbreviation “BP” means 4,4’- biphenol; the abbreviation “TMPAE” means trimethylolpropane allyl ether; the abbreviation “DHB” refers to dihydroxy-butene; the abbreviation “DCB” refers to dichloro-butene; and the abbreviation “TMBPF” means tetramethyl Bisphenol F.

[0044] As used herein, 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. BP A 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. 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 ER . 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 (ICso) for ERP of 900 + / - 70 nM measured by competitive binding assay.

[0045] As used herein, the terminology “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.

[0046] As used herein, the terminology “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.

[0047] 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’), to make the sulfone recurring unit (Ra) by reacting with the at least one dihalodiaryl sulfone monomer (CC). 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-l-yloxy)methyl]-(ACl) or 1,3- propanediol,2-(hydroxymethyl)-2-[(7-octen-l-yloxy)methyl]- (AC1).

[0048] The expression "weight average molecular weight (Mw)” is hereby used according to its usual meaning and mathematically expressed:

[0049] Mw= (E Ni* Mi2) I E Ni*Mi wherein the summation E is over all the chain lengths from 1 to 00, Mi is the discrete value for the molecular weight of polymer molecule, and Ni is the number of polymer molecules with weight Mi.

[0050] The expression "number average molecular weight (Mn)" is hereby used according to its usual meaning and mathematically expressed as:

[0051] Mn = (E Ni*Mi) I E Ni wherein the summation E is over all the chain lengths from 1 to 00, and Mi and Ni are the same as defined in the expression “Mw”.

[0052] As used herein and unless explicitly stated otherwise, the polydispersity index (PDI) is hereby expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). This parameter gives an indication of how broad a range of molecular weights are in the PAES copolymer.

[0053] For the purpose of the present invention, the expression “substantially all” in combination with a recited amount of recurring unit(s) is hereby intended to mean that minor amounts, generally below 1 mol%, preferably below 0.5 mol%, of other recurring units may be tolerated, e.g., as a result of lower purity in monomers used.

[0054] For the purpose of the present invention, the expression “substantially equimolar” used with reference to the overall amount of hydroxyl groups from dihydroxy mononer(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 [that is to say, the at least one dihydroxy aliphatic allyl monomer (AA’) when used and the at least one diol (BB)] and the overall amount of halogen groups from all dihalo monomers [that is to say, the at least one dihalodiaryl sulfone monomer (CC) and the at least one dihalogenated aliphatic allyl monomer (AA”) when used], 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.

[0055] In the present specification, the choice of an element from a group of elements (such as a Markush group) also explicitly describes:

[0056] - the choice of two or the choice of more than two elements from the group,

[0057] - 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.

[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 elements and / or the characteristics of a polymer, 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 elements and / or characteristics of the polymer, 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 application, where an element or component is said to be included in and / or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components. Any element or component recited in a list of elements or components may be omitted from such list. Further, it should be understood that elements, embodiments, and / or features of processes or methods described herein can be combined in a variety of ways without departing from the scope and disclosure of the present teaching, whether explicit or implicit herein.

[0060] 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.

[0061] The term "comprising" (or “comprise”) includes "consisting essentially of (or “consist essentially of’) and also "consisting of' (or “consist of’).

[0062] 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. For example, when a polymer, composition, compound, product, polymer, or solution “consists essentially of’ required elements, it is generally understood that any additional element may be present in not more than 1 wt% based on the total weight of the polymer, composition, compound, product, polymer, solution, etc. or not more than 1 mol% based on the total number of moles of the polymer, composition, compound, product, polymer or solution. In the particular context of the PAES polymer, the expression ‘consisting essentially of is used for defining constituents of the PAES polymer to take into account end chains, defects, irregularities and monomer rearrangements which might be comprised in said PAES polymer in minor amounts, without this modifying essential properties of the PAES polymer.

[0063] The indeterminate article "a" in expressions like "a monomer" etc... is intended to mean “one or more” or “at least one” unless specifically stated otherwise.

[0064] The use of the singular ‘a’ or ‘one’ herein includes the plural unless specifically stated otherwise.

[0065] 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.

[0066] Detailed Description

[0067] 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 PAES copolymer containing C=C moi eties present in the main polymeric chain and / or on side chains and which presents appropriate set of characteristics and properties.

[0068] Preferred unsaturated PAES copolymers may be made by condensation of a dihalodiphenylsulfone (CC) with dihydroxy monomers which are endocrine safe, particularly

[0069] - at least one diol (BB) selected from 4,4 ’-biphenol and / or tetramethyl

[0070] Bisphenol F (TMBPF) as aromatic diol (BB’), and / or isosorbide as alicylic diol (BB”), preferably selected from 4,4’-biphenol and / or isosorbide, and

[0071] - at least one dihydroxy aliphatic allyl diol (AA’) selected from the group consisting of olefinic C4-C10 diols (AA’i) and dihydroxy allyl C7-C15 ethers (AA’2), preferably selected from dihydroxybutene (DHB) and / or TMPAE.

[0072] Other particular unsaturated PAES copolymers may be made by condensation of a dihalodiphenylsulfone (CC) with dihydroxy monomers which are endocrine safe, particularly:

[0073] - at least one diol (BB) selected from 4,4 ’-biphenol and / or tetramethyl

[0074] Bisphenol F (TMBPF) as aromatic diol (BB’), and / or an acyclic diol (B’”) selected from C2-C6 alkylene glycols, preferably selected from 4,4’- biphenol and / or ethylene glycol, and

[0075] - at least one allyl aliphatic diol (AA’) selected from the group consisting of olefinic C4-C10 diols (AA’i) and dihydroxy allyl C7-C15 ethers (AA’2), preferably selected from dihydroxy butene (DHB) and / or TMPAE.

[0076] Yet other particular unsaturated PAES copolymers may be made by condensation of a dihalodiphenylsulfone (CC) and at least one dihalogenated allyl monomer (AA”) with dihydroxy monomers which are endocrine safe, particularly at least one diol (BB) selected from 4,4 ’-biphenol, tetramethyl Bisphenol F (TMBPF), and / or isosorbide, preferably selected from 4,4’-biphenol and / or isosorbide.

[0077] Still yet other particular unsaturated PAES copolymers may be made by condensation of a dihalodiphenylsulfone (CC) and at least one dihalogenated allyl monomer (AA”) with dihydroxy monomers which are endocrine safe, particularly at least one diol (BB) selected from 4,4’-biphenol and / or tetramethyl Bisphenol F (TMBPF) as aromatic diol (BB’), and / or an acyclic diol (B’”) selected from C2-C6 alkylene glycols, preferably selected from 4,4’ -biphenol and / or ethylene glycol.

[0078] When using an endocrine-safe aromatic diol (BB’) - meaning which does not have high estrogenic activity, the PAES copolymer according to the invention which incorporates the 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 diallylbisphenol A or dially 1-bisphenol S, and therefore such a PAES copolymer according to the invention would present lower risk for human health.

[0079] The PAES copolymer according to the invention can also be effectively prepared using the less-expensive dichlorodiphenylsulfone monomer (DCDPS), thereby providing a more cost effective production, despite the fact that the aliphatic allyl monomers (AA) may have poorer reactivity with DCDPS, when compared to the very reactive difluorodiphenylsulfone monomer (DFDPS).

[0080] Such a PAES copolymer according to the invention provides an improvement over previous PAES polymers made from condensation of DCDPS with only bisphenols having high endocrine safety risk.

[0081] Poly(aryl ether sulfone) polymer (PAES)

[0082] The Applicant has now found that a poly(arylethersulfone) copolymer [PAES] according to the invention can be made by condensation of

[0083] - at least one allyl monomer (AA) having from 4 to 15 carbon atoms and comprising at least one C=C bond, said aliphatic allyl monomer (AA) being selected from dihydroxy aliphatic allyl monomers (AA’) comprising at least two hydroxyl groups and / or dihalogenated aliphatic allyl monomers (AA”) comprising at least two halogen groups,

[0084] - at least one diol (BB) selected from the group consisting of aromatic diols (BB’), alicyclic diols (BB”), acyclic diols (BB’”), and 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- at least one dihalodiaryl sulfone monomer (CC).

[0085] The at least one diol (BB) represents at least 25 mol% based on all dihydroxy monomers used during condensation.

[0086] The at least one dihalodiaryl sulfone monomer (CC) represents at least 50 mol% based on all dihalogenated monomers used during condensation. When the allyl monomer (AA) comprises, or consists of, at least one dihydroxy aliphatic allyl monomer (AA’), the molar ratio rl of the at least one dihydroxy aliphatic allyl monomer (AA’) to the diol (BB) is

[0087] - at most 45:55, preferably at most 40:60, more preferably at most 35:65, still more preferably at most 30:70, and

[0088] - at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88.

[0089] Preferred molar ratios rl of the at least one dihydroxy aliphatic allyl monomer (AA’) o 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.

[0090] When no dihalogenated aliphatic allyl monomer (AA”) is used in the allyl monomer (AA) during condensation, the allyl monomer (AA) consists of at least one dihydroxy aliphatic allyl monomer (AA’).

[0091] When the aliphatic allyl monomer (AA) comprises, or consist of, at least one dihalogenated aliphatic allyl monomer (AA”), the molar ratio r2 of the at least one dihalogenated aliphatic allyl monomer (AA”) to the dihalogenated sulfone monomer (CC) is:

[0092] - at most 40:60, preferably at most 35:65, more preferably at most 30:70, still more preferably at most 25:75, and

[0093] - at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88 or at least 15:85.

[0094] Preferred molar ratios r2 of the at least one dihalogenated allyl monomer (AA’) to the diol (BB) may be from 5:95 to 40:60, from 7:93 to 35:65, from 10:90 to 35:65, from 12:88 to 30:70 or from 15:85 to 25:75.

[0095] While not preferred, when no dihydroxy allyl monomer (AA’) is used in the aliphatic allyl monomer (AA) during condensation, the allyl monomer (AA) consists of at least one dihalogenated aliphatic allyl monomer (AA”).

[0096] The PAES copolymer according to the invention 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 -dihydroxy benzonitrile, 3, 4-dihydroxy benzonitrile, etc.

[0097] The PAES copolymer according to the invention 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. Presence of C=C bonds in PAES copolymer

[0098] The PAES copolymer according to the present invention has reactive allyl groups comprising C=C bonds on its main polymeric chain and / or on side chains.

[0099] The reactive allyl moieties comprising C=C bonds in the PAES copolymer according to the present invention originate from the at least one allyl monomer (AA).

[0100] When at least one dihydroxy aliphatic allyl monomer (AA’) comprises an olefinic diol (AA’i), at least some of the C=C bonds in the PAES copolymer are on the main PAES polymeric chain.

[0101] 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 PAES copolymer are on side chains, preferably the furthest away from the junction of the side chain with the main polymeric chain.

[0102] When the aliphatic allyl monomer (AA) comprises, or consist of, at least one dihalogenated monomer (AA”), at least some of the C=C bonds in the PAES copolymer are on side chains, preferably the furthest away from the junction of the side chain with the main polymeric chain.

