Upcycling of polyarylethersulfone to make a reactive macromer product

Abstract

A process for upcycling a polymeric waste material containing a polyarylethersulfone (PAES polymer) having less than 20 mol% reactive end groups, comprising depolymerizing the PAES polymer in the presence of a phenolic nucleophile and an alkali salt-forming carbonate agent in a polar aprotic solvent to obtain a PAES reactive macromer of lower molecular weight which is recovered. A composite comprising a resin matrix, reinforcing fibers and the PAES reactive macromer. An article made from a self-crosslinking PAES reactive macromer. Such a PAES reactive macromer contains more than 60 mol% of reactive end group(s) Ref, at most 20 mol% halide end group(s) X, and at most 20 mol% of unreactive end group(s) Ne, based on the total amount of moles of end groups. Preferably, Ref contains at least one group selected from –OH, -NH2, -COOH, –C≡CH, –C≡C–Ar, and / or an OH group connected to –Ara--W-Ara-, wherein Ar is an aryl group, Ara is an allyl-substituted aryl group, and W is a single bond, –C(CH3)2– and / or –SO2–. Preferably, Ne is an alkoxy group, such as methoxy, and X is Cl.

Description

Upcycling of polyarylethersulfone to make a reactive macromer productCross-Reference to Related Applications

[0001] This application claims priority to U.S. application No. 63 / 612740 filed on December 20, 2023 and to European application No. 24162163.0 filed on March 7, 2024, the entire content of these applications being incorporated herein by reference for all purposes.Technical Field

[0002] The present disclosure relates to a chemical upcycling process using a source of polarylethersulfone (PAES) as a reactant for manufacturing a PAES reactive macromer product and the use of such macromer product to make composites or to make articles from self-crosslinking macromer.Background Art

[0003] Products made from or incorporating plastic are a part of almost any workplace or home environment. Generally, the plastics that are used to create these products are formed from virgin plastic materials. That is, the plastics are produced from petroleum and are not made from existing plastic materials. Once the products have outlived their useful lives, they are generally sent to waste disposal or a recycling plant.

[0004] The omnipresence of plastics and the importance of environmental policy have led to the increased importance of recycled plastic materials. Virgin polymer composition replacement is considered to represent a significant way forward to solve the global plastic waste problem, stop the depletion of limited natural resources, and facilitate a circular economy. Recycling is one of the most significant actions which aims to reduce fossil oil usage, carbon dioxide emissions, the hazards associated with waste disposal, and the high rates of plastic pollution.

[0005] Recycling plastic has a variety of benefits over creating virgin plastic from petroleum. Generally, less energy is required to manufacture an article from recycled plastic materials derived from post-consumer and post-industrial waste materials and plastic scrap (collectively referred to in this specification as “waste plastic material”) than from the comparable virgin plastic. Recycling plastic materials obviates the need for disposing of plastic materials or products.

[0006] Generally, there are two ways to recycle plastics: physical recovery and chemical recovery. Mechanical recycling, also known as secondary recycling without changing the basic structure of the material, is a process of recovering waste plastic material for re-use in manufacturing plastic products via mechanicalmeans. Compare with chemical recycling, when available in large amounts, clean and mono-type plastic is more ideal for mechanical recycling and a win-win situation from an environmental and economic perspective. However, the availability of clean and homopolymeric-based material for mechanical recyclability is low. Chemical (tertiary) recycling is a term used to refer to advanced technology processes which convert plastic materials into smaller molecules, usually, liquids or gases, which are suitable for use as a feedstock for the production of new petrochemicals and plastics. Hence, most previous methods for chemical recycling of polymer compositions include repurposing polymers by depolymerization into lower molecular weight products which can only be used in applications other than originally targeted.

[0007] Given the demand for improved sustainability and circular economy, upcy cling a polymer waste is highly desired. Such recycling would be viewed as efficient resource utilization where no waste is generated and the polymer is cycled into a higher-value application than the application from which the polymer waste originated. Such an upcy cling process would be eco-friendly with high efficiency. Polymers reuse in their originally intended application is in general quite limited, such an upcy cling would be an improvement over incumbent technologies in which polymers are down-cycled for less-demanding and / or lower-value applications thus limiting their end-use.

[0008] The amorphous sulfone polymers are used successfully in modem industries such as automotive, electronic equipment, medical devices, and aerospace because the sulfone polymers exhibit a unique property profile that includes not only the benefits of high strength and temperature resistance but also inherent transparency in addition to other attributes. As a result, they are especially well qualified for all applications where traditional materials such as glass and metal are to be substituted.

[0009] Polyarylethersulfones (PAES polymers) are highly thermally stable polymers with excellent toughness and impact strength. These resins are made by polycondensation reactions typically using dihalodiphenyl sulfone (the sulfone monomer) along with other aromatic diols such as Bisphenol A, 4,4’ -bi phenol or dihydroxy diphenyl sulfone (also known as Bisphenol S).

[0010] PAES polymers can be used as toughening agents in epoxy resin composites. The toughness or the impact properties of such an epoxy composite can be enhanced by increasing the amount of poly sulfones in the matrix.

[0011] Due to the chemistry employed in the synthesis of sulfone polymers, these sulfone polymers do not have appreciable concentration of chemically reactive functional groups. As a consequence, these materials have poor solubility in the epoxycomposite matrix, which makes difficult the incorporation of PAES polymers into epoxy composite matrix. Furthermore most of the commercial poly sulfones have high molecular weight which lowers the solubility of the polymer in an epoxy matrix. Additionally, high molecular weight polymers also increase the viscosity of an epoxy formulation which makes the composite fabrication challenging.

[0012] To overcome the above challenges, special PAES polymers which have a low molecular weight and have chemical reactive functional end groups are used in such applications. PAES polymers featuring reactive end-groups possess a higher solubility than PAES without them, and as such, have been used to improve interfacial properties in epoxy resins.

[0013] An example of such a PAES polymer is Virantage® poly ethersulfone, commercially available from Solvay Specialty Polymers, which has a low molecular weight and aromatic hydroxyl or amine end groups. The amine and hydroxyl end groups of these polymers react with the epoxy matrix to form the cross-linked structure used for the composite applications.

[0014] US2014 / 329973 (Solvay Specialty Polymers USA) describes epoxy resin compositions comprising epoxy resins, one curing agent, one accelerator and at least two PAES polymers presenting distinct reactive end-groups.

[0015] An another class of functional groups can be used for self-crosslinking. These functional groups are self-reacting which means that there is no other polymer matrix like an epoxy. Acetylene and phenyl acetylene groups can thermally cyclodimerize and cyclo-trimerize at high temperatures such as 320 °C and 370 °C respectively. The cured materials using this technology generally have a high thermal performance since they do not contain any epoxy resins (which are aliphatic and hence have a lower thermal degradation temperature).

[0016] It is understood by the person skilled in the art that low molecular chain end- functionalized PAES polymers can be synthesized using stoichiometrically unbalanced monomer feed. Indeed in order to produce a low molecular weight intermediate often called a macromer, polymerization may be conducted with at least one monomer in excess relative to stoichiometry. The macromer resulting from the polymerization of a dihydroxy aromatic monomer with a molar excess of a dihalo aromatic sulfone has halide end groups, but if the dihydroxy aromatic monomer is in molar excess relative to stoichiometry, then the macromer resulting from the polymerization terminates in phenolic hydroxy groups.

[0017] In instances when an even more reactive PAES macromer is desired, the halide end groups of the macromer are typically reacted - a step generally termed “endcapping” during which the halide end groups are replaced by reactive end groups such as amines by reaction with an end-capping reagent, such as 3-aminophenol.The end-capping agent may be included with the initial monomer charge to the polymerization reaction.

[0018] In practice, however, the theoretical relationship between monomers ratio and final degree of polymerization is difficult to obtain. The condensation reaction is very sensitive to monomer concentration; and small deviations caused, for example, by ordinary imprecision in weighing as well as by the process of sampling during the long period of reaction required, can upset the delicate balance of monomers and polycondensation product.

[0019] Low molecular weight PAES polymers may also be generated through chemical depolymerisation of high molecular weight PAES materials. Since a PAES polymer is a polymer composed of sulfone as well as ether linkages, due to the strong electron withdrawing effect of the sulfone groups, the ether linkages are activated towards nucleophilic attack.

[0020] EP0532893 (Hercules Inc.) relates to a process of preparing a reactive reduced molecular weight polyarylene polyether from a starting polyarylene poly ether, in particular a PAES polymer, which includes contacting the starting polyarylene polyether with a nucleophilic reagent for a period of time sufficient to reduce the molecular weight of the starting poly arylene poly ether, and then recovering the reactive reduced molecular weight polyarylene poly ether. The most preferred nucleophiles used are alkali metal hydroxides, alkali metal sulfides, alkali metal hydrogensulfides, ammonia, alkylamines, hydrazines, and thiol or amino substituted triazoles. Such reactive reduced molecular weight polyarylenes preferably have tertiary amine reactive end groups. They are intended for use in combination with various other resins including epoxy, bismaleimide, cyanide ester, phenol-formaldehyde, urethane, polyester, vinyl ester, siloxane, cyclopentadiene and higher oligomers, acetylenic, and cyclic polycarbonate resins, or mixtures thereof. For example, a polyethersulfone ‘PES’ (Starting Polymer C) having a Mw of 35 000 g / mol is decomposed into a reduced molecular weight PES of a Mw from 5 780 to 10 100 g / mol (see Ex. 3, 8, 11, 12). Such a process does not provide a suitable yield in Bisphenol S. This patent teaches the reduction of the molecular weight of the starting polymer, but not purifying to recover monomer(s).