[0103] Olefin Content in PAES copolymer

[0104] The PAES copolymer may have an olefin content, based on the total weight of the PAES copolymer, of at least 2 wt.%, at least 3 wt.%, at least 4 wt.%, at least 5 wt.%, at least 6 wt.%, at least 7 wt.%, or at least 8 wt.%.

[0105] The PAES copolymer may have an olefin content, based on the total weight of the PAES copolymer, of at most 40 wt.%, at most 35 wt.%, at most 30 wt.%, or at most 28 wt.%.

[0106] The olefin content in the PAES copolymer is preferably measured by1H- NMR. A particular suitable method for measuring the olefin content is detailed in the examples section below.

[0107] Preferably, the PAES copolymer according to the present invention has an olefin content, based on the total weight of the PAES copolymer, 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.%.

[0108] Aliphatic Allyl Monomer (AA)

[0109] The at least one allyl monomer (AA) represents at least 2 mol%, preferably at least 3 mol%, at least 4 mol%, at least 5 mol%, or at least 6 mol%, based on the total number of moles of all monomers. The at least one allyl monomer (AA) represents at most 40 mol%, preferably at most 35 mol%, at most 30 mol%, at most 25 mol%, at most 20 mol%, at most 19 mol%, at most 18 mol%, at most 17 mol%, at most 16 mol%, or at most 15 mol%, based on the total number of moles of all monomers.

[0110] Preferably, the at least one allyl monomer (AA) represents from 3 mol% to 25 mol%, preferably from 4 mol% to 20 mol%, from 5 mol% to 18 mol%, or from 6 mol% to 16 mol%, based on the total number of moles of all monomers.

[0111] The at least one allyl monomer (AA) having from 4 to 15 carbon atoms and comprising at least one unsaturated C=C bond may be selected from dihydroxy aliphatic allyl monomers (AA’) and / or dihalogenated aliphatic allyl monomers (AA”).

[0112] The at least one allyl monomer (AA) preferably contains only one C=C bond.

[0113] The at least one allyl monomer (AA) is preferably acyclic.

[0114] Dihydroxy aliphatic allyl monomer (AA’)

[0115] When used during condensation, the at least one dihydroxy monomer (AA’) may represent at least 4 mol%, preferably at least 6 mol%, at least 8 mol%, at least 10 mol%, or at least 12 mol%, based on the total number of moles of all dihydroxy monomers used during condensation

[0116] When used during condensation, the at least one dihydroxy monomer (AA’) may represent less than 50 mol%, or at most 40 mol%, preferably at most 35 mol%, or at most 32 mol%, or at most 30 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0117] Preferably when used during condensation, the at least one dihydroxy monomer (AA’) represents from 6 mol% to 45 mol%, preferably from 8 mol% to 40 mol%, 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.

[0118] The at least one dihydroxy monomer (AA’) may be of general formula (A’): HO-E’-OH, in which E’ is an aliphatic allyl moiety.

[0119] The at least one dihydroxy monomer (AA’) is preferably acyclic.

[0120] The aliphatic allyl moiety E’ is preferably acyclic.

[0121] 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.

[0122] Olefinic diol (AA ’1) A suitable olefinic diol (AA’i) 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.

[0123] The olefinic diol (AA’i) is preferably acyclic.

[0124] 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 (co) position.

[0125] A preferred olefinic diol (AA’i) is an a, co-dihydroxy alkene having 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.

[0126] The C=C bond in the olefinic diol (AA’i) is preferably not at the alpha (a) position (also termed primary position), nor omega (co) position.

[0127] The olefinic diol (AA’i) preferably contains only one C=C bond.

[0128] 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-l,3-pentenediol; and any combination thereof.

[0129] More 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; and any combination thereof.

[0130] Most preferably, the olefinic diol (AA’i) is l,4-dihydroxy-2-butene.

[0131] Allyl ether (AA ’2)

[0132] A suitable allyl ether (AA’2) 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.

[0133] The allyl ether (AA’2) is preferably acyclic.

[0134] The allyl ether (AA’2) has at least two hydroxyl groups, which are preferably spaced by at least 3 carbon atoms.

[0135] The allyl ether (AA’2) preferably contains only one C=C bond.

[0136] The allyl ether (AA’2) may be of formula HO-E'2-OH. in which E’2 is a moiety comprising two pendant groups R2’ and R2”, wherein R2’ is a C2+ ether pendant group with at least one ether -O- bond, and R2” is a C3+ olefinic pendant group, preferably having the C=C bond in the alpha position; or wherein R2’ is a C3+ olefinic pendant group comprising at least one ether - O- bond, preferably having the C=C bond in the alpha position, and R2” is a pendant group being a hydroxyl group or a Ci+ alkyl or alcohol group.

[0137] Preferably, the allyl ether (AA’2) is selected from the group consisting of those of formulae (Al) to (A43) in TABLE 1.

[0138] More preferably, the allyl ether (AA’2) is trimethylolpropane allyl ether (TMPAE) of formula (Al) : H2C=CHCH2OCH2C(C2H5)(CH2OH)2.

[0139] TABLE 1: Suitable allyl ethers (AA’2)

[0140] Dihalogenated aliphatic allyl monomer (AA”) When used during condensation, the at least one dihalogenated monomer (AA”) may represent at least 4 mol%, preferably at least 6 mol%, at least 8 mol%, at least 10 mol%, or at least 12 mol%, based on the total number of moles of all halogenated monomers used during condensation

[0141] When used during condensation, the at least one dihalogenated monomer (AA”) may represent less than 50 mol%, or at most 40 mol%, preferably at most 35 mol%, or at most 32 mol%, or at most 30 mol%, based on the total number of moles of all halogenated monomers used during condensation.

[0142] Preferably when used during condensation, the at least one dihalogenated monomer (AA”) represents from 6 mol% to 45 mol%, preferably from 8 mol% to 40 mol%, from 10 mol% to 35 mol%, or from 12 mol% to 32 mol%, based on the total number of moles of all halogenated monomers used during condensation.

[0143] The at least one dihalogenated monomer (AA”) may be of general formula (A”): X-E”-X’, in which E” is an aliphatic allyl moiety, and each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl.

[0144] The dihalogenated monomer (AA”) is preferably acyclic.

[0145] The aliphatic allyl moiety E” is preferably acyclic.

[0146] When used during condensation, the at least one dihalogenated monomer (AA”) is selected from the group consisting of dihalogenated alkenes comprising 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.

[0147] The at least one dihalogenated monomer (AA”) has two halogen groups, preferably Cl and / or F, more preferably two Cl groups, which are preferably spaced by at least 3 carbon atoms.

[0148] In the at least one dihalogenated monomer (AA”), at least one of the halogen groups is preferably in the alpha (a) position or omega (co) position.

[0149] A preferred dihalogenated monomer (AA”) is an a,co-dichloro alkene having 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.

[0150] The at least one C=C bond in the at least one dihalogenated allyl monomer (AA”) is preferably not at the alpha (a) or omega (co) position.

[0151] The at least one dihalogenated monomer (AA”) preferably contains only one C=C bond. A suitable dihalogenated monomer (AA”) may be selected from the group consisting of 1 ,4-di chlorobutene; 1,5-di chloropentene; 1,6-di chlorohexene; 1,7- dichloroheptene; 1,8-di chlorooctene; 1,9-di chlorononene; 1,10-di chlorodecene; 2,2,4-trimethyl-l,3-dichloropentene; and any combination thereof.

[0152] Preferably, the dihalogenated monomer (AA”) is selected from the group consisting of l,4-dichloro-2-butene, l,5-dichloro-2-pentene, 1,6-di chi oro-2- hexene, l,6-dichloro-3-hexene, 1,8-di chloro-2-octene, l,8-dichloro-4-octene, 2,8-dichloro-l -octene.

[0153] Most preferably, the dihalogenated monomer (AA”) is 1,4-di chi oro-2 - butene.

[0154] Diol (BB)

[0155] The at least one 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%, at least 35 mol%, at least 40 mol%, at least 45 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, or at least 70 mol%.

[0156] The at least one diol (BB) may represent 100 mol%, or at most 99 mol%, at most 98 mol%, at most 97 mol%, at most 96 mol%, at most 95 mol%, at most 92 mol%, at most 90 mol%, or at most 85 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0157] Particularly when used in the condensation, the at least one diol (BB) may represent from 50 mol% to 100 mol%, preferably from 60 mol% to 90 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0158] The at least one diol (BB) may be selected from the group consisting of aromatic diols (BB’), alicyclic diols (BB”), acyclic diols (BB’”), and any combination thereof, in particular any combination of at least one aromatic diol (BB’) and at least one alicyclic diol (BB”), 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’”).

[0159] In particular, the at least one diol (BB) may be selected from at least one aromatic diol (BB’), at least one alicyclic diol (BB”), or any combination of at least one aromatic diol (BB’) and at least one alicyclic diol (BB”). Alternatively, the at least one diol (BB) may be selected from at least one aromatic diol (BB’), at least one acyclic diol (BB’”), or any combination of at least one aromatic diol (BB’) and at least one acyclic diol (BB’”).

[0160] It should be understood that the at least one diol (BB) contains at least two hydroxyl groups. This means that, in the context of the present invention, the diol (BB) also encompasses any compound with more than two hydroxyl groups. A compound (BB*) which has 3 to 6 hydroxyl groups, particularly 3 or 4 hydroxyl groups, may be envisioned to use in the diol (BB), or as the diol (BB), to make a sulfone recurring unit by reacting with the at least one dihalodiaryl sulfone monomer (CC). For 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.

[0161] The at least one diol (BB) may be of general formula (B): HO-W-OH, in which W is an aromatic, cycloaliphatic or acyclic moiety.

[0162] Aromatic diol (BB’)

[0163] 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’).

[0164] Alternatively, the at least one diol (BB) may exclude any aromatic diol (BB’).

[0165] 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%, at least 35 mol%, at least 40 mol%, at least 45 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, or at least 70 mol%.

[0166] When used in the condensation, the at least one aromatic diol (BB’) may represent 100 mol%, or at most 99 mol%, at most 98 mol%, at most 97 mol%, at most 96 mol%, at most 95 mol%, at most 92 mol%, at most 90 mol%, or at most 85 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0167] Particularly when used in the condensation, the at least one aromatic diol (BB’) may represent from 50 mol% to 100 mol%, preferably from 60 mol% to 90 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0168] When the at least one aromatic diol (BB’) represents the sole dihydroxy monomer used during condensation, in such instance no dihydroxy monomer (AA’), no alicylic diols (BB”) and no acyclic diols (BB’”) are used during condensation.

[0169] 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 l,l,l-tris-(4-hydroxyphenyl)- ethane.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] Preferably, the two or more aromatic rings in the at least one aromatic diol (BB’) or in the aromatic moiety W’ 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>l, preferably p=l.

[0174] At least one aromatic ring in the at least one 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.

[0175] Preferably though, each aromatic ring in the at least one aromatic diol (BB’) or aromatic moiety W’ does not have any nitrogen atom. For example, the at least one 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,

[0176] More preferably, none of the aromatic rings in the at least one aromatic diol (BB’) or aromatic moiety W’ has any heteroatom. In such instance, the backbone of each aromatic ring in the at least one aromatic diol (BB’) or aromatic moiety W’ is made only of interconnected carbon atoms.

[0177] 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.