[0021] JP2009173902A (Sumitomo Chenical Co.) relates to a decomposition method for decomposing an aromatic ether compound with a basic compound having a >14 acid dissociation constant (pKa) at 25°C in the presence of a solvent. Among the basic compounds, quaternary ammonium hydroxide, alkali metal alkoxide, or alkaline earth metal alkoxide is particularly preferable. Decomposition of a PES polymer (Example 1) though led to a low yield of Bisphenol S.

[0022] A process for making highly -branched polyarylene ether polymers from linear polyarylene ether polymers is disclosed in US2005154178A1 (Xerox Corporation). Such process comprises (A) providing a reaction medium which comprises (i) an optional solvent, (ii) a polyfunctional phenol compound of the formula Ar(OH)x wherein x>3 and wherein Ar is an aryl moiety or an alkylaryl moiety, provided that when Ar is an alkylaryl moiety at least three of the -OH groups are bonded to an aryl portion thereof, (iii) one or more of linear polyarylene ether polymers. In Examples I-III, a linear polysulfone (PSU) is depolymerized and re-polymerization with a triol and cesium carbonate to yield a highly -branched polysulfone polymer for which the molecular weight is significantly reduced compared to the initial linear polysulfone (a 2.7-fold to 4.2- fold reduction in Mw) and its poly dispersity index (PDI) is significantly increased which provides evidence of a much higher degree of branching of the polymer backbone. The resulting sulfone polymer is structurally different from its original linear polysulfone polymer. Moreover, US2005154178A1 does not mention the recycling of polymeric waste.Summary of invention

[0023] The invention is as disclosed below and in the appended claims.

[0024] A first aspect of the present invention provides a process for upcy cling a polymeric waste material comprising at least one polyarylethersulfone to generate a reactive macromer product.

[0025] A second aspect of the present invention relates to the PAES reactive macromer product obtained by the process according to the present invention

[0026] A third aspect of the present invention relates to the PAES reactive macromer product.

[0027] A fourth aspect of the present invention relates to the PAES reactive macromer product which is self-crosslinking.

[0028] A fifth aspect of the present invention relates to a composite comprising a resin matrix, reinforcing fibers and the PAES reactive macromer product.

[0029] A sixth aspect of the present invention relates to an article made from the PAES reactive macromer product which is self-crosslinked by thermal treatmentDetailed Description of the present invention

[0030] Definitions

[0031] In the present application:- any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present disclosure, and each embodiment thus defined may be combined with another embodiment, unless otherwise indicated or clearly incompatible;- 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 individuals 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;- 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;- the term "comprising" (or “comprise”) includes "consisting essentially of (or “consist essentially of’) and also "consisting of (or “consist of’); and- the use of the singular ‘a’ or ‘one’ herein includes the plural unless specifically stated otherwise; and- it should be understood that the elements, properties, and / or the characteristics of a (co)polymer, product or article, a process, or a use, described in the present specification, may be combined in all possible ways with the other elements, properties and / or characteristics of the (co)polymer, product or article, process or use, explicitly or implicitly, this being done without departing from the scope of the present description.

[0032] The term “consisting essentially of’ in relation to a 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 composition, product, polymer, solution, process, method, etc can be included in such an embodiment. For example, when a 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 composition, compound, product, polymer, solution, etc or not more than 1 mol% based on the total number of moles of the composition, compound, product, polymer or solution.

[0033] In the present disclosure, the term “recurring unit” designates the smallest unit of a PAES polymer which is repeating in the chain and which is composed of a condensation of a diol compound and a dihalo compound. The term “recurring unit” is synonymous to the terms “repeating unit” and “structural unit”.

[0034] As used herein, the term “homopolymer” encompasses a polymer which only has one type of recurring unit.

[0035] As used herein, the term “copolymer” encompasses a polymer which may have two or more different types of recurring units.

[0036] The term "solvent" is used herein in its usual meaning that, it indicates a substance capable of dissolving another substance (solute) to form a uniformly dispersed mixture at the molecular level. In the case of a polymeric solute, it is common practice to refer to a solution of the polymer in a solvent when the resulting mixture is transparent and no phase separation is visible in the system. Phase separation is taken to be the point, often referred to as the "cloud point", at which the solution becomes turbid or cloudy due to the formation of polymer aggregates.

[0037] The term "membrane" is used herein in its usual meaning, that is to say, it refers to a discrete, generally thin, interface that moderates the permeation of chemical species in contact with it. A membrane generally comprises a polymer. Examples of membranes are water purification membranes and hemodialysis membranes.

[0038] The term “upcy cling” is a process of transforming a low-value material such as a polymeric waste material into at least one new material of higher value.

[0039] The term “post-consumer” polymeric material (or article) refers to a finished good that is used and then recycled; this may provide a source of polymeric waste material that can be used in the present method. The typical post-consumer polymeric material may include, but is not limited to, packaging, membranes, compounds, automotive components, electronic components, consumer product components such as but not limited to plastic bottles and particularly baby bottles, battery components, or any used or end-of-life three-dimensional injection- molded, extruded or printed articles or parts thereof.

[0040] The term “post-industrial” polymeric material (or article), also known as “preconsumer” polymeric material (or article), refers to waste generated from manufacturing processes that lead to the creation of the source polymeric material which can be used in the present method. For example, when a polymer is formed into bottles, polymeric scraps may be generated and they do not end up in the final bottle products. If these polymeric scraps are ground, shredded, or re-pelletized, and used again in making the same article or another article, they will be referred to as “post-industrial” polymeric material. Typical pre-consumer polymeric material may include, but is not limited to, whole articles, parts thereof, or scraps thereof, of packaging, films, fibers, membranes, off-specification compounds, or polymeric products including off-specification polyarylethersulfones, automotive components, electronic components, consumer product components such as plastic bottles and particularly baby bottles, battery components, or any three- dimensional injection-molded, extruded or printed articles or parts thereof.

[0041] In other words, post-consumer polymeric material (or article or waste) refers to finished goods, while post-industrial polymeric material (or article or waste)refers to waste material generated from a manufacturing process that manufactures polymers or polymeric based articles.

[0042] The weight average molecular weight (Mw) and the number average molecular weight (Mn) may be estimated by gel-permeation chromatography (GPC) using a mobile phase and calibrated with polystyrene or polymethylmethacrylate standards. The mobile phase may be selected from any solvent for the PAES polymers and macromers described herein, for example, the solvent(s) described herein, such as methylene chloride, N-alkyl-2-pyrrolidone like N-Methyl-2 -pyrrolidone (NMP), N-butyl-2-pyrrolidinone, etc., dimethyl sulfoxide (DMSO), l,3-dimethyl-2- imidazolidinone (DMI), tetramethylene sulfone (sulfolane), N,N'- dimethylacetamide (DMAc) or any mixture thereof. Unless explicitly stated otherwise, Mwand Mnof PAES polymers and macromers 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.

[0043] The polydispersity index (PDI) is hereby expressed as the ratio of weight average molecular weight (Mw) to the number average molecular weight (Mn).

[0044] The term “reactive” end group as used herein is meant to include those groups having reactive sites that can be reacted with other molecules or resins, containing epoxide, anhydride, cyanide ester, thiocyanate ester, maleimide, carboxyl, amine, acyl halide, isocyanate, hydroxyl, or halide groups via condensation, nucleophilic addition, alkylation reactions or other reactions known to those skilled in the art. The reactive end groups produced when practicing this invention are substantially comprised of a residue of the nucleophile used to effect the depolymerization together with the residue of a cleaved recurring unit formed during the depolymerization. For example, the use of aminophenol as the nucleophile leaves -NEE reactive groups, which are the residue of the nucleophile used to effect the depolymerization together with -OH reactive groups, which are the residue of a cleaved recurring unit formed during the depolymerization.

[0045] The term “unreactive” end group as used herein is meant to include those groups that do not react with other molecules or resins, containing epoxide, anhydride, cyanide ester, thiocyanate ester, maleimide, carboxyl, amine, acyl halide, isocyanate, hydroxyl, or halide groups via condensation, nucleophilic addition, alkylation reactions or other reactions known to those skilled in the art. The unreactive end groups when practicing this invention are substantially comprised of a residue of an unreactive end-capping agent, like an alkyl halide. For example, the use of methyl chloride as end-capping agent which react with -OH end groups leaves unreactive methoxy (-O-CH3) end groups.

[0046] The indeterminate article "a" in expressions like "a polymeric material" etc... is intended to mean "one or more", or "at least one" unless indicated otherwise.