[0178] Preferably, no aromatic ring in the at least one aromatic diol (BB’) or aromatic moiety W’ should have a nitrile -C=N pendant group.

[0179] In particular, the aromatic diol (BB’) should not comprise dihydroxy benzonitriles, such as 2,6-dihydroxybenzonitrile, 2,5 -dihydroxy benzonitrile, 3,4- dihydroxybenzonitrile, etc.

[0180] 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 l,l,l-tris-(4-hydroxyphenyl)-ethane, and any combination of two or more thereof.

[0181] 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- hydroxy phenoxy) diphenyl sulfone, 4,4’-bis(4-(4-(4- hydroxyphenylsulfonyl)phenoxy)phenoxy) diphenyl sulfone; bisphenol F, and 2,2’-diallyl bisphenol F.

[0182] Yet more particularly, the aromatic diol (BB’) may exclude any diol selected from the group consisting of bisphenol A, 2,2 ’-diallyl bisphenol A, bisphenol S, 2,2’-diallyl bisphenol S, bisphenol F, and 2,2’-diallyl bisphenol F.

[0183] Preferably, the at least one aromatic diol (BB’) is selected from the group consisting of 4,4 ’-bi phenol, diallyl biphenol, tetramethyl bisphenol F, and any combination of two or more thereof.

[0184] More preferably, the at least one aromatic diol (BB’) is selected from the group consisting of 4,4’ -biphenol, tetramethyl bisphenol F, and any combination thereof. Still more preferably, the at least one aromatic diol (BB’) consists of 4,4’- biphenol and optionally diallyl biphenol and / or tetramethyl bisphenol F.

[0185] Most preferably, the at least one aromatic diol (BB’) is 4,4’-biphenol.

[0186] Alicyclic diol (BB”)

[0187] The at least one diol (BB) may comprise at least one alicyclic diol (BB”), or substantially all of the diol (BB) may be at least one alicylic diol (BB”).

[0188] Alternatively, the at least one diol (BB) may exclude any alicyclic diol (BB”).

[0189] When used during condensation, the at least one alicyclic diol (BB”) may represents at least 2 mol%, preferably at least 4 mol%, at least 6 mol%, at least 8 mol%, or at least 10 mol%, based on the total number of moles of all dihydroxy monomers used in the condensation.

[0190] When used during condensation, the at least one alicyclic diol (BB”) may represent 100 mol%, or at most 99 mol%, at most 98 mol%, at most 97 mol%, at most 96 mol%, at most 95 mol%, at most 92 mol%, at most 90 mol%, at most 85 mol%, at most 80 mol%, at most 75 mol%, at most 70 mol%, at most 65 mol%, at most 60 mol%, at most 55 mol%, at most 50 mol%, at most 45 mol%, at most 40 mol%, preferably at most 35 mol%, at most 30 mol%, at most 25 mol%, at most 20 mol%, at most 19 mol%, at most 18 mol%, at most 17 mol%, at most 16 mol%, or at most 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0191] Particularly when used during condensation, the at least one alicyclic diol (BB”) may represent from 50 mol% to 100 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0192] When the at least one alicyclic diol (BB”) may represent the sole dihydroxy monomer used during condensation, in such instance no dihydroxy monomer (AA’), no aromatic diol (BB’) and no acyclic diol (BB’”) are used during condensation.

[0193] When a dihydroxy monomer (AA’) is used during condensation, in such instance the at least one alicyclic diol (BB”) may represent at most 90 mol%, preferably at most 85 mol%, at most 80 mol%, at most 75 mol%, at most 70 mol%, at most 65 mol%, or at most 60 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0194] Particularly when used during condensation, the at least one alicyclic diol (BB”) may represent from 2 mol% to 45 mol%, preferably from 4 mol% to 40 mol%, 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.

[0195] When used in combination with at least one 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%, at most 30 mol%, at most 25 mol%, at most 20 mol%, at most 19 mol%, at most 18 mol%, at most 17 mol%, at most 16 mol%, or at most 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0196] Preferably, when used in combination with at least one 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%, from 8 mol% to 30 mol%, 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.

[0197] The at least one alicyclic diol (BB”) may be of general formula (B”): H0-W”-0H, in which W” is a cycloaliphatic moiety comprising at least one nonaromatic ring. The cycloaliphatic moiety W” does not contain any aromatic ring.

[0198] The at least one alicyclic diol (BB”) cycloaliphatic moiety W” may contain only one non-aromatic ring.

[0199] Preferably, the at least one alicyclic diol (BB”) or cycloaliphatic moiety W” may contain two or more non-aromatic rings. Two or more of the non- aromatic rings in the at least one 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(CH3)2- , -SO2-, or an alkylene group -(CH2)P- with p>l, preferably p=l.

[0200] At least one non-aromatic ring in the at least one 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.

[0201] Alternatively, non-aromatic ring(s) in the at least one 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.

[0202] When used during condensation, the at least one alicyclic diol (BB”) may be particularly selected from the group consisting of those complying with formulae (DI) to (DI 1) and any combination thereof : wherein each Q’, being the same or different in formula (Dl l), is an acyclic moiety.

[0203] The acyclic moiety Q’ in formula (Dl l) 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-l,3-propanediol; 2,2- dimethylpropane-l,3-diol; 2,2,4-trimethyl-l,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.

[0204] Q’ in formula (DI 1) 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(CHs)], tetramethylene [CH2-CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2- butyl-l,3-propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,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; preferably, represented by any one of following formulae (VI’), (VI”), (VI’”) and

[0205] (VI””):

[0206] -[CH2-CH2-O]Z-CH2-CH2- (VF),

[0207] -[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (VI”),

[0208] -[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (VI’”),

[0209] -[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.

[0210] The alicyclic diol (BB”), when used, is preferably a bio-based diol, such as selected from 2,3-di-O-alkylene-l-threitols; l,4:3,6-dianhydrohexitols and / or l,4:3,6-dianhydrohexitols with acyclic aliphatic end groups.

[0211] The alicyclic diol (BB”) is more preferably selected from the group consisting of l,4:3,6-dianhydrohexitols such as isosorbide (of formula DI), isomannide (of formula D2), isoidide (of formula D3); 2,3-di-O-alkylene-l- threitols such as 2,3-O-isopropylidene-l-threitol (of formula D4) and / or 2,3-di-O- methylene-l-threitol; and / or l,4:3,6-dianhydrohexitols with acyclic aliphatic end groups such as isosorbide with acyclic aliphatic end groups (of formula DI 1).

[0212] Yet more preferably, the at least one alicyclic diol (BB”) is selected from the group consisting of isosorbide (of formula DI) and 2,3-O-isopropylidene-l- threitol (of formula D4).

[0213] Most preferably, the at least one alicyclic diol (BB”) is isosorbide (of formula DI).

[0214] Acyclic diol (BB’”)

[0215] The at least one diol (BB) may comprise at least one acyclic diol (BB’”).

[0216] Alternatively, the at least one diol (BB) may exclude any acyclic diol (BB’”). When used during condensation, the at least one acyclic diol (BB’”) may represent at least 2 mol%, preferably at least 4 mol%, at least 6 mol%, at least 8 mol%, at least 10 mol%, or at least 12 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0217] When used during condensation, the at least one acyclic diol (BB’”) may represent 100 mol%, or at most 99 mol%, at most 98 mol%, at most 97 mol%, at most 96 mol%, at most 95 mol%, at most 92 mol%, at most 90 mol%, at most 85 mol%, at most 80 mol%, at most 75 mol%, at most 70 mol%, at most 65 mol%, at most 60 mol%, at most 55 mol%, at most 50 mol%, at most 45 mol%, at most 40 mol%, preferably at most 35 mol%, at most 30 mol%, at most 25 mol%, at most 20 mol%, at most 19 mol%, at most 18 mol%, at most 17 mol%, at most 16 mol%, or at most 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0218] Particularly when used during condensation, the at least one acyclic diol (BB’”) may represent from 2 mol% to 45 mol%, preferably from 4 mol% to 40 mol%, 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.

[0219] Preferably, when used in combination with at least one 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%, from 8 mol% to 30 mol%, 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.

[0220] When the at least one alicyclic diol (BB”) represents the sole dihydroxy monomer used during condensation, in such instance no dihydroxy monomer (AA’), no aromatic diol (BB’) and no alicylic diol (BB”) are used during condensation.

[0221] When a dihydroxy monomer (AA’) is used during condensation, in such instance the at least one acyclic diol (BB’”) may represent at most 90 mol%, preferably at most 85 mol%, at most 80 mol%, at most 75 mol%, at most 70 mol%, at most 65 mol%, or at most 60 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0222] 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%, at most 30 mol%, at most 25 mol%, at most 20 mol%, at most 19 mol%, at most 18 mol%, at most 17 mol%, at most 16 mol%, or at most 15 mol%, based on the total number of moles of all dihydroxy monomers used during condensation.

[0223] Preferably, when used in combination with at least one aromatic diol (BB’) during condensation, the at least one acyclic diol (BB’”) represents from 4 mol% to 35 mol%, preferably from 6 mol% to 30 mol%, from 8 mol% to 30 mol%, 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.

[0224] The at least one acyclic diol (BB’”) may be a linear or branched aliphatic diol.

[0225] In addition to the oxygen atoms of the two hydroxyl groups, the at least one 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.

[0226] Alternatively, the at least one acyclic diol (BB’”) may have a backbone made only of connected carbon atoms.

[0227] 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-l,3-propanediol; 2,2- dimethylpropane-l,3-diol (also known as neopentyl glycol); 2,2,4-trimethyl-l,3- pentanediol; 2-ethyl-2-butyl-l,3-propanediol; poly(ethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.

[0228] 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.

[0229] Non-limiting examples of acyclic diols (BB’”) which are branched aliphatic diols are 2-methyl- 1,3 -propanediol, 2,2-dimethylpropane-l,3-diol, 2,2,4-trimethyl-l,3-pentanediol, 2-ethyl-2-butyl-l,3-propanediol, propylene glycol, and / or polypropylene glycol).

[0230] 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-l,3- propanediol; neopentyl glycol; 2,2,4-trimethyl-l,3-pentanediol, and any combination of two or more thereof.

[0231] A still more preferred acyclic diol (BB’) includes ethylene glycol.

[0232] The most preferred acyclic diol (BB’”) is ethylene glycol.

[0233] 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.

[0234] The acyclic moiety W’” may be represented by formula (V):

[0235] -[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-l,3-propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,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, represented by any one of following formulae (V’), (V”), (V’”) and

[0236] (V””):

[0237] -[CH2-CH2-O]Z-CH2-CH2- (V’),

[0238] -[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (V”),

[0239] -[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (V’”),

[0240] -[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.

[0241] 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.

[0242] Although not preferred, when the acyclic diol (BB’”) of formula (B’”): H0-W”’-0H in which 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’”): H0-W”’-0H 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. Preferably, when the acyclic diol (BB’”) of formula (B’”): HO-W”’-OH in which W’” is represented by any one of following formulae (V’), (V”), (V’”) and (V””), 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 formu

[0243] Dihalodiaryl Sulfone Monomer (CC)

[0244] The at least one dihalodiaryl sulfone monomer (CC) may represent at least 50 mol%, preferably at least 55 mol%, at least 60 mol%, at least 65 mol%, or at least 70 mol%, based on the total number of moles of all dihalogenated monomers used during condensation.

[0245] The at least one dihalodiaryl sulfone monomer (CC) may represent at most 100 mol%, or at most 99 mol%, at most 98 mol%, at most 97 mol%, at most 96 mol%, at most 95 mol%, at most 92 mol%, at most 90 mol%, or at most 85 mol%, based on the total number of moles of all dihalogenated monomers used during condensation.

[0246] 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.

[0247] The at least one dihalodiaryl sulfone monomer (CC) may represent substantially the sole dihalogenated monomer used during condensation. In such instance no dihalogenated aliphatic allyl monomers (AA”) is used during condensation.

[0248] The at least one dihalodiaryl sulfone monomer (CC) may be of general formula (C): X-Ar-SCh-Ar’-X’, in which the -Ar-SCh-Ar’- is a diaryl sulfone moiety.

[0249] Each of X, X in formula (C), independent from each other, is Cl or F; preferably both X,X’ are Cl.

[0250] 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.

[0251] Each of Ar, Ar may be of formula (IV): wherein each of 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.

[0252] 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).

[0253] 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 the formula (C) are unsubstituted arylene groups.

[0254] The at least one dihalodiaryl sulfone monomer (CC) may be selected from the group consisting of: 4,4’ -di chlorodiphenyl sulfone (DCDPS), monosulfonated 4,4’ -di chlorodiphenyl 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.

[0255] Preferably, the at least one dihalodiaryl sulfone monomer (CC) is selected from the group consisting of: DFDPS, DCDPS and / or disodium bis(4-chloro-3- sulfophenyl)sulfone (dsDCDPS).

[0256] In particular, dichlorodiphenylsulfone (DCDPS) of formula (C*): Cl-Ar- SCh-Ar’-Cl, in which Ar and Ar’ are both unsubstituted arylene groups, may represent at least 50 mol%, preferably at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol%, based on the total number of moles of the at least one dihalodiaryl sulfone monomer (CC) used during condensation.

[0257] Most preferably, the at least one dihalodiaryl sulfone monomer (CC) is DCDPS.

[0258] Recurring units of PAES copolymer The PAES copolymer according to the invention may comprise at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 96 mol%, at least 97 mol%, at least 98 mol%, or at least 99 mol%, based on the total amount of moles of recurring units in the PAES copolymer, of

[0259] - at least one recurring unit selected from recurring unit (Ra) of formula (I) and / or recurring unit (Rb) of formula (II):

[0260] [-Ar-SO2-Ar’-O-E’-O-] (I),

[0261] [-E”-0-W-0-] (II), and

[0262] - at least one recurring unit (Rc) of formula (III):

[0263] [-Ar-SO2-Ar’-O-W-O-] (III), wherein

[0264] • E’ is an aliphatic allyl moiety derived from at least one dihydroxy monomer (AA’) of formula (A’): HO-E’-OH;

[0265] • E” is an aliphatic allyl moiety derived from at least one dihalogenated monomer (AA”) of formula (A”): X-E”-X’, in which each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl;

[0266] • W is an aromatic, alicyclic or acyclic moiety derived from the at least one diol (BB) of formula (B): HO-W-OH; and

[0267] • -Ar-SO2-Ar’- is a diaryl sulfone moiety derived from the at least one dihalodiaryl sulfone monomer (CC) of formula (C): X-Ar-SO2-Ar’-X’, 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 each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl.

[0268] The PAES copolymer according to the invention may particularly comprise at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 96 mol%, at least 97 mol%, at least 98 mol%, or at least 99 mol%, based on the total amount of moles of recurring units in the PAES copolymer, of:

[0269] - recurring unit (Ra) of formula (I) and recurring unit (Rc’) of formula (III’); or

[0270] - recurring unit (Ra) of formula (I) and recurring unit (Rc”) of formula (III”); or

[0271] - recurring unit (Ra) of formula (I) and recurring unit (Rc’”) of formula (III’”); or

[0272] - recurring unit (Ra) of formula (I), recurring unit (Rc’) of formula (III’) and recurring unit (Rc”) of formula (III”); or

[0273] - recurring unit (Ra) of formula (I), recurring unit (Rc’) of formula (III’) and recurring unit (Rc’”) of formula (III’”); or - recurring unit (Ra) of formula (I), recurring unit (Rc”) of formula (III”) and recurring unit (Rc’”) of formula (III’”); wherein the formulae (I), (III’), (III”) and (III’”) are as follows :

[0274] [-Ar-SO2-Ar’-O-E’-O-] (I),

[0275] [-Ar-SO2-Ar’-O-W’-O-] (III’),

[0276] [-Ar-SO2-Ar’-O-W”-O-] (III”),

[0277] [-Ar-SO2-Ar’-O-W’”-O-] (III’”), wherein

[0278] • E’ is an aliphatic allyl moiety derived from at least one dihydroxy monomer (AA’) of formula (A’): HO-E’-OH;

[0279] • W’ is an aromatic moiety derived from the at least one aromatic diol (BB’) of formula (B’): HO-W’-OH;

[0280] • W” is a cycloaliphatic moiety derived from the at least one alicyclic diol (BB”) of formula (B”): HO-W”-OH;

[0281] • W’” is a cycloaliphatic moiety derived from the at least one acyclic diol (BB’”) of formula (B’”): HO-W’”-OH; and

[0282] • -Ar-SO2-Ar’- is a diaryl sulfone moiety derived from the at least one dihalodiaryl sulfone monomer (CC) of formula (C): X-Ar-SO2-Ar’-X’, 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 each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl.

[0283] In such an instance, E’ is preferably derived from trimethylolpropane allyl ether (TMPAE), 1,4-butenediol, or both, more preferably derived from TMPAE; W’ is preferably derived from 4,4’biphenol, TMBPF, or both, more preferably derived from 4,4’biphenol; W” is preferably derived from a bio-based alicyclic diol, more preferably derived from isosorbide; and W’” is preferably derived from C2-Cs alkylene glycols, more preferably derived from ethylene glycol..

[0284] The PAES according to the invention may alternatively comprise at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 96 mol%, at least 97 mol%, at least 98 mol%, or at least 99 mol%, based on the total amount of moles of recurring units in the PAES copolymer, of:

[0285] - recurring unit (Rb’) of formula (IF) and recurring unit (Rc’) of formula (III’); or

[0286] - recurring unit (Rb”) of formula (II”) and recurring unit (Rc”) of formula (III”) ; or - recurring unit (Rb’”) of formula (II’”) and recurring unit (Rc’) of formula (III’), or

[0287] - recurring unit (Rb’) of formula (II’), recurring unit (Rc’) of formula (III’), recurring unit (Rb”) of formula (II”) and recurring unit (Rc”) of formula (III”); or

[0288] - recurring unit (Rb’) of formula (II’), recurring unit (Rc’) of formula (III’), recurring unit (Rb’”) of formula (II’”) and recurring unit (Rc’”) of formula (III’”); or

[0289] - recurring unit (Rb’) of formula (II’), recurring unit (Rc’) of formula (III’), recurring unit (Rb”) of formula (II”), recurring unit (Rc”) of formula (III”); recurring unit (Rb’”) of formula (II’”) and recurring unit (Rc’”) of formula (Hi’”); wherein the formulae (II’), (III’), (II”), (III”), (II’”) and (III’”) are as follows:

[0290] [-E”-0-W’-0-] (IF),

[0291] [-Ar-SO2-Ar’-O-W’-O-] (III’),

[0292] [-E”-0-W”-0-] (II”),

[0293] [-Ar-SO2-Ar’-O-W”-O-] (III”),

[0294] [-E”-0-W”’-0-] (IF”),

[0295] [-Ar-SO2-Ar’-O-W’”-O-] (III’”), wherein

[0296] • E” is an aliphatic allyl moiety derived from at least one dihydroxy allyl monomer (AA”) of formula (A”): HO-E’-OH

[0297] • W’ is an aromatic moiety derived from the at least one aromatic diol (BB’) of formula (B’): HO-W’-OH;

[0298] • W” is an alicyclic moiety derived from the at least one alicyclic diol (BB”) of formula (B”): H0-W”-0H;

[0299] • W’” is an acyclic moiety derived from the at least one acyclic diol (BB’”) of formula (B’”): H0-W”’-0H; and

[0300] • -Ar-SO2-Ar’- is a diaryl sulfone moiety derived from the at least one dihalodiaryl sulfone monomer (CC) of formula (C): X-Ar-SO2-Ar’-X’, 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 each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl.

[0301] In such an instance, E” is preferably derived from an a, co-di chloro C4-C15 alkene, more preferably derived from l,4-dichloro-2-butene; W’ is preferably derived from 4,4 ’-biphenol, TMBPF, or both, more preferably derived from 4,4’biphenol; W” is preferably derived from a bio-based alicyclic diol, more preferably derived from isosorbide; and W’” is preferably derived from C2-C5 alkylene glycols, more preferably derived from ethylene glycol.

[0302] The preferred recurring unit (Ra) for the PAES copolymer is represented by formula (1-1) or (1-2) shown below, more preferably by formula (1-1):

[0303] The preferred recurring unit (Rb’) for the PAES copolymer is represented by formula (II’-l) or (II’-2) shown below, more preferably by formula (II- 1):

[0304] The preferred recurring unit (Rb”) for the PAES copolymer is represented by any one of formulae (II”- 1) to (II”-4) shown below, more preferably by formula ( - ).

[0305] The preferred recurring unit (Rc’) for the PAES copolymer is represented by formula (III’-l) or (IIF-2) shown below, preferably by formula (III’-l):

[0306] The preferred recurring unit (Rc”) for the PAES copolymer may be represented by any one of formulae (III”-1) to (III”-4) shown below, preferably by formula (III”-1):

[0307] A preferred recurring unit (Rc’”) for the PAES copolymer may be represented by formula (III”’-1):

[0308] Properties of the PAES copolymer

[0309] One of the advantages of the PAES copolymer in which its recurring units consist essentially of recurring unit (Ra) of formula (1-1) or (1-2), at least one recurring unit selected from recurring unit (Rc’) of formula (III’-l) or (III’-2) and recurring unit (Rc”) of any of formula (III”-1) to formula (III”-4) is that such as PAES copolymer is free of bisphenol A, preferably free of bisphenol A, 2,2’-diallyl bisphenol A, bisphenol S, and 2,2’-diallyl bisphenol S.

[0310] The PAES according to the invention is advantageously transparent and amorphous. The amorphous PAES 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”).

[0311] The glass transition temperature (Tg) of the PAES copolymer 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.

[0312] The decomposition temperature of the PAES copolymer 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.

[0313] When the PAES copolymer comprises recurring unit (Ra) of formula (1-1), recurring unit (Rc’) of formula (III’-l) and optionally recurring unit (Rc”) of any of formula (III”- 1 ) to formula (III”-4), preferably of formula (III”- 1), or when the PAES copolymer comprises recurring unit (Rb’) of formula (II’- 1), recurring unit (Rc’) of formula (III’-l), optionally recurring unit (Rb”) of any of formula (II”-1) to formula (II”-4), preferably of formula (II”-1), and optionally recurring unit (Rc”) of any of formula (III”-1) to formula (III”-4), preferably of formula (III”-1), the unsaturated PAES copolymer is characterized by:

[0314] - a decomposition temperature measured by thermogravimetric analysis

[0315] (TGA) of at least 395 °C, and

[0316] - a glass transition temperature measured by differential scanning calorimetry (DSC) of at least 180 °C.