[0047] Should the disclosure of any patents, patent applications, and publications that 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.

[0048] Disclosure of preferred embodiments of the present invention

[0049] The present invention addresses the recyclability of polyarylethersulfone (PAES polymer) where the polymer is effectively upcycled into a high value reactive macromer product. Since a phenolic nucleophile is added to the reaction medium, the type of sulfone macromer obtained after this process has the same recurring unit(s) as the starting sulfone material.

[0050] One of the benefits of the present invention is that the resulting reactive macromers can notably be used to increase the solubility of the PAES in certain materials (e.g., epoxy resins, polyurethane resins or unsaturated polyesters).

[0051] Another benefit is to reclaim virgin poly arylethersulfones produced in commercial plant operations or post-industrial polyarylethersulfone waste that do not meet certain product specifications, sometimes referred to as “off-specification” polyarylethersulfone (such as having a high yellow color index, generating hazy solutions, and / or having too low or too high Mwfor a specific intended application such as unsuitable for forming films or fibers in membrane applications). This polyarylethersulfone waste that does not meet certain product specifications becomes unsalable and therefore many times is disposed of in a landfill. By using the method according to this invention, the polyarylethersulfone manufacture commercial plants can achieve near 100% efficiency and reduce their environmental footprint while improving the production economics.

[0052] An aspect of the present invention relates to a process for chemically upcycling a polymeric material comprising at least one polyarylethersulfone (PAES polymer), comprising• in a reaction medium containing a polar aprotic solvent, a functional phenolic nucleophile, an alkali salt-forming carbonate agent, and a polymeric waste material comprising at least one PAES polymer having an initial number-average molecular weight (Mn1), depolymerizing the PAES polymer to obtain a PAES reactive macromer having a lower numberaverage molecular weight (MN);• optionally adding a protonating agent during or at the end of the depolymerization, wherein the protonating agent is different than the functional phenolic nucleophile, and• recovering the PAES reactive macromer to obtain a reactive macromer product.

[0053] Polymeric waste material

[0054] The polymeric waste material present in the reaction medium (RM) in the process of the present invention may be considered a waste, such as end-of-life products or articles, industrial scraps, and / or unsalable (e.g., off-specification, surplus) products or articles.

[0055] The polymeric waste material may be in solid form, such as pellets, fibers, flakes, powder, pieces of shredded or ground articles, coagulated particles, or any other solid 3-D objects, or in form of a solution or slurry in which at least part of the PAES polymer is dissolved before being subjected to the depolymerizing step.

[0056] The polymeric waste material comprises at least one material selected from the group consisting of post-consumer and post-industrial polymeric articles, postindustrial polymeric articles including article scraps, off-specification polyarylethersulfone products; and any combination thereof. The post-consumer and post-industrial polymeric articles preferably are selected from the group consisting of membranes, automotive components, electronic components, consumer product components such as baby bottles, composites, battery components, plumbing parts, animal cages, any parts or scraps thereof, and any combinations thereof.

[0057] The polymeric waste material may comprise at least 50% by weight (wt.%), based on the total weight of the polymeric waste material, of the PAES polymer. The polymeric material preferably comprises at least 55% wt.%, at least 60% wt.%, at least 65% wt.%, at least 70% wt.%, at least 75% wt.%, at least 80% wt.%, at least 85% wt.%, at least 90% wt.%, at least 95% wt.% or at least 99% wt.%, based on the total weight of the polymeric material, of the PAES polymer.

[0058] The polymeric waste material may consist essentially of the PAES polymer.

[0059] In alternate embodiments, the polymeric waste material comprises the PAES polymer and at least one additional component such as at least one non-PAES other polymer, at least one filler, and / or at least one additive.

[0060] Polyarylethersulfone (PAES polymer) in polymeric waste material

[0061] The polymeric waste material present in the reaction medium in the process of the present invention comprises at least one PAES polymer.

[0062] The PAES polymer may comprise 3 types of end groups, being at least one halide group X, at least one reactive end group Re1and at least one unreactive end group Ne.

[0063] The at least one reactive end group Re1in the PAES polymer is present in an amount of at most 20 mol%, or less than 20 mol%, or at most 15 mol%, based on the total amount of moles of end groups in the PAES polymer.

[0064] The at least one reactive end group Re1in the PAES polymer is preferably present in an amount of at least 0.5 mol%, or at least 1 mol%, or at least 1.5 mol% and up to 15 mol%, based on the total amount of moles of end groups in the PAES polymer.

[0065] In other embodiments, the at least one reactive end group Re1in the PAES polymer may be present in an amount of at least 1 microEq / g polymer and at most 15 microEq / g polymer, or at most 10 microEq / g polymer.

[0066] The at least one reactive end group Re1in the PAES polymer is preferably an -OH end group. The -OH end group is preferably connected to a divalent aryl group.

[0067] The at least one halide end group X in the PAES polymer may be present in an amount of from at least 50 mol%, preferably more than 50 mol%, more preferably at least 55 mol%, yet more preferably at least 60 mol%, and up to 95 mol%, preferably up to 90 mol%, more preferably up to 85 mol%, based on the total amount of moles of end groups in the PAES polymer.

[0068] In other embodiments, the at least one halide end group X in the PAES polymer is preferably present in an amount of at least 20 microEq / g polymer, or at least 25 microEq / g polymer, at least 30 microEq / g polymer, and / or at most 100 microEq / g polymer, or at most 95 microEq / g polymer.

[0069] The at least one halide end group X in the PAES polymer is preferably Cl and / or F, more preferably Cl.

[0070] The at least one unreactive end group Ne in the PAES polymer is present in an amount of at least 1 mol% and up to 50 mol%, preferably up to 45 mol%, more preferably up to 40 mol%, based on the total amount of moles of end groups in the PAES polymer.

[0071] The at least one unreactive end group Ne in the PAES polymer is preferably present in an amount of at least 1 microEq / g polymer and at most 30 microEq / g polymer, or at most 25 microEq / g polymer.

[0072] The at least one unreactive end group Ne in the PAES polymer is preferably selected from phenoxy groups, alkoxy groups, or combination thereof, more preferably is an alkoxy group, yet more preferably is a methoxy group.

[0073] Any suitable method may be used to determine the concentration of the end groups. For example, titration, NMR, FTIR or a halogen analyzer may be used. The concentration of the end groups (e.g., methoxy, amine and hydroxyl end groups) is preferably determined by titration and / orHNMR. Suitable methods are detailed in the examples below.

[0074] The PAES polymer comprises at least one recurring unit represented by formula (K) as follows:in which- in the formula (K), each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, sulfonic acid (-SO3H), alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and- in the formula (K), each i is independently zero or an integer of 1 to 4.

[0075] The PAES polymer may be a polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 98 mol.%, based on the total number of moles of recurring units of PAES POLYMER, of at least one recurring unit selected from those of formulaewherein : each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, sulfonic acid (-SO3H), alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and each i is independently an integer of 1 to 4.

[0076] The PAES polymer may be a homopolymer having one recurring unit selected from those of the formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’) or may be a copolymer comprising two or more recurring units selected from those of the formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’). In some embodiments, each R, in the recurring units selected from those of the formulae (L’), (N’), (O’), (Q’), as provided above, may be independently selected from the group consisting of sulfonic acid (-SO3H), alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently selected from integers from 1 to 4.

[0077] In particular, the PAES polymer may be a copolymer comprising at least 60 mol.%, based on the total number of moles of recurring units in the PAES polymer, or consisting essentially of,- the recurring units of formulae (L) and (L’),- the recurring units of formulae (N) and (N’),- the recurring units of formulae (O) and (O’),- the recurring units of formulae (Q) and (Q’), in which each R, in the recurring units of formulae (L’), (N’), (O’), (Q’), may be independently selected from the group consisting of sulfonic acid (-SO3H), alkalior alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently selected from integers of 1 to 4

[0078] In a preferred embodiment in the process for producing a reactive macromer product, the PAES polymer preferably comprises at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%, based on the total weight of the PAES polymer, of a sulfone polymer selected from the group consisting of:- PPSU,- PSU,- PES,- sulfonated PSU (sPSU),- sulfonated PES (sPES),- sulfonated PPSU (sPPSU),- any copolymer derived from at least two diols selected from biphenol, bisphenol A, bisphenol S, and / or hydroquinone and a dihalo monomer selected from sulfonated dihalodiphenylsulfone and / or dihalodiphenylsulfone,- a block polymer in the form A-B or A-B-A, comprising at least two blocks having different recurring units selected from those of formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’);- a block copolymer in the form A-B or A-B-A, comprising at least one block having one recurring unit selected from those of formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), and at least one polyalkylene oxide (PAO) block or polyvinylpyrrolidone (PVP) block, such as a polyethyleneglycol (PEG) block, a polypropyleneglycol (PPG) block or a PVP block; and- any combination of two or more thereof, wherein the formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’) are defined earlier.