[0317] Molecular weights of the PAES copolymer

[0318] The PAES copolymer according to the invention has advantageously a weight average molecular weight (Mw) above 15000 g / mol or at least 20000 g / mol or at least 25000 g / mol, preferably at least 30,000 g / mol. Upper limit for the number average molecular weight (Mw) of the PAES copolymer 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 PAES copolymer according to the invention 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.

[0319] Any suitable method may be used to determine the molecular weight for the PAES copolymer. For example,1H- NMR and gel -permeation chromatography (GPC), also known as size exclusion chromatography (SEC), may be used. Unless explicitly stated otherwise, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the size average molecular weight (Mz) of the PAES copolymer are estimated by GPC, preferably calibrated with polystyrene standards and performed using a mobile phase. The mobile phase may be selected from any solvent for the PAES copolymer described herein, such as N-Methyl-2-pyrrolidone (NMP), N,N'- dimethylacetamide (DMAc), tetrahydrofuran (THF), sulfolane, or methylene chloride, preferably methylene chloride, NMP or DMAc, more preferably methylene chloride. Mw, Mnof the PAES are preferably determined by GPC, calibrated with polystyrene standards and performed using methylene chloride as mobile phase. A particular suitable GPC method is detailed in the examples below.

[0320] The molecular weight distribution (MWD) of the PAES copolymer may be characterized by a poly dispersity index (PDI) expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The PDI of the PAES copolymer may be advantageously at least 2.0, preferably at least 2.1, and / or the PDI of the PAES may be advantageously at most 3.5, preferably at most 3.3, more preferably at most 3.2.

[0321] Other properties / characteristics of the PAES copolymer

[0322] The PAES copolymer contains advantageously less than 10 ppm, preferably less than 5 ppm of Bisphenol A (BP A), more preferably less than 1 ppm of BPA, said ppm being based on total weight of the PAES copolymer.

[0323] The PAES copolymer 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 PAES copolymer.

[0324] The PAES copolymer preferably is substantially free (e.g., less than 1 ppm) of BPA and of BPS.

[0325] The PAES copolymer more preferably is substantially free (e.g., less than 1 ppm) of BPA, diallyl BPA, BPS and diallyl BPS. The BPS content in the PAES copolymer may be measured by liquid chromatography analysis of a solution of the PAES copolymer in DMF after precipitation of the polymer by acetonitrile. A suitable analytical method is described below.

[0326] Determination of content of residual BPS in the PAES copolymer

[0327] A 0.5-g sample of PAES is dissolved in 10 mL DMF. After dissolution, 10 mL of acetonitrile are added under agitation to precipitate the polymer. The solution is filtered through a 0.22-pm syringe filter and analyzed (20pL injection volume) by Liquid Chromatography using a Supelco Discovery® Cl 8 HPLC column (4.6 mm x 25 mm, 5 pm particle size).

[0328] The mobile phase has the following gradient composition:

[0329] The detector is a UV detector set at 254 nm. The concentration of BPS is determined using external standards of BPS.

[0330] The BPA content in the PAES copolymer may be measured by gas chromatography analysis of a solution of the PAES copolymer in DMF or trichloromethane. A suitable analytical method for measuring BPA content is described below.

[0331] Determination of content of residual BPA in the PAES

[0332] A 0.25-g sample of PAES is dissolved into 5 mL trichloromethane. The solution is filtered through a 0.22 -micron syringe filter and analyzed by Gas Chromatography using a Restek™ RTX™-5MS capillary column (30m length, 0.25mm ID, 0.25 pm film thickness), a constant pressure of 14.5 psi of helium. The GC conditions are :

[0333] • Injector:

[0334] Injection vol: 2 pL

[0335] • Inlet:

[0336] Mode: Split

[0337] Temp: 290 °C split Ratio: 3:1

[0338] • Detector: FID

[0339] Makeup: helium Temp: 300 °C

[0340] H2 Flow: 30 mL / min

[0341] Air Flow: 400 mL / min

[0342] Makeup Flow: 35 mL / min

[0343] Constant Makeup and Fuel Flow

[0344] • Oven:

[0345] Initial Temp: 35 °C

[0346] • Ramp:

[0347] 35 °C, Hold 1 min

[0348] Ramp @ 20 °C / min to 325 °C, Hold 10 min

[0349] The concentration of BPA is determined using external standards of BP A. The PAES copolymer contains advantageously no more than 10 wt%, preferably no more than 8 wt%, more preferably no more than 5 wt%, most preferably no more than 2 wt%, of an oligomer fraction having a number molecular weight of less than 3000 g / mol, said wt% being based on total weight of the PAES copolymer.

[0350] The content of such an oligomer fraction having a number molecular weight of less than 3000 g / mol in the PAES copolymer may be measured from slice data of GPC chromatogram by help of gel-permeation chromatography software which is calibrated with polystyrene standards, in which case it corresponds to:

[0351] M = 3000 wherein AU (detector response in mV) is the y-axis unit and log M (logarithm of molecular weight) is the x-axis unit.

[0352] The PAES copolymer has advantageously a residual polar aprotic solvent content of less than 3000 ppm, preferably less than 2500 ppm, more preferably less than 2000 ppm of, most preferably less than 1000 ppm and most preferably less than 500 ppm, said ppm being based on total weight of the PAES copolymer.

[0353] The PAES copolymer preferably is substantially free (e.g., less than 500 ppm) of polar aprotic solvent. The content of residual polar aprotic solvent in the PAES copolymer may be measured by GC analysis of a solution of the PAES copolymer in a solvent like DMF (or a different solvent if DMF is the solvent that needs to be quantified). A suitable method for measuring content of residual polar aprotic solvent is described below.

[0354] Determination of content of residual polar aprotic solvent in the PAES

[0355] A 0.25 g sample of PAES is dissolved into 5 mL DMF and the solution is filtered through a 0.22-micron syringe filter and analyzed by Gas Chromatography (GC) using a Restek RTX-200ms (30m X 250um X 0.25um) column, a constant Flow of hydrogen as carrier gas of 1.6 mL / min.

[0356] The GC conditions are:

[0357] • Injector: injection vol: 1.5 pL

[0358] • Inlet:

[0359] Mode: Split

[0360] Temp: 270 °C

[0361] Pressure: 59 kPa (8.5744 psi)

[0362] Split Ratio: 10:1

[0363] Split Flow 16 mL / min

[0364] • Detector: FID

[0365] Makeup: N2

[0366] Temp: 310 °C

[0367] H2 Flow: 40 mL / min

[0368] Air Flow: 400 mL / min

[0369] Makeup Flow: 15 mL / min

[0370] Constant Makeup and Fuel Flow

[0371] • Oven:

[0372] Initial Temp: 30 °C

[0373] • Ramp:

[0374] 30 °C, Hold 4 min

[0375] Ramp @ 40 °C / min to 105 °C, Hold 1 min Ramp @ 40 °C / min to 175 °C, Hold 0 min Ramp @ 30 °C / min to 300 °C, Hold 0 min

[0376] The residual level of solvent is determined using external standards in DMF of selected polar aprotic solvents (sulfolane, NMP) used in condensation reaction medium. Process for making the PAES copolymer

[0377] The present invention further relates to a process for making the PAES copolymer comprising at least one recurring unit selected from recurring unit (Ra) of formula (I) and / or recurring unit (Rb) of formula (II) and further comprising at least one recurring unit (Rc) of formula (III), wherein:

[0378] • the recurring unit (Ra) of formula (I) is derived from condensation of the at least one dihalodiaryl sulfone monomer (CC) and at least one dihydroxy monomer (AA’);

[0379] • the recurring units (Rb) of formula (II) is derived from condensation of at least one diol (BB) and at least one dihalogenated monomer (AA”); and

[0380] • the recurring unit (Rc) of formula (III) is derived from condensation of the at least one dihalodiaryl sulfone monomer (CC) and the at least one diol (BB).

[0381] The process preferably comprises reacting in a reaction medium comprising a polar aprotic solvent, a base and a monomers mixture comprising:

[0382] - the at least one allyl monomer (AA) being selected from dihydroxy aliphatic allyl monomers (AA’) and / or dihalogenated aliphatic allyl monomers (AA”),

[0383] - 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

[0384] - the at least one dihalodiaryl sulfone monomer (CC), under condensation conditions effective to form the PAES copolymer having reactive allyl groups comprising C=C on its main polymeric chain and / or on side chains.

[0385] Monomer (AA) such as monomers (AA’) and / or (AA”), monomer (BB) such as monomers (BB’), (BB”), and / or (BB’”), and monomer (CC) are described above.

[0386] 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).

[0387] The at least one diol (BB) represents at least 25 mol% based on all dihydroxy monomers present in the reaction mixture during condensation. The at least one dihalodiaryl sulfone monomer (CC) represents at least 50 mol% based on all dihalogenated monomer present in the reaction mixture during condensation.

[0388] 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. Examples of quinoxaline diols may be 2,6-dihydroxy quinoxaline or 2,3-dihydroxy quinoxaline.

[0389] The reaction medium preferably does not include a benzonitrile compound selected from dihalogenated benzonitriles and / or dihydroxy benzonitriles, such as 2,6-dichlorobenzonitrile, 3,4-dichlorobenzonitrile,2,6-dihydroxybenzonitrile, 2,5 -dihydroxy benzonitrile, 3, 4-dihydroxy benzonitrile, etc.

[0390] 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.

[0391] Alternatively, the reaction can also be conducted in two or more stages, for example:

[0392] - 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

[0393] - 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.

[0394] Total wt% monomers

[0395] 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:

[0396] - at least 30 wt%, preferably at least 35 wt%, more preferably at least 38 wt%, and / or

[0397] - at most 60 wt%, preferably at most 55 wt%, more preferably at most 50 wt%. Base

[0398] The reaction medium comprises a base.

[0399] 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 ‘Tb ase ’is:

[0400] - 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 - at most 3.0, or at most 2.8, or at most 2.75, or at most 2.5, or at most 2.4.

[0401] The base preferably comprises an anhydrous alkali metal carbonate.

[0402] 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.

[0403] The average particle size (Dso) 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 (Dso) of at least 20 microns and at most 50 microns is used.

[0404] The base used during condensation (in the reaction medium) is preferably anhydrous.

[0405] As used herein, the term “anhydrous” refers to a substance containing less than 2 wt% moisture, preferably less than 1% moisture, more preferably less than 0.5% moisture, most preferably less than 0.25% moisture as measured by Karl- Fisher titration or by loss on drying test.

[0406] Polar aprotic solvent

[0407] The dihydroxy and dihalogenated monomers and the base are dissolved and / or dispersed in a polar aprotic solvent.