[0079] As used herein, a polyethersulfone (PES) comprises at least 90 mol. %, at least 95 mol. %, or at least 98 mol. % of, or consists essentially of, recurring units (RPES) of the formula (O), the mol. % being based on the total number of moles of recurring units in the PES polymer. PES can be prepared by known methods and is notably available as VERADEL® PES from Solvay Specialty Polymers USA, L.L.C.

[0080] As used herein, a polysulfone (PSU) comprises at least 90 mol. %, at least 95 mol. %, or at least 98 mol. % of, or consists essentially of, recurring units (RPSU) of the formula (L), the mol. % being based on the total number of moles of recurring units in the PSU polymer. PSU can be prepared by known methods and is notably available as Udel® PSU from Solvay Specialty Polymers USA, L.L.C.

[0081] As used herein, a polyphenylsulfone (PPSU) comprises at least 90 mol. %, at least 95 mol. %, or at least 98 mol. % of, or consists essentially of, recurring units (RPPSU) of the formula (Q), the mol. % being based on the total number of moles of recurring units in the PPSU polymer). PPSU can be prepared by known methods and is notably available as RADEL® PPSU from Solvay Specialty Polymers USA, L.L.C.

[0082] As used herein, a sulfonated polyethersulfone (sPES) comprises at least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 98 mol. % of, or consists essentially of, a combination of recurring units (RPES) of the formula (O) and recurring units (RSPES) of the formula (O’), the mol. % being based on the total number of moles of recurring units in the sPES polymer, wherein each R in the formula (O’) is independently selected from the group consisting of sulfonic acid (-SO3H), alkali or alkaline earth metal sulfonate and alkyl sulfonate; and each i is independently an integer of 1 to 4.

[0083] As used herein, a sulfonated polysulfone (sPSU) comprises at least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 98 mol. % of, or consists essentially of, recurring units (RPSU) of the formula (L) and recurring units (RSPSU) of the formula (L’), the mol. % being based on the total number of moles of recurring units in the sPSU polymer, wherein each R in the formula (L’) is independently selected from the group consisting of sulfonic acid (-SO3H), alkali or alkaline earth metal sulfonate and alkyl sulfonate; and each i is independently an integer of 1 to 4.

[0084] As used herein, a sulfonated polyphenylsulfone (sPPSU) comprises at least 60 mol. %, at least 70 mol. %, at least 80 mol. %, at least 90 mol. %, at least 95 mol. %, or at least 98 mol. % of, or consists essentially of, recurring units (RPPSU) of the formula (Q) and recurring units (RSPPSU) of the formula (Q’), the mol. % being based on the total number of moles of recurring units in the sPPSU polymer, wherein each R in the formula (Q’) is independently selected from the group consisting of sulfonic acid (-SO3H), alkali or alkaline earth metal sulfonate and alkyl sulfonate; and each i is independently an integer of 1 to 4.

[0085] When used, the block polymer in the form A-B or A-B-A in the PAES polymer may comprise at least one block polymer having recurring units selected from those of PPSU, sPPSU, PSU, sPSU, PES, sPES, and at least one polyalkylene oxide or polyvinylpyrrolidone (PVP) block, such as a PEG block, PPG block or PVP block.

[0086] As used herein, a polyvinylpyrrolidone (PVP) block or polymer may comprise at least 90 mol.%, at least 95 mol.%, or at least 98 mol.% of, or may consist essentially of, recurring units Rp of following formula:said mol.% being based on the total number of moles of recurring units in the PVP block or polymer, in which n is an integer of at least 3, or at least 5, or at least 8, or at least 10, or at least 20, or at least 30, or at least 40, or at least 50, and at most 200, or at most 175, or at most 150, or at most 100.

[0087] As used herein, a “polyalkylene oxide” (PAO polymer) is understood to mean those polyalkylene oxides obtained by polymerisation of alkylene oxide such as ethylene oxide, 1,2-propylene oxide. The PAO polymer may be generally represented by the following formula: — [(CHRa)yO]z— H in which Rais H or an alkyl; y may be 1 to 3; z may be from 2 to 500. Polyethylene glycol (PEG) and polypropylene glycol (PPG) are examples of polyalkylene oxides.

[0088] In yet more preferred embodiments in the process for producing a PAES reactive macromer product, the PAES polymer comprises at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%, or consists of, a sulfone polymer selected from the group consisting of PPSU, PSU, PES, sPSU, sPES, sPPSU, and any combination thereof, the wt.% being based on the total weight of the PAES polymer.

[0089] In alternate embodiments in the process for producing a PAES reactive macromer product, the PAES polymer may in some instances consist of a blend of PES / PPSU, of PES / PSU, of PSU / PPSU, of PES / PSU / PPSU, of PES / sPES, of PSU / sPSU, or of PPSU / sPPSU.

[0090] In yet even more preferred embodiments in the process for producing a PAES reactive macromer product, the PAES polymer comprises at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%, or consists of, a sulfone polymer selected from the group consisting of PES, sPES, and any combination thereof, the wt.% being based on the total weight of the PAES polymer. The PAES polymer is yet more preferably selected from the group consisting of PES and sulfonated PES.

[0091] The PAES polymer is most preferably PES.

[0092] The PAES polymer may be produced by a variety of methods. The PAES polymer is preferably derived by polycondensation from at least one aromatic diol monomer (AA’) and at least one aromatic dihalo monomer (BB’).

[0093] For example U.S. Pat. Nos. 4,108,837 and 4,175,175 describe the preparation of polyarylethers and in particular polyarylethersulfones. Several one-step and two-step processes are described in these patents, which patents are incorporated herein by reference in their entireties. In these processes, a double alkali metal salt of a dihydric phenol (aromatic diol AA’) is reacted with a dihalobenzenoid compound (aromatic dihalo BB’) in the presence of a polar aprotic solvent under substantially anhydrous conditions. In a two-step process, the aromatic diol AA’ is first converted, in situ, in the presence of the solvent to the alkali metal salt derivative by reaction with an alkali metal or an alkali metal compound. An alkali metal salt is produced as a byproduct of the polymerization.

[0094] For PAES polymer manufacture, the preferred starting aromatic diol monomer (AA’) may be selected from the group consisting of 4,4’ -biphenol, bisphenol A, bisphenol S (4,4’-dihydroxydiphenyl sulfone), hydroquinone, resorcinol, and any combination thereof.

[0095] For PAES polymer manufacture, the preferred starting aromatic dihalo monomer (BB’) may be selected from the group consisting of 4,4’-dihalodiphenylsulfones and sulfonated derivatives thereof, preferably selected from 4,4’- difluorodiphenylsulfone (DFDPS), 4,4’-dichlorodiphenylsulphone (DCDPS), disulfonated DCDPS, and / or disulfonated DFDPS, and any combination thereof, more preferably selected from DCDPS and / or disulfonated DCDPS.

[0096] For PAES polymer manufacture, more than one aromatic diol monomer (AA’) may be used. For example, a first aromatic diol monomer (AA’)i may be selected from the group consisting of 4,4 ’-biphenol, bisphenol A, bisphenol S, and hydroquinone, and a second aromatic diol monomer (AA’)2 may be selected from the same group but is different from the first aromatic diol monomer (AA’)i .

[0097] The PAES copolymer has a number-average molecular weight (Mn1) of at least 10 000 g / mol, or at least 15 000 g / mol, or at least 16 000 g / mol, or at least 17 000 g / mol, or at least 18 000 g / mol, and / or at most 50 000 g / mol, or at most 45 000 g / mol, or at most 40 000 g / mol, or at most 35 000 g / mol.

[0098] The Mn1of the PAES polymer may be from 10,000 g / mol to 50,000 g / mol, or from 15,000 g / mol to 45,000 g / mol, or from 16,000 g / mol to 40,000 g / mol.

[0099] The weight average molecular weight Mw1of the PAES polymer may be at least 20 000 g / mol, or at least 30000 g / mol, or at least 35 000 g / mol, or at least 40 000 g / mol, or at least 45 000 g / mol, and / or at most 100 000 g / mol, or at most 90 000 g / mol, or at most 85 000 g / mol, or at most 80 000 g / mol, or at most 75 000 g / mol.

[0100] The Mw1of the PAES polymer may be from 20,000 g / mol to 100,000 g / mol, or from 35,000 g / mol to 90,000 g / mol or from 40,000 g / mol to 85,000 g / mol.

[0101] The weight average molecular weight (Mw1) and the number-average molecular weight (Mn1) of the PAES polymer is preferably determined by gel permeationchromatography (GPC) using methylene chloride as a mobile phase and calibrated with polystyrene standards.

[0102] Optional additive(s) in polymeric waste material

[0103] The polymeric waste material may further comprise an additive such as another polymer which is different than the PAES polymer (such as PVP, PEG, PPG), a solid filler, and / or one or more additional additives selected from ultraviolet light stabilizers, heat stabilizers, acid scavengers (i.e. zinc oxide, magnesium oxide), antioxidants, colorants, processing aids, lubricants, flame retardants, and / or electrical conductivity additive (i.e., carbon black, carbon nanotubes and carbon nanofibrils).

[0104] Optional other polymer in polymeric waste material

[0105] The polymeric waste material may further comprise another polymer which is different than the PAES polymer. The other polymer is preferably not a PAES, also referred to as a “non-PAES polymer”.

[0106] The other polymer in the polymeric waste material preferably may be a poreforming polymer such as polyvinylpyrrolidone (PVP), a polyalkylene oxide such as polyethylene glycol (PEG), or any combination thereof.

[0107] In instances when the polymeric waste material further comprises another polymer, the polymeric material may include:- a blend of the PAES polymer and the other polymer,- a coating or layer of at least one PAES polymer on top of at least a portion of a solid surface made from the other polymer, and / or- a block copolymer comprising at least one block of the PAES polymer and at least another block of the other polymer.

[0108] For example, the polymeric waste material may comprise a blend of a PAES polymer and a pore-forming polymer such as polyvinylpyrrolidone (PVP), a polyalkylene oxide (e.g., PEG, PPG) with a molecular weight of at least 200, preferably from 200 to 900, or any combination thereof.

[0109] In another example, the polymeric waste material may comprise, as the other polymer, a block copolymer in the form A-B or A-B-A, wherein the blocks A, and B represent at least one PAES polymer block and at least one polyalkylene oxide block, such as a PES:PEG, PPSU:PEG or PSU:PEG block copolymer.

[0110] In other embodiments, the other polymer in the polymeric waste material may be a polycarbonate (PC).

[0111] The polymeric waste material preferably comprises at most 25 wt.%, at most 20 wt.%, at most 15 wt.%, at most 10 wt.%, or at most 8 wt.%, of the other polymer(s), based on the total weight of the polymeric material.

[0112] Optional solid filler in polymeric waste material

[0113] The polymeric waste material may further comprise a solid filler. The filler is preferably non-polymeric. The filler may be a reinforcing filler. Indeed when it is desired to form a polymeric molded article with reduced weight but a high mechanical strength, the polymeric material may be reinforced by fillers.

[0114] In such instances, the polymeric waste material preferably comprises at most 60 wt.%, at most 55 wt.%, at most 50 wt.%, at most 45 wt.%, at most 40 wt.%, at most 35 wt.%, or at most 30 wt.% of the filler, and / or at least 2 wt.%, at least 4 wt.%, at least 6 wt.%, at least 8 wt.%, or at least 10 wt.%, of the filler, said wt.% being based on the total weight of the recycled polymeric material.

[0115] The filler may be in the form of particulate fillers, non-fibrous fillers, and fibrous fillers. A particulate reinforcing filler may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, and magnesium carbonate) or glass balls (e.g., hollow glass microspheres). A fibrous reinforcing filler is considered herein to be a tri-dimensional material having length, width, and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a fibrous material has an aspect ratio, defined as the ratio between the average length and the largest of the average width and average thickness of at least 5, at least 10, at least 20, or at least 50. A fibrous reinforcing filler may be selected from glass fibers, carbon fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, and / or steel fibers. Aramid fibers would be considered a polymeric filler. A “non-fibrous” filler is considered herein to have a tridimensional structure having a length, width, and thickness, wherein both length and width are significantly larger than its thickness. A non-fibrous reinforcing filler may contain glass or carbon.

[0116] In preferred embodiments, the polymeric waste material may further comprise a non-polymeric filler selected from mineral fillers, carbon fibers, and / or glass fibers.

[0117] Optional other additive(s) in polymeric waste material

[0118] The polymeric waste material may further comprise one or more additional additives selected from the group consisting of ultraviolet light stabilizers, heat stabilizers, acid scavengers (i.e. zinc oxide, magnesium oxide), antioxidants, colorants, processing aids, lubricants, flame retardants, and / or conductivity additive (i.e. carbon black, carbon nanotubes and carbon nanofibrils).

[0119] In such instances, the polymeric waste material preferably comprises at most 15 wt.%, at most 10 wt.%, at most 7.5 wt.%, or at most 5 wt.%, of the one or more additional additives, and / or at least 0.01 wt.%, at least 0.05 wt.%, at least 0.08wt.%, at least 0.1 wt.%, or at least 1 wt.%, of the one or more additional additives, said wt.% being based on the total weight of the polymeric waste material.

[0120] In preferred embodiments, the one or more optional additives in the polymeric waste material may be selected from the group consisting of :• at least one PVP,• at least one PEG,• at least one PPG,• at least one solid filler,• at least one colorant, and• any combination thereof; preferably selected from the group consisting of:• at least one PVP,• at least one PEG,• at least one glass filler, at least one carbon filler, and / or at least one mineral filler, in the form of fibers and / or particles,• at least one inorganic pigment,• at least one organic dye, and• any combination thereof; more preferably selected from the group consisting of:• at least one PVP.

[0121] Functional Phenolic Nucleophile in the reaction medium

[0122] At least one functional phenolic nucleophile is present in the reaction medium.

[0123] The at least one functional phenolic nucleophile is selected from the group consisting of:- monophenols with at least one functional group complementary to epoxy reactions, such a functional group being selected from aromatic monocarboxylic or dicarboxylic acids, primary alcohols, and / or aliphatic carboxylic acids,- monophenols with at least one thermally -induced self-reacting functional group, such a functional group being selected from phenyl ethynyl, ethynyl, cyano and / or allyl groups;- phenols with multifunctional groups capable of reacting with epoxy resins and in free radical reactions, such multifunctional groups being selected from a combination of allyl and phenol groups and / or a combination of vinylene & carboxylic acid; and- any combination thereof.

[0124] Preferably, the at least one phenolic nucleophile is selected from the group consisting of:monophenols with at least one functional group selected from aminophenols, aromatic monocarboxylic acids and / or dicarboxylic acids, preferably 3 -aminophenol, 4-aminophenol, or hydroxybenzoic acid; monophenols with at least one thermally-induced self-reacting functional group selected from phenylethynyl groups and / or ethynyl groups, preferably 4- hydroxyphenylacetylene or 4-(2-phenylethynyl)phenol; phenols with multifunctional groups being allyl and phenol groups, preferably 2,2’-diallyl bisphenol A, 2,2’-diallyl bisphenol S, or 2,2’-diallyl biphenol; more preferably 2,2’ -diallyl bisphenol A.

[0125] More preferably, the at least one phenolic nucleophile is selected from the group consisting of: monophenols with at least one functional group complementary to epoxy reactions:- monophenols with at least one thermally -induced self-reacting functional group:phenols with multifunctional groups:in which W is a bond, -C(CH3)2- and / or -SO2-, preferably W is -C(CH3)2- and / or -SO2-.

[0126] The at least one functional phenolic nucleophile may further comprise a diol: HO- Y-OH selected from the group consisting of bisphenol A, bisphenol S, 4,4’- biphenol, hydroquinone, and any combination thereof:(hydroquinone).

[0127] Such a diol HO-Y-OH may be used in the reaction medium in order for the unit -Y- to be integrated into the polymeric chain of the PAES reactive macromer during the depolymerisation step. This would offer the flexibility of tuning some of the PAES macromer’ s properties, especially in term of altering its solubility parameter. In composite applications, an enhancement in its solubility into a resin matrix would in turn improve its compatibility with such a resin matrix.

[0128] The content of the functional phenolic nucleophile in the reaction medium may be calculated based on the equation 1 / n when ‘n’ is the number of recurring units desired for the PAES reactive macromer. That is to say, the shorter the chain length of the desired PAES reactive macromer (i.e., the lower the number of recurring units), the higher amount of nucleophile needed in the reaction medium.

[0129] For example, when the PAES reactive macromer has the recurring unit of formula (K) being -CeFU-SCh-CeFE-O- for which the formula weight is 232.25 g / mol, and if it is desired to obtain a Mnfof about 4877 g / mol for the PAES reactive macromer which is equivalent to 21 recurring units of formula (K), the molarequivalent of the phenolic nucleophile should be 1 / 21 = 0.0476 molar Equivalent based on 1 molar equivalent of recurring unit of formula (K).

[0130] Generally, the content of the functional phenolic nucleophile in the reaction medium may be from 0.2 to 0.02 molar Equivalent relative to 1 molar Equivalent of recurring units in the PAES polymer.

[0131] The following Table 1 provides the estimate of nucleophile molar Equivalent when a desired Mnfof the PAES reactive macromer having all recurring units of formula (K) varies from 1 500 g / mol to 9 000 g / mol.

[0132] Table 1

[0133] For example, for a desired Mnffrom 1 500 g / mol to 9 000 g / mol of the PAES reactive macromer, the content of the functional phenolic nucleophile in the reaction medium may be from 0.15 to 0.026 molar Equivalent relative to 1 molar Equivalent of recurring unit of formula (K) in the PAES polymer.

[0134] For a desired Mnffrom 2 000 g / mol to 8 000 g / mol of the PAES reactive macromer, the content of the functional phenolic nucleophile in the reaction medium may be from 0.116 to 0.029 molar Equivalent relative to 1 molar Equivalent of recurring unit of formula (K) in the PAES polymer.