[0408] The polar aprotic solvent employed is one generally known in the art and widely used for the manufacture of aromatic sulfone polymers. For example, sulfur containing solvents known and generically described in the art as dialkyl sulfoxides and dialkylsulfones wherein the alkyl groups may contain from 1 to 8 carbon atoms, including cyclic alkylidene analogs thereof, are disclosed in the art for use in the manufacture of PAES copolymer. Specifically, among the sulfur- containing solvents that may be suitable for the purposes of this invention are dimethylsulfoxide, dimethylsulfone, diphenylsulfone, diethylsulfoxide, di ethylsulfone, diisopropylsulfone, tetrahydrothiophene- 1, 1 -dioxide (commonly called tetramethylene sulfone or sulfolane) and tetrahydrothiophene- 1 -monoxide and mixtures thereof. Nitrogen-containing polar aprotic solvents, including N,N- dimethylacetamide (DMAc), N,N-dimethylformamide (DMF) and N-methyl pyrrolidone (NMP) and the like have been disclosed in the art for use in these processes, and may also be found useful in the practice of this invention. The polar aprotic solvent is preferably selected from the group consisting of l,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene- 1,1 -di oxide (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, tetrahydrofuran (THF), and any mixture of two or more thereof.

[0409] The polar aprotic solvent is more preferably selected from the group consisting of DMI, DMSO, sulfolane, NMP, NBP, NEP, DMAc, DMF, THF, and any combination thereof.

[0410] The p condensation reaction to polymerize the monomers and prepare the PAES is more advantageously carried out in the polar aprotic solvent being sulfolane, DMAc or NMP.

[0411] Optional co-solvent

[0412] 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.

[0413] 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.

[0414] 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 azeotrope-forming solvents for use in such condensation polymerization processes include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like, preferably chlorobenzene. The azeotrope-forming solvent and the polar aprotic solvent are typically employed in a weight ratio (w / w) 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.

[0415] The condensation reaction though is preferably carried out without an azeotrope-forming co-solvent.

[0416] Preparation of the reaction medium

[0417] A reaction medium, containing the following ingredients: the dihydroxy and dihalogenated monomers, the base, and the polar aprotic solvent, is formed by :

[0418] 1 / mixing all of these ingredients together, or

[0419] 2 / pre-mixing some of the ingredients together to obtain a pre-mixture, and then adding the missing ingredient(s) to the pre-mixture.

[0420] The mixing or pre-mixing is preferably carried at a ‘mixing’ temperature not suitable for the condensation reaction, such as a mixing temperature of at most 150 °C, or at most 130 °C, or at most 110 °C.

[0421] The adding step in 2 / may be done while at reaction temperature which is >110 °C, or > 130 °C, or >150 °C, or while at a ‘mixing’ temperature not suitable for the condensation reaction, such as a mixing temperature of at most 150 °C, or at most 130 °C, or at most 110 °C.

[0422] Hydroxyl / halogen molar ratio r3 in reaction medium

[0423] The molar ratio of halogen groups (preferably chlorine) and the hydroxyl groups 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.

[0424] The molar ratio r3 between the overall amount of hydroxyl groups from the at least one dihydroxy monomer (AA’) when used and the at least one diol (BB) [aromatic diol (BB’), alicyclic diol (BB”) and / or acyclic diol (BB’”)] and the overall amount of halogen groups from the at least one dihalodiaryl sulfone monomer (CC) and the at least one dihalogenated monomer (AA”) when used, may be 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. 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’) if used and diol (BB) [aromatic diol (BB’), alicyclic diol (BB”) and / or acyclic diol (BB’”)] compared to the starting dihalodiaryl sulfone mononer (CC) and the dihalogenated monomer (AA”) if used. 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.

[0425] When it is desired to have less reactive end groups in the PAES copolymer, 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 mononer (CC) and dihalogenated monomer (AA”) if used compared to the starting dihydroxy monomer (AA’) if used, aromatic diol (BB’), and optional alicyclic diol (BB”), whereby an excess of chlorine end groups is preferable. In such instance, the molar ratio (l / 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.

[0426] Base / diol(s) molar ratio rbase in reaction medium

[0427] As described previously, the molar ratio rbase of the base relative to all dihydroxy monomers used in the reaction medium may be selected to be:

[0428] - 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

[0429] - at most 3.0, or at most 2.8, or at most 2.75, or at most 2.5, or at most 2.4.

[0430] Reaction temperature

[0431] The reaction medium to prepare the PAES copolymer is kept at a temperature suitable for condensation to occur. Such a suitable temperature for the reaction medium may be:

[0432] - 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 - 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.

[0433] 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.

[0434] Reaction conversion

[0435] The process to manufacture the PAES copolymer is such that the reaction conversion is at least 90%, preferably at least 95%.

[0436] Reaction time

[0437] The time for reaction to prepare the PAES copolymer may be from about 3 hours to 24 hours, or from about 4 hours to 20 hours, or from 5 hours to 18 hours.

[0438] Reaction pressure

[0439] 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.

[0440] Recovery of PAES copolymer in solid form

[0441] The PAES copolymer of the invention can be recovered by methods well known and widely employed in the art such as, for example, coagulation, solvent evaporation and the like.

[0442] The resulting PAES copolymer 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 KC1). The additional solvent may be different than the polar aprotic solvent used in the reaction, but preferably it is the same.

[0443] Alternatively, the PAES copolymer may be isolated by precipitation and / or coagulation by contacting the reaction medium, optionally after salt removal by filtration, with a non-solvent for the PAES copolymer such as a C1-C5 alcohol, water, or any mixture thereof. The precipitate / coagulate 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. The resulting PAES copolymer 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 PAES copolymer are well known in the art.

[0444] The PAES copolymer according to the present invention 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’j, such as 4,4’-biphenol or TMBPF, is used, potentially a higher renewable content especially when a bio-sourced alicyclic diol (BB”), such as diols of any of formulae (DI) to (D4), is used in making such a PAES copolymer.

[0445] Use of the PAES copolymer

[0446] Functionalization of the PAES copolymer

[0447] A third aspect of the invention relates to the use of the PAES copolymer as a polymeric scaffold comprising reactive allyl groups (or unsaturated groups) in its main polymeric chain and / or side chains to permit functionalization of the PAES copolymer by reaction of at least some of the reactive allyl groups (or unsaturated groups) with at least one functional group.

[0448] Thermal crosslinking of the PAES copolymer

[0449] A fourth aspect of the invention relates to a crosslinkable composition comprising the PAES copolymer of the present invention and optionally a free radical initiator and its use or a method to make a crosslinked material.

[0450] Preferably, the PAES copolymer in the crosslinkable composition comprises reactive allyl groups (or unsaturated groups) in side chains.

[0451] More preferably, the PAES copolymer in the crosslinkable composition comprises recurring unit (Ra) of formula (1-1), recurring unit (Rc’) of formula (III’-l) and optionally recurring unit (Rc”) of formula (III”-1). In such instances, the molar ratio of the recurring unit (Rc’) of formula (III’-l) to the recurring unit (Ra) of formula (1-1) and optionally the recurring unit (Rc”) of formula (III”-1) in the PAES copolymer is:

[0452] - at most 45:55, preferably at most 40:60, more preferably at most 35:65, still more preferably at most 30:70, and

[0453] - at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88. The term “crosslinkable” as used herein means that the PAES copolymer is not cured or crosslinked yet, and comprises crosslinkable C=C moieties which will cause or promote substantial crosslinking when subjecting or exposing the PAES copolymer to a treatment including heat, humidity and / or water.

[0454] The term "crosslinking" means that the PAES copolymer is subjected or exposed to a treatment which induced crosslinking of its crosslinkable C=C moieties to form bonds between PAES copolymer species.

[0455] The term “crosslinked” as used herein means that the PAES copolymer was subjected or exposed to a treatment which induced crosslinking of its crosslinkable C=C moieties. The crosslinked polymer material is preferably insoluble in NMP.

[0456] The crosslinkable composition preferably comprises a solvent in which the PAES copolymer is soluble, preferably comprises methylene chloride.

[0457] The content of the PAES copolymer in the crosslinkable composition is limited by the solubility limit of the PAES copolymer in the solvent. Preferably the crosslinkable composition comprises at least 10 wt%, at least 12 wt%, or at least 15 wt%, or at least 18 w% and at most 30 wt%, or at most 25 wt%, of the PAES copolymer, said wt% being based on the total weight of the crosslinkable composition.

[0458] Preferably, the free radical initiator is present in the crosslinkable composition.

[0459] The free radical initiator when present in the crosslinkable composition may be selected from 2,2'-Azobis(2-methylpropionitrile) (AIBN), 2,2'- azobis(2,4-dimethylvaleronitrile) (ADVN), or benzoyl peroxides, preferably AIBN.

[0460] More preferably, AIBN as free radical initiator is present in the crosslinkable composition.

[0461] The use of the crosslinkable composition to make a crosslinked material preferably includes thermal crosslinking at a temperature from 20°C to 110°C, preferably from 20°C to 100°C, more preferably from 35°C to 100°C, still more preferably from 50°C to 95°C, yet still more preferably from 60°C to 95°C.

[0462] 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. EXAMPLES

[0463] 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.

[0464] RAW MATERIALS

[0465] • DCDPS (4,4’ -di chlorodiphenyl sulfone), available from Solvay Speciality Polymers

[0466] • BPS (4,4’ -dihydroxy di phenyl sulfone, also known as bisphenol S), available from Nicca

[0467] • BPA, available from Covestro

[0468] • BP (4,4’ biphenol), available from SI Group, Inc.

[0469] • TMPAE (trimethyloylpropane allyl ether), ISOSO (isosorbide), DCB (1,4- di chloro 2-butene), DHB (cis l,4-dihydroxy-2-butene), chlorobenzene, DMSO (dimethylsulfoxide), NMP (N-Methyl-2-pyrrolidone), AIBN (2,2'- Azobis(isobutyronitrile), available from Sigma- Aldrich, U.S.A.

[0470] • K2CO3 (Potassium Carbonate), available from Armand products

[0471] • Sulfolane, available from Chevron Phillips.

[0472] TEST METHODS

[0473] GPC Method for Sulfone Polymers - Molecular weight (Mn, Mw)

[0474] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5 pl 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.

[0475] Thermal gravimetric analysis (TGA)

[0476] 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.

[0477] M NMR (Proton Nuclear Magnetic Resonance) 'H 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.

[0478] Differential Scanning Calorimetry (DSC)

[0479] DSC was used to determine glass transition temperatures (Tg). DSC experiments were carried out using a TA Instrument QI 00. 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.

[0480] Example 1: Synthesis of the allyl functionalized PPSU copolymer (PO-A) by polycondensation of DCDPS (monomer CC) with 30 mol% TMPAE (as monomer AA’) and 70 mol% BP (as monomer BB’)

[0481] A batch of the PPSU copolymer (PO-A) was prepared according to following Scheme 1 :

[0482] C2H5HO-CH2-C-CH2OH

[0483] CH2H o CH2CH Sulfolane II CH2K2CO3

[0484] 210 °C

[0485] Trimethylolpropane allyl ether in which n=70 mol% and m=30 mol% in the illustrated structure of the PPSU copolymer (PO-A).

[0486] Procedure: The polymerization took place in a 2-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation setup. 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 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 (PO-A) was then washed with methanol and water and again with methanol and dried at 110°C.