[0135] Preferably, the content of the functional phenolic nucleophile in the reaction medium may be from 0.04 to 0.06 molar Equivalent relative to 1 molar Equivalent of recurring unit of formula (K) in the PAES polymer.

[0136] Optional Aromatic Dihalo Monomer in the reaction medium

[0137] When an aromatic dihalo monomer is present in the reaction medium, the aromatic dihalo monomer may be selected from the group consisting of 4,4’- difluorodiphenylsulfone (DFDPS), 4,4’ -di chlorodiphenylsulfone (DCDPS), disulfonated derivatives thereof, and any combination thereof. More preferably, the aromatic dihalo monomer may be selected from the group consisting of DCDPS, disulfonated DCDPS, and combination thereof.

[0138] The presence of the additional aromatic dihalo monomer during depolymerisation favors the termination of the PAES reactive macromer with the functional reactive end group(s) originating from the nucleophile.

[0139] Preferably, the content of the optional aromatic dihalo monomer in the reaction medium may be from 0.5 to 0.8 molar Equivalent , preferably from 0.5 to 0.7 molar Equivalent, relative to 1 molar Equivalent of the nucleophile used in the reaction medium.

[0140] Alkali salt-forming carbonate agent in the reaction medium

[0141] The alkali salt-forming carbonate agent comprises, or consists of, an alkali metal carbonate, preferably potassium carbonate (K2CO3), sodium carbonate (Na2COs), and / or cesium carbonate (CS2CO3), more preferably potassium carbonate and / or sodium carbonate, yet more preferably potassium carbonate.

[0142] The content of the alkali salt-forming carbonate agent in the reaction mixture may be from 0.03 to 0.08 Equivalent of the alkali salt-forming carbonate agent, said Equivalent being relative to 1 molar equivalent of recurring units (such as of formula (K)) in the PAES polymer.

[0143] The alkali metal carbonate acts to deprotonate any aromatic phenol to form an alkali metal salt of such a phenol.

[0144] Polar aprotic solvent (S) in the reaction medium

[0145] The depolymerisation of the PAES polymer to prepare the PAES reactive macromer is carried out in the reaction medium (RM) comprising at least one polar aprotic solvent (S). The polar aprotic solvent (S) is preferably selected such that the PAES polymer in the polymeric waste material is soluble in this solvent.

[0146] The polar aprotic solvent (S) may be selected from the group consisting of 1,3- dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethylsulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene- 1,1 -di oxide (commonly called tetramethylene sulfone or sulfolane), N-alkyl-2-pyrrolidone like N-Methyl-2-pyrrolidone (NMP), N- butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropyleneurea (DMPU), dimethylformamide (DMF), tetrahydrothiophene- 1 -monoxide, and any combination thereof.

[0147] The polar aprotic solvent (S) is preferably selected from the group consisting of NMP, NBP, NEP, DMF, DMAc, DMI, DMSO, diphenylsulfone, sulfolane, and any combination thereof.

[0148] The polar aprotic solvent (S) is more preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, NMP, diphenylsulfone, and any combination thereof; most preferably selected from the group consisting of sulfolane, DMSO, DMAc, NMP, diphenylsulfone, and any combination thereof.

[0149] Addition steps in the process

[0150] The various ingredients of the reaction medium (that is to say, the polymeric waste material, the at least one functionalized phenolic nucleophile, the optional dihalo aromatic mononer, the alkali salt-forming carbonate agent and the polar aprotic solvent (S), optional components (such as aromatic dihalo monomer)) may be added simultaneously or sequentially to a reactor vessel to form the reaction medium.

[0151] In some cases, the polymeric waste material comprising the PAES polymer may be added to the reactor vessel in solid form, such as pellets, fibers, powder, flakes, pieces of shredded or ground articles, coagulated solids (e.g., coagulated polymer beads, particles, or prills), any other solid 3-D objects, or any mixture thereof. The pellets for example may be in any shape, such as cylindrical, spherical, or ovoid. In particular, when the polymeric waste material may comprise a post-industrial waste from a polyarylethersulfone manufacturing plant, such waste may be obtained after a coagulation step (in coagulated form) and subsequently not dried before being recycled and used as a reactant in the current process. The shape and size of the polymeric waste material are not critical so long as the PAES polymer in the polymeric waste material can dissolve, at least in part, preferably completely, in the polar aprotic solvent.

[0152] In some embodiments, the polymeric waste material comprising the PAES polymer may be added directly to the reactor vessel in solid form, and at least some of the PAES polymer may be “pre-dissolved” with some or all of the polar aprotic solvent (S) before adding the other components (nucleophile, optional dihalo aromatic mononer, alkali salt-forming carbonate agent) of the reaction medium (RM). It may be necessary to heat during pre-dissolution in order to facilitate the dissolution of PAES polymer. The dissolution may be favored at a temperature of at least ambient temperature, but should not exceed the boiling point of the solvent (S), preferably from 50°C to 150°C or from 70°C to 130°C.

[0153] In other embodiments, the nucleophile, the polymeric waste material comprising the PAES polymer, and optionally a dihalo aromatic mononer may be added directly to the reactor vessel, and the nucleophile, the optional dihalo aromatic mononer and at least part of the PAES polymer are pre-mixed and dissolved with the polar aprotic solvent (S) before adding the alkali salt-forming carbonate agent to the reactor vessel. It may be necessary to heat during pre-mixing in order to facilitate the dispersion and dissolution of the nucleophile, the optional dihalo aromatic mononer, and the PAES polymer. Dissolution may be favored at a temperature of at least ambient temperature but should not exceed the boiling point of the solvent (S), preferably from 50°C to 150°C or from 70°C to 130°C.

[0154] In alternate embodiments, the polymeric waste material comprising the PAES polymer may be added to the reactor vessel in form of a solution or slurry in which at least some of the PAES polymer is “pre-dissolved” ex-situ, that is to say, not in the reactor vessel, before being added to the reactor vessel. In such instances, the polymeric waste material may be mixed with a polar aprotic solvent (So). It may be necessary to heat the mixture of the polymeric waste material+ solvent (So) in order to facilitate the dissolution of PAES polymer into the solvent (So). The dissolution may be favored at a temperature of at least ambient temperature but should not exceed the boiling point of the solvent (So), preferably from 50°C to 150°C or from 70°C to 130°C. Such pre-dissolution preferably takes place in a vessel separate from the reactor vessel (e.g., a feed tank). In instances when the resulting pre-dissolved material is in the form of a slurry containing solids such as insoluble fillers originating from the polymeric waste material, the solids may be removed (e.g., the slurry is filtered) to recover a PAES polymer solution. The PAES polymer solution is then added to the reactor vessel. The polar aprotic solvent (So) into which the PAES polymer may be pre-dissolved is preferably the same polar aprotic solvent (S) used in the reaction medium, but not necessarily. Such polar aprotic solvent (So) is particularly selected for its ability to completely dissolve the PAES polymer and optionally the nucleophile when it is mixed ex-situ with PAES polymer. Any of the solvents described herein for the polar aprotic solvent (S) is equally suitable for pre-dissolving the PAES polymer and optionally the nucleophile before addition to the reactor vessel. The polar aprotic solvent (So) is preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, DMF, NMP, and combinations thereof. When the polar aprotic solvent (S) and (So) are the same, they are preferably selected from sulfolane, DMSO, DMAc, NMP, or combinations thereof.

[0155] In yet alternate embodiments, the various addition steps for preparing the reaction medium (RM) may be carried out as follows:- the at least one nucleophile, the polymeric waste material comprising PAES polymer and optionally a dihalo aromatic mononer are loaded into the reactor vessel with the solvent (S) to mix and dissolve the at least one nucleophile, the optional dihalo aromatic mononer and the PAES polymer into the polar aprotic solvent (S), preferably by heating at a temperature of from ambient temperature to less than the boiling point of the solvent (S), preferably from 50°C to 150°C or from 70°C to 130°C; and- then the alkali salt-forming carbonate agent is added to the reactor vessel after the dissolution of nucleophile, optional dihalo aromatic mononer and PAES polymer.

[0156] Depolymerisation step

[0157] Without wishing to be limited by theory, it is believed that the trans-etherification chemistry effects the scrambling of the ether bonds of the recurring units of the PAES polymer resulting in forming the PAES reactive macromer during the depolymerisation step in the process of the present invention.

[0158] In particular, the trans-etherification scrambles the ether bonds of the recurring units of the PAES polymer, so that the resulting polymer PAES reactive macromer is generally identical in chemical structure (i. e. , same recurring unit(s)), except that the added functionalized phenolic nucleophile changes the composition and distribution of the end groups of the PAES reactive macromer compared to the composition and distribution of the end groups of the starting PAES polymer.

[0159] The main advantage of the process according to the present invention is that it utilizes a one-pot synthesis (in the same reactor vessel) to make a PAES reactive macromer product from a polymeric waste material containing the PAES polymer used as a reactant.

[0160] Thus, the reaction medium (RM) in the reactor vessel comprises the polymeric waste material containing the PAES polymer, the at least one phenolic nucleophile, the alkali salt-forming carbonate agent, an optional dihalo aromatic monomer, and the polar aprotic solvent (S), before the depolymerisation starts.

[0161] The reaction medium (RM) may further contain a polar aprotic solvent (So) if used to pre-dissolve the PAES polymer, as previously described.

[0162] The reaction medium (RM) preferably comprises from 5 to 40 wt.%, from 10 to 35 wt.%, from 5 to 40 wt.%, from 15 to 35 wt.%, from 20 to 35 wt.%, or from 20 to 30 wt.%, or from 25 to 30 wt.%, based on the total weight of the reaction medium, of the PAES polymer.

[0163] The reaction time to form the PAES reactive macromer may be from 30 minutes to 6 hours, preferably from 45 minutes to 6 hours, more preferably from 1 hour to 4 hours.

[0164] The reaction temperature to form the PAES reactive macromer is at least 150°C. The reaction temperature is preferably at least 160°C, at least 165°C, at least 170°C, at least 175°C, at least 180°C, at least 185°C, at least 190°C, at least 195°C, or at least 200°C; and / or at most 350°C, at most 300°C, at most 295°C, at most 290°C, at most 285°C, at most 280°C, at most 275°C, at most 270°C, at most 265°C, or at most 260°C. Preferred ranges for the reaction temperature to form the PAES reactive macromer may be from about 150°C to about 350°C, from about 160°C to about 350°C, from about 160°C to about 295°C, from about 160°C to about 290°C, from about 165°C to about 285°C or from about 170°C to about 280°C.

[0165] Recovery of PAES reactive macromer

[0166] At the end of the depolymerisation, the PAES reactive macromer is separated from the other components of the reaction medium.

[0167] The non-polymeric components (such as fillers) originating from the starting polymeric waste material may be removed from the reaction medium, before or after separation of the PAES reactive macromer, by suitable methods such as dissolving and filtering, screening or extracting.

[0168] The PAES reactive macromer may be first recovered in the form of a PAES reactive macromer solution. This step may include filtration of the reaction medium to remove solid (insoluble) components and recover a PAES reactive macromer solution. The PAES reactive macromer solution should contain PAES reactive macromer dissolved in the solvent (S) (used during depolymerisation) and optionally the solvent (So).

[0169] The PAES reactive macromer is preferably recovered in solid form from the solvent (S) and optionally the solvent (So) (if used for pre-dissolution of the PAES polymer). This step may include filtration of the reaction medium to remove solid components (such as insolubles originating from the polymeric waste material) and recover a PAES reactive macromer solution. In some embodiments when there are not many alkali salts being formed during the depolymerisation, a filtration step may be omitted in the process of the present invention.

[0170] To recover the PAES reactive macromer in solid form, the PAES reactive macromer solution may be subjected to precipitation of the PAES reactive macromer solution from the solvent(s), preferably by coagulation, or devolatilization of the solvent(s) from the PAES reactive macromer solution.

[0171] The coagulation is based on precipitation of the PAES reactive macromer with a non-solvent or poor solvent. This coagulation step is preferably carried out by forming droplets of the PAES reactive macromer solution into a precipitation bath which comprises the non-solvent or poor solvent to form polymeric beads of PAES reactive macromer. The non-solvent may be selected from C1-C5 alcohol such as methanol, ethanol, n-propanol, isopropanol, butanol, ethyl acetate, methyl acetate, acetone, butanone, water, or any mixture thereof. Preferred non-solvent include ethanol, methanol, water, or any mixture thereof. The poor solvent may be a mixture of non-solvent and solvent (S) and / or (So). The non-solvent or poor solvent may comprise at least 50 wt.%, preferably at least 60 wt.%, of water and / or C1-C5 alcohol such as methanol, or ethanol.

[0172] The recovered solid PAES reactive macromer can be subjected to one or more washes with a washing liquid to further remove salts or other ingredients that remain in the macromer solids. The washing liquid is preferably water and / or Cl-C5 alcohol (e.g., methanol, ethanol, n-propanol, isopropanol). The washing liquid (e.g., water and / or methanol) is preferably at a temperature of at least 50°C, or at least 60°C, or at least 65°C. The washing liquid should be at a temperature not exceeding its boiling point. The washing liquid is preferably at a temperature of at most 90°C, or at most 85°C, or at most 80°C, or at most 75°C. The washing liquid is more preferably water at a temperature of from 60°C to 80°C, or from 65°C to 75°C. There may be two or more washes, using different washing liquids, such as first one or more washes with water and subsequently one or more washes with methanol.

[0173] The solid PAES reactive macromer may be dried at a temperature generally from about 50°C to 120°C, preferably from about 80°C to 120°C, more preferably at about 90-120°C, yet more preferably at about 90-110°C, preferably under vacuum.

[0174] The dried PAES reactive macromer can be used for preparing a composite material or an article.

[0175] Optional steps in the process

[0176] The process according to the present invention may further comprise at least one of the following steps, between the depolymerisation step and the recovery step: i. cooling: decreasing the temperature of the reaction medium; ii. quenching: adding a solvent (Sq), which may be the same or different than the polar aprotic solvent (S), to quench the reaction medium, generally to stop the depolymerisation reaction; and / or iii. end-capping: adding a reactive end-capping agent such as aminophenol or similar amine functionalized phenols to convert OH end groups of the formed PAES reactive macromer to more reactive amine end groups; iv. protonating: adding a protonating agent (such as oxalic acid, acetic acid and the like organic acids) to form -OH end groups from the phenoxide end groups.

[0177] In some embodiments of the process according to the present invention, only one optional step may be carried out.

[0178] Alternatively, at least two optional steps are carried out.

[0179] Step (i): Cooling may be affected by stopping the heating of the reaction medium. Cooling may be effected by adding, directly into the reaction medium, a further amount of the polar aprotic solvent (S) or another solvent which is at a temperature of at least 50°C less, at least 60°C less, or at least 70°C less, than the reaction medium temperature. The solvent added to the reaction medium for cooling is preferably at ambient temperature. The solvent added for cooling is preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, NMP, MCB, and any combination thereof. Alternatively, cooling may be affected by passing acooling fluid (without being mixed with the reaction medium (RM)) inside cooling tubes or using a cooling jacket for the reactor vessel.

[0180] Step (ii): Quenching may be carried out at the end of the reaction to decrease the polymer content of the reaction medium to a value of 20 wt.% or less based on the total weight of the quenched reaction medium. The solvent (Sq) added for quenching is preferably the same as the polar aprotic solvent (S) used during the reaction, but not necessarily. The solvent (Sq) is preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, NMP, MCB, and any combination thereof. After quenching, the polymer content of the quenched reaction medium is preferably from 5 to 20 wt.%, more preferably from 10 to 15 wt.%, based on the total weight of the quenched reaction medium.

[0181] The cooling and quenching steps (i) and (ii) may be carried out simultaneously by using a solvent (Sq) having a cooler temperature than the reaction temperature of the reaction medium at end of the reaction.

[0182] Step (iii): The end-capping (also called termination) preferably converts halide end groups of the formed PAES reactive macromer to more reactive end groups. The end-capping agent is preferably an aminophenol or similar amine functionalized phenols. The end-capping step (iii) may take place before or after the cooling of the reaction medium. As such the end-capping step (iii) may be carried out at the end of the depolymerisation reaction, either at reaction temperature or at a lower temperature than the reaction temperature.

[0183] The end-capping step (iii) to convert halide end groups in the PAES reactive macromer to more reactive end groups (such as amine group) may be omitted in the process of the present invention. For example, when the final PAES reactive macromer product already comprises at least 70 mol%, or even at least 75 mol%, of reactive end groups Refbased on the total number of moles of end groups in the PAES reactive macromer, the end-capping step (iii) may be omitted.

[0184] Step (iv): adding a protonating agent during or at the end of the depolymerization to form -OH end groups from phenoxide end groups. The protonating agent is different than the functional phenolic nucleophile. The protonating agent is preferably a carboxylic acid, preferably oxalic acid or acetic acid, more preferably oxalic acid. The protonating step (iv) preferably takes place after the cooling of the reaction medium. As such the protonating step (iv) is generally carried out at the end of the depolymerisation step at a lower temperature than the reaction temperature, preferably at a temperature of about 70 to 90°C.

[0185] The protonating step (iv) may be omitted in the process of the present invention. For example, when the final PAES reactive macromer product already comprises at least 70 mol%, or even at least 75 mol%, of reactive end groups Refbased on thetotal number of moles of end groups in the PAES reactive macromer, the protonating step (iv) may be omitted.

[0186] PAES Reactive Macromer

[0187] Another aspect of the present invention is a PAES reactive macromer.

[0188] The PAES reactive macromer is preferably obtained by the process according to the present invention.

[0189] The PAES reactive macromer comprises 3 different types of end groups, being- at least one halide group X,- one or more reactive end groups Ref, and- at least one unreactive end group Ne, with the proviso that the one or more reactive end groups Refin the PAES reactive macromer are present in an amount of more than 50 mol%, preferably more than 60 mol%, based on the total amount of moles of end groups in the PAES reactive macromer.