[0487] Characterization of the PPSU copolymer (PO-A)

[0488] TABLE 2a summarizes the characteristics (Mw, Mn, PDI, Tg, TGA) of the copolymer (PO-A).

[0489] JH 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 copolymer (PO-A). The TMPAE content was estimated to be around 27 mol%.

[0490] % olefin content (byJH NMR) : 27 mol%.

[0491] Example 2: Synthesis of the allyl-functionalized isosorbide-co-PPSU copolymer (PO-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’)

[0492] A batch of isosorbide-co-PPSU copolymer (PO-B) was prepared according to following Scheme 2: in which n=75 mol%, m= 12.5 mol% and p=12.5 mol% in the illustrated structure of the isosorbide-co-PPSU copolymer (PO-B).

[0493] Procedure: The polymerization took place in a 2-L glass reactor vessel fitted with an overhead stirrer, a nitrogen inlet and an overhead distillation setup. 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.

[0494] Characterization of the isosorbide-co-PPSU copolymer (P0-B)

[0495] TABLE 2a summarizes the characteristics (Mw, Mn, PDI, Tg, TGA) of the copolymer (P0-B).

[0496] JH 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 copolymer (P0-B). The TMPAE content was estimated to be around 11 mol%. The isosorbide content in the copolymer was estimated to be around 20.09 mol%.

[0497] % olefin content (byJH NMR): 11 mol%.

[0498] Example 3: Synthesis of the allyl functionalized PESU copolymer (P0-C) by polycondensation of DCDPS (as monomer CC) with 18 mol% TMPAE (as monomer AA’) and 82 mol% BPS (as monomer BB’)

[0499] A batch of allyl-functionalized PESU copolymer (P0-C) was prepared according to following Scheme 3:

[0500] CH2CH Sulfolane ii CH2K2CO3

[0501] 210 °C

[0502] Trimethylolpropane allyl ether in which n=82 mol% and m=18 mol% in the illustrated structure of the PESU copolymer (PO-C).

[0503] Procedure: 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.

[0504] Characterization of the PES copolymer (PO-C)

[0505] TABLE 2a summarizes the characteristics (Mw, Mn, PDI, Tg, TGA) of the copolymer (PO-C).

[0506] 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 copolymer (PO-C). % olefin content (by H NMR): 16.5 mol%.

[0507] Example 4: Synthesis of the olefin-functionalized PPSU copolymer (PO-D) by polycondensation of 80 mol% DCDPS (as monomer CC) and 20 mol% DCB (as monomer AA”) with biphenol (as monomer BB’)

[0508] A batch of the PPSU copolymer (PO-D) was prepared according to following Scheme 4:

[0509] H H

[0510] CIH2C-C=C-CH2CI +

[0511] 1 ,4 dichlorobutene

[0512] Sulfolane K2CO3 in which n=20 mol% and m=80 mol% in the illustrated structure of the PPSU copolymer (PO-D).

[0513] Procedure: 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 (229.72 g, 0.8 mol), BP (186.21 g, 1 mol), and potassium carbonate (152 g, 1.11 mol) were added to the vessel first, followed by the addition of sulfolane (400 g). The reaction mixture was heated from room temperature to 90 °C using a 150°C / min heating ramp and purged with nitrogen (N2) for 30 minutes, after which chlorobenzene was added, and the temperature of the reaction was increased to 210 °C such that all the chlorobenzene was distilled off. After four hours, a second charge of sulfolane (458 g) was added, and the reaction mixture was cooled to 90°C. Then DCB (1,4- dichlorobutene) (25 g, 0.2 mol) was added all at once, and the reaction was continued for four more hours or till the reaction mixture began too viscous to mix. The reaction mixture was cooled and then filtered to remove the salts. The copolymer in the filtrate was then coagulated into methanol. The coagulated polymer was washed with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0514] Characterization of the PPSU copolymer (PO-D)

[0515] TABLE 2b summarizes the characteristics (Mw, Mn, PDI, Tg, TGA) of the copolymer (PO-D).1H NMR: The presence of unsaturated groups was confirmed by the appearance of a signal around 5.98 ppm which indicated the incorporation of 15.1 mol% DCB monomer in the copolymer (PO-D).

[0516] Olefin content (by 'H-NMR): 15.1 mol%.

[0517] Example 5: Synthesis of the olefin functionalized PPSU copolymer (PO-E) by polycondensation of DCDPS (as monomer CC) with 30 mol% DHB (as monomer AA’) and biphenol (as monomer BB’)

[0518] A batch of the PPSU copolymer (PO-E) was prepared according to following Scheme 5: in which n=30 mol% and m=70 mol% in the illustrated structure of PPSU copolymer (PO-E).

[0519] Procedure: 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 (287.16 g, 1 mol), BP (130.34 g, 0.7 mol), cis 1,4 - dihydroxy 2- butene (26.43 g DHB, 0.3 mol), and potassium carbonate (203.2 g, 1.47 mol) were added to the vessel first, followed by the addition of sulfolane (556.41 g). The reaction mixture was heated from room temperature to 190 °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 polymer. After endcapping, the reaction mixture was cooled and then filtered to remove the salts. The copolymer in the filtrate was then coagulated into methanol. The coagulated copolymer was washed with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0520] Characterization of the PPSU copolymer (PO-E)

[0521] TABLE 2b summarizes the characteristics (Mw, Mn, PDI, Tg, TGA) of the copolymer (PO-E).1H NMR: The presence of unsaturated groups was confirmed by the appearance of a signal around 8 ppm which indicated the incorporation of 8.6 mol% DHB monomer in the copolymer (P0-E).

[0522] Olefin content (by 'H NMR): 8.6 mol%

[0523] Example 6: Synthesis of the allyl functionalized PSU copolymer (PO-F) by polycondensation of DCDPS (as monomer CC) with 30 mol% TMPAE (as monomer AA’) and bisphenol A (as monomer BB’)

[0524] A batch of the PSU copolymer (PO-F) was prepared according to following Scheme 6:

[0525] C ii H CH2in which m=30 mol% and n=70 mol% in the illustrated structure of PSU copolymer (PO-F).

[0526] Procedure: 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 (287.16 g, 1 mol), BPA (159.8 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 (152 g, 1.1 mol), and NMP (432 g). The reaction mixture was heated from room temperature to 190 °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 polymer (meaning, to react the - OH endgroups to form methoxy endgroups). After endcapping the reaction mixture was cooled and then filtered to remove the salts. Then the copolymer in 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.

[0527] Characterization of the copolymer (PO-D)

[0528] TABLE 2b summarizes the characteristics (Mw, Mn, PDI, Tg, TGA) of the copolymer (PO-F).

[0529] JH 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 25.8 mol% TMPAE monomer in the copolymer (PO-F).

[0530] % olefin content (byJH NMR) : 25.8 mol%.

[0531] TABLE 2a

[0532] TABLE 2b

[0533] Example 7: Thermal crosslinking of allyl functionalized PPSU copolymer (PO-A) with a free radical initiator to form a crosslinked material

[0534] For the thermal crosslinking test, AIBN (2,2'-Azobis(isobutyronitrile) was used as free radical initiator. This initiator thermally decomposed to form free radicals as shown in Scheme 7:

[0535] The free radicals then reacted with the unsaturated groups of the allyl functionalized PPSU copolymer (PO-A) to form a crosslinked structure, the crosslinking reaction and the resulting idealized structure of the crosslinked material (in which n=70 mol% and m=30 mol%) being shown in following Scheme 8:

[0536] Crosslinking procedure: 4 g of the PPSU copolymer (PO-A) was dissolved in 16 g of methylene chloride, and to this solution, an amount (0.5g) of AIBN was added and stirred to get a clear solution. This solution was then heated in an air circulated oven at 90 °C for 1 and 3 hours. After the heat treatment, each of the heat-treated samples was then tested for solubility in N-methylpyrrolidone (NMP). The material was immersed in NMP at room temperature for at least 12 hours at least. Both heat-treated samples were completely insoluble after the immersion test, indicating that the resulting polymeric materials were crosslinked.

[0537] While preferred embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the teaching of this invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications 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.

[0538] What is claimed is:

Claims

C L A I M S1. A polyarylethersulfone (PAES) copolymer made by condensation of :- at least one aliphatic allyl monomer (AA) comprising at least 4 carbon atoms and at most 15 carbon atoms and at least one C=C bond, said aliphatic allyl monomer (AA) being selected from dihydroxy aliphatic allyl monomers (AA’) comprising at least two hydroxyl groups and / or dihalogenated aliphatic allyl monomers (AA”) comprising two halogen groups,- at least one diol (BB) being selected from the group consisting of aromatic diols (BB’), alicyclic diols (BB”), acyclic diols (BB’”), and any combination thereof, and- at least one dihalodiaryl sulfone monomer (CC); wherein the at least one diol (BB) represents at least 25 mol% based on all dihydroxy monomers, and wherein the at least one dihalodiaryl sulfone monomer (CC) represents at least 50 mol% based on all dihalogenated monomers, said (PAES) copolymer having reactive allyl groups comprising C=C on its main polymeric chain and / or on side chains.

2. The PAES copolymer of claim 1, comprising at least 80 mol%, based on the total amount of moles of recurring units in the PAES, of- at least one recurring unit selected from recurring unit (Ra) of formula (I) and / or recurring unit (Rb) of formula (II):[-Ar-SO2-Ar’-O-E’-O-] (I),[-E”-O-W-O-] (II), and- at least one recurring unit (Rc) of formula (III):[-Ar-SO2-Ar’-O-W-O-] (III), wherein• E’ is an aliphatic allyl moiety derived from at least one dihydroxy aliphatic allyl monomer (AA’) of formula (A’): HO-E’-OH;• E” is an aliphatic allyl moiety derived from at least one dihalogenated monomer (AA”) of formula (A”): X-E”-X’, in which each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl;• W is a moiety derived from the at least one diol (BB) of formula (B): HO- W-OH; and• -Ar-SCh-Ar’- is a diaryl sulfone moiety derived from the at least one dihalodiaryl sulfone monomer (CC) of formula (C): X-Ar-SCh-Ar'-X'. 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 X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl.

3. The PAES copolymer of claim 1 or 2, comprising at least 80 mol%, based on the total amount of moles of recurring units in the PAES, of :- recurring unit (Ra) of formula (I) and recurring unit (Rc’) of formula (III’); or- recurring unit (Ra) of formula (I) and recurring unit (Rc”) of formula (III”); or- recurring unit (Ra) of formula (I) and recurring unit (Rc’”) of formula (III’”); or- recurring unit (Ra) of formula (I), recurring unit (Rc’) of formula (III’) and recurring unit (Rc”) of formula (III”); or- recurring unit (Ra) of formula (I), recurring unit (Rc’) of formula (III’) and recurring unit (Rc’”) of formula (III’”); or- recurring unit (Ra) of formula (I), recurring unit (Rc”) of formula (III”) and recurring unit (Rc’”) of formula (III’”); wherein the formulae (I), (III’), (III”) and (III’”) are as follows :[-Ar-SO2-Ar’-O-E’-O-] (I),[-Ar-SCh-Ar’-O-W’-O-] (III’),[-Ar-SO2-Ar’-O-W”-O-] (III”),[-Ar-SO2-Ar’-O-W’”-O-] (III’”), wherein• E’ is an aliphatic allyl moiety derived from at least one dihydroxy aliphatic allyl monomer (AA’) of formula (A’): HO-E’-OH;• W’ is an aromatic moiety derived from the at least one aromatic diol (BB’) of formula (B’): HO-W’-OH;• W” is a cycloaliphatic moiety derived from the at least one alicyclic diol (BB”) of formula (B”): H0-W”-0H;• W’” is a acyclic moiety derived from the at least one acyclic diol (BB’”) of formula (B’”): H0-W”’-0H; and• -Ar-SCh-Ar’- is a diaryl sulfone moiety derived from the at least one dihalodiaryl sulfone monomer (CC) of formula (C): X-Ar-SCh-Ar'-X'. 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 each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl.

4. The PAES copolymer of claim 1 or 2, comprising at least 80 mol%, based on the total amount of moles of recurring units in the PAES, of- recurring unit (Rb’) of formula (IT) and recurring unit (Rc’) of formula (III’); or- recurring unit (Rb”) of formula (II”) and recurring unit (Rc”) of formula (III”) ; or- recurring unit (Rb’) of formula (IF”) and recurring unit (Rc’) of formula (HF”), or- recurring unit (Rb’) of formula (II’), recurring unit (Rc’) of formula (III’), recurring unit (Rb”) of formula (II”) and recurring unit (Rc”) of formula (III”); or- recurring unit (Rb’) of formula (II’), recurring unit (Rc’) of formula (III’), recurring unit (Rb’”) of formula (II’”) and recurring unit (Rc’”) of formula (III’”); or- recurring unit (Rb’) of formula (II’) , recurring unit (Rc’) of formula (III’), recurring unit (Rb”) of formula (II”), recurring unit (Rc”) of formula (III”); recurring unit (Rb’”) of formula (II’”) and recurring unit (Rc’”) of formula (III’”); wherein the formulae (II’), (III’), (II”), (III”), (IF”) and (III’”) are as follows:[-E”-0-W’-0-] (IF),[-Ar-SO2-Ar’-O-W’-O-] (III’),[-E”-0-W”-0-] (II”),[-Ar-SO2-Ar’-O-W”-O-] (III”),[-E”-0-W”’-0-] (IF”),[-Ar-SO2-Ar’-O-W’”-O-] (III’”), wherein• E” is an aliphatic allyl moiety derived from at least one dihalogenated aliphatic allyl monomer (AA”) of formula (A”): HO-E’-OH;• W’ is an aromatic moiety derived from the at least one aromatic diol (BB’) of formula (B’): HO-W’-OH;• W” is an alicyclic moiety derived from the at least one alicyclic diol (BB”) of formula (B”): H0-W”-0H;• W’” is an acyclic moiety derived from the at least one acyclic diol (BB’”) of formula (B’”): H0-W’”-0H; and• -Ar-SCh-Ar’- is a diaryl sulfone moiety derived from the at least one dihalodiaryl sulfone monomer (CC) of formula (C): X-Ar-SCh-Ar'-X'. 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 each of X, X’, independent from each other, is Cl or F, preferably both X, X’ are Cl.

5. The PAES copolymer of any one of claims 1 to 4, wherein at least one aliphatic allyl monomer (AA) is used during condensation and comprises or consists of:- at least one dihydroxy C4-C15 aliphatic allyl monomer (AA’) selected from the group consisting of olefinic C4-C15 diols (AA’i) and dihydroxy allyl C4-C15 ethers (AA’2), preferably selected from the group consisting of olefinic C4-C10 diols (AA’i) and dihydroxy allyl C7-C15 ethers (AA’2); and / or- at least one dihalogenated aliphatic allyl monomer (AA”) selected from the group consisting of dihalogenated C4-C15 alkenes, preferably selected from a,co- di chloro C4-C10 alkenes.

6. The PAES copolymer of any one of claims 1 to 5, wherein at least one dihydroxy aliphatic allyl monomer (AA’) is used during condensation and comprises or consists of:- an olefinic diol (AA’i) 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-l,3-pentenediol; and any combination thereof; preferably being l,4-dihydroxy-2-butene; and / or- a dihydroxy allyl ether (AA’2) selected from the group consisting of those of formulae (Al) to (A43) in TABLE 1, preferably being trimethylolpropane allyl ether (TMPAE) of formula (Al): H2C=CHCH2OCH2C(C2H5)(CH2OH)2.

7. The PAES copolymer of any one of claims 1 to 7, wherein at least one aromatic diol (BB’) is used during condensation and is selected from the group consisting of bisphenol A, bisphenol A derivatives such as 2,2’-diallyl-bisphenol A, bisphenol S, bisphenol S derivatives such as 2,2’ -diallyl bisphenol S, 4,4’- biphenol, biphenol derivatives such as 2,2’ -diallyl biphenol, bisphenol F, bisphenol F derivatives such as tetramethyl bisphenol F or 2,2 ’-diallyl bisphenol F, hydroquinone, resorcinol, aromatic triols such as l,l,l-tris-(4- hydroxyphenyl)-ethane, and any combination thereof; more preferably selected from the group consisting of 4,4’ -biphenol, 2,2’ -diallyl-4, 4’ -biphenol, tetramethyl bisphenol F, and any combination thereof; yet more preferably selected from the group consisting of 4,4’ -biphenol, tetramethyl bisphenol F, and any combination thereof, still more preferably being 4,4’ -biphenol.

8. The PAES copolymer of any one of claims 1 to 7, wherein at least one alicyclic diol (BB”) is used in the condensation and is selected from the group consisting of those complying with following formulae (DI) to (Dll) and any combination thereof, preferably selected from the group consisting of isosorbide (of formula DI), 2,3-O-isopropylidene-l-threitol (of formula D4), tetrahydrofurandimethanol (of formula D5), and isosorbide with acyclic aliphatic end groups (of formula Dll), more preferably is isosorbide (of formula DI):wherein each Q’, being the same or different in formula (DI 1), is an acyclic moiety.

9. The PAES copolymer of any one of claims 1 to 8, wherein the at least one acyclic diol (BB’”) is used in the condensation and is selected from the group consisting of 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-l,3- propanediol; 2,2-dimethylpropane-l,3-diol (also known as neopentyl glycol); 2,2,4-trimethyl-l,3-pentanediol; 2-ethyl-2-butyl-l,3-propanediol; poly(ethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof; more preferably selected from the group consisting of ethylene glycol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 2-methyl-l,3-propanediol; neopentyl glycol; 2,2,4-trimethyl-l,3- pentanediol, and any combination of two or more thereof.

10. The PAES copolymer of any one of claims 1 to 9, wherein the at least one dihalodiaryl sulfone monomer (CC) is selected from the group consisting of: 4,4 ’-di chlorodiphenyl sulfone (DCDPS), monosulfonated 4,4’ -di chlorodi phenyl sulfone (msDCDPS), disulfonated 4,4 ’-di chlorodiphenyl sulfone (dsDCDPS), 4,4’ difluorodiphenyl sulfone (DFDPS), monosulfonated 4,4’ difluorodiphenyl sulfone (msDFDPS), disulfonated 4,4’ difluorodiphenyl sulfone (dsDFDPS), and any combination thereof, preferably selected from the group consisting of: DFDPS, DCDPS and / or disodium bis(4-chloro-3-sulfophenyl)sulfone (dsDCDPS), most preferably is DCDPS.

11. The PAES copolymer of any one of claims 1 to 10, wherein when the aliphatic allyl monomer (AA) comprises or consists of at least one dihydroxy aliphatic allyl monomer (AA’), the molar ratio rl of the at least one dihydroxy monomer (AA’) to the diol (BB) 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; or when the aliphatic allyl monomer (AA) comprises or consists of at least one dihalogenated aliphatic allyl monomer (AA”), the molar ratio r2 of the at least one dihalogenated aliphatic allyl monomer (AA”) to the dihalogenated sulfone monomer (CC) is:- at most 40:60, preferably at most 35:65, more preferably at most 30:70, still more preferably at most 25:75, and- at least 5:95, preferably at least 7:93, more preferably at least 10:90, still more preferably at least 12:88 or at least 15:85.

12. The PAES copolymer of any one of claims 1 to 11, being free of bisphenol A, preferably being free of bisphenol A and bisphenol S.

13. The PAES copolymer of any one of claims 1 to 12, having an olefin content based on the total weight of the PAES copolymer, of at least 2 wt.% and at most 45 wt.%, said wt.% olefin content being measured by 'H'NMR.

14. The PAES copolymer of any one of claims 1 to 13, comprising recurring unit (Ra) represented by following formula (1-1), recurring unit (Rc’) represented by following formula (III’-l), and optionally recurring unit (Rc”) represented by following formula (III”-1):

15. A process for manufacturing the PAES copolymer of any one of claims 1 to 14, comprising: reacting in a reaction medium comprising a polar aprotic solvent, a base and a monomers mixture comprising:- the at least one aliphatic allyl monomer (AA) being selected from dihydroxy aliphatic allyl monomers (AA’) and / or dihalogenated aliphatic allyl monomers (AA”),- the at least one diol (BB) selected from aromatic diols (BB’), alicyclic diols (BB”), or any combination thereof, and- the at least one dihalodiaryl sulfone monomer (CC), under condensation conditions effective to form the PAES copolymer having reactive allyl groups comprising C=C on its main polymeric chain and / or on side chains.

16. The process according to claim 15, wherein the condensation conditions include at least one of the following:• a base comprising an alkali metal carbonate selected from the group consisting of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, preferably selected from sodium carbonate and / or potassium carbonate, more preferably being potassium carbonate;• a total weight % monomer concentration [hereinafter “total wt% monomers”], based on the total weight of the monomers and the polar aprotic solvent, of at least 30 wt%, preferably at least 35 wt%, more preferably at least38 wt%, and / or at most 60 wt%, preferably at most 55 wt%, more preferably at most 50 wt%;• a reaction temperature of more than 150 °C, preferably at least 160°C, preferably at least 170°C, and less than 230 °C, preferably at most 220 °C, more preferably at most 215 °C, yet more preferably at most 210 °C;• a molar ratio r3 between the overall amount of hydroxyl groups from all dihydroxy monomers and the overall amount of halogen groups from all dihalogenated monomers in the reaction medium being 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;• the polar aprotic solvent is selected from the group consisting of 1,3- dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene- 1,1 -di oxide (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 of these solvents; preferably selected from the group consisting of DMI, NMP, NBP, NEP, DMAc, DMF, sulfolane, and any mixture of two or more of these solvents; more preferably selected from the group consisting of DMI, NMP, DMAc, sulfolane, and any mixture of two or more of these solvents.

17. Use of the PAES copolymer of any one of claims 1 to 14 as a polymeric scaffold comprising reactive allyl groups in its main polymeric chain and / or side chains to permit functionalization of the PAES copolymer by reaction of at least some of the reactive allyl groups with at least one functional group.

18. Use of a crosslinkable composition comprising the PAES copolymer of any one of claims 1 to 14 and optionally a free radical initiator to form a crosslinked material.

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