[0190] In the PAES reactive macromer, the 3 different types of end groups in the PAES reactive macromer may be as follows:- the at least one halide group X is selected from Cl and / or F, preferably is Cl;- the one or more reactive end groups Refare selected from hydroxy groups, aliphatic or aromatic carboxylic acids, alcohols, phenylethynyl groups, ethynyl groups, cyano groups, allyl groups, primary amine groups, secondary amine groups, tertiary amine groups, multifunctional groups and any combination thereof, said multifunctional group being selected from a combination of allyl and phenol groups and / or a combination of vinylene and carboxylic acid groups; and- the at least one unreactive end group Ne is selected from phenoxy groups, alkoxy groups, or combination thereof, preferably is an alkoxy group, more preferably is a methoxy group.

[0191] The one or more reactive end group Refin the PAES reactive macromer is preferably selected from hydroxy groups, aliphatic or aromatic carboxylic acids, alcohols, phenylethynyl groups, ethynyl groups, cyano groups, allyl groups, primary amine groups, secondary amine groups, tertiary amine groups, multifunctional groups and any combination thereof, said multifunctional group being selected from a combination of allyl and phenol groups and / or a combination of vinylene and carboxylic acid groups.

[0192] In some embodiments, the one or more reactive end group Refin the PAES reactive macromer may comprise a combination of at least one hydroxy group and of another group selected from aliphatic or aromatic carboxylic acids, alcohols, phenylethynyl groups, ethynyl groups, cyano groups, allyl groups, primary amine groups, secondary amine groups, tertiary amine groups, multifunctional groupsand any combination thereof, such a multifunctional group being selected from a combination of allyl and phenol groups and / or a combination of vinylene and carboxylic acid groups.

[0193] The one or more reactive end group Refin the PAES reactive macromer is preferably at least one end group which is connected to an -Ar- group and selected from -OH, -NH2 , -COOH, -C=CH, and / or -C=C-Ar, and / or an -OH end group connected to a -Ara'-W-Ara- group, in which Ar is a divalent aryl group, Arais a divalent allyl-substituted aryl group, and W is a single bond, - C(CHS)2- or -SO2-, preferably -C(CHs)2-

[0194] The at least one halide end group X in the PAES reactive macromer may be present in an amount of at least 0.5 mol% and up to 20 mol%, based on the total amount of moles of end groups in the PAES reactive macromer.

[0195] The at least one halide end group X in the PAES reactive macromer is preferably Cl and / or F, more preferably Cl.

[0196] The at least one unreactive end group Ne in the PAES reactive macromer is preferably selected from phenoxy groups, alkoxy groups, or combination thereof, more preferably is an alkoxy group, yet more preferably is a methoxy group.

[0197] In preferred embodiments, the 3 different types of end groups in the PAES reactive macromer are as follows:- the at least one halide end group X in the PAES reactive macromer is Cl;- the one or more reactive end groups Refin the PAES reactive macromer are at least one end group which is connected to an -Ar- group and selected from -OH, -NH2 , -COOH, -C=CH, and / or -C=C-Ar, and / or an -OH end group connected to a -Ara'-W-Ara- group, in which Ar is a divalent aryl group, Arais a divalent allyl-substituted aryl group, and W is a single bond, -C(CHs)2- or -SO2-, preferably -C(CHs)2-; and- the at least one unreactive end group Ne in the PAES reactive macromer is a methoxy group.

[0198] In some particular embodiments, the PAES reactive macromer is selfcrosslinking. In such instance, the PAES reactive macromer contains reactive end groups that are self-reacting, and there is no need for another polymer (such as an epoxy resin) to react with the functional groups of the PAES reactive macromer. Such a reactive group may be preferably selected from phenyl ethynyl, ethynyl, cyano and / or allyl groups. For example, acetylene and phenyl acetylene groups can thermally cyclo-dimerize and cyclo-trimerize at high temperatures such as 320 and 370 °C respectively. The cured materials using this technology generally have a high thermal performance.

[0199] The PAES reactive macromer preferably has a total reactive end group Refcontent of at least 100 pEq / g macromer, at least 120 pEq / g macromer, at least 140 pEq / g macromer, or at least 150 pEq / g macromer and / or at most 600 pEq / g macromer, at most 550 pEq / g macromer, at most 500 pEq / g macromer, or at most 450 pEq / g macromer.

[0200] The PAES reactive macromer preferably has a total unreactive end group Ne content of at least 1 pEq / g macromer and at most 5 Op Eq / g macromer, at most 45 pEq / g macromer, at most 40 pEq / g macromer, or at most 35 pEq / g macromer.

[0201] The PAES reactive macromer preferably has a total halide end group X content of at least 1 pEq / g macromer and at most 50 pEq / g macromer, at most 45 pEq / g macromer, at most 40 pEq / g macromer, or at most 35 pEq / g macromer.

[0202] The one or more reactive end groups Refin the PAES reactive macromer are preferably present in an amount of at least 70 mol% and up to 99 mol%, based on the total amount of moles of end groups in the PAES reactive macromer.

[0203] The at least one unreactive end group Ne in the PAES reactive macromer is preferably present in an amount of at least 0.5 mol% and up to 20 mol%, based on the total amount of moles of end groups in the PAES reactive macromer.

[0204] The at least one halide end group X in the PAES reactive macromer is preferably present in an amount of at least 0.5 mol% and up to 20 mol%, based on the total amount of moles of end groups in the PAES reactive macromer.

[0205] The PAES reactive macromer comprises at least one recurring unit represented by formula (K) as follows:in which- in the formula (K), each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, sulfonic acid (-SO3H), alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and- in the formula (K), each i is independently zero or an integer of 1 to 4.

[0206] The PAES reactive macromer may be a polymer comprising at least 50 mol%, based on the total number of moles of recurring units in the PAES reactive macromer, of at least one recurring unit selected from those of the formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), as provided earlier in relation to the PAES polymer. The PAES reactive macromer may be a homopolymer having a recurring unit selected from those of the formulae (L), (L’), (N), (N’), (O), (O’),(Q), (Q’), or may be a copolymer comprising two or more recurring units selected from those of the formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’). In preferred embodiments, each R, in the recurring units selected from those of the formulae (L’), (N’), (O’), (Q’), may be independently selected from the group consisting of sulfonic acid (-SO3H), alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently selected from integers from 1 to 4.

[0207] In particular, the PAES reactive macromer may be a copolymer comprising at least 60 mol.%, based on the total number of moles of recurring units of PAES reactive macromer, or consisting essentially of,- the recurring units of formulae (L), (L’),- the recurring units of formulae (N), (N’),- the recurring units of formulae (O), (O’), or- the recurring units of formulae (Q), (Q’), in which each R, in recurring units of formulae (L’), (M’), (N’), (O’) may be independently selected from the group consisting of sulfonic acid (-SO3H), alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently an integer of from 1 to 4.

[0208] When the PAES polymer is added as a reactant comprises a recurring unit selected from those of the formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), the PAES reactive macromer also comprises the same recurring unit as in the PAES polymer.

[0209] The PAES reactive macromer preferably comprises at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%, based on the total weight of the PAES reactive macromer, of a sulfone polymer selected from the group consisting of:- PPSU,- PSU, - PES,- sulfonated PSU (sPSU),- sulfonated PES (sPES),- sulfonated PPSU (sPPSU),- any copolymer derived from at least two diols selected from biphenol, bisphenol A, bisphenol S, and / or hydroquinone and a dihalo monomer selected from sulfonated dihalodiphenylsulfone and / or dihalodi phenylsulfone,- a block polymer in the form A-B or A-B-A, comprising at least two blocks having different recurring units selected from those of formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’);- a block copolymer in the form A-B or A-B-A, comprising at least one block having one recurring unit selected from those of formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), and at least one polyalkylene oxide (PAO) block or polyvinylpyrrolidone (PVP) block, such as a polyethyleneglycol (PEG) block, a polypropyleneglycol (PPG) block or a PVP block; and- any combination of two or more thereof, wherein the formulae (L), (L’), (N), (N’), (O), (O’), (Q), (Q’) are defined earlier.

[0210] The PAES reactive macromer more preferably comprises at least 50 wt.% of a sulfone polymer selected from the group consisting of PPSU, PSU, PES, sPSU, sPES, sPPSU, and any combination thereof, the wt.% being based on the total weight of the PAES reactive macromer.

[0211] The PAES reactive macromer is more preferably selected from the group consisting of PES and sulfonated PES.

[0212] The PAES reactive macromer may have a number average molecular weight Mwfof at least 3 000 g / mol, preferably at least 4 000 g / mol, more preferably at least 6 000 g / mol, yet more preferably at least 7 000 g / mol and / or at most 30 000 g / mol, preferably at most 25 000 g / mol, more preferably at most 20 000 g / mol.

[0213] The PAES reactive macromer may have a number average molecular weight Mnfof at least 1 500 g / mol, preferably at least 2 000 g / mol, more preferably at least 3 000 g / mol and / or at most 9 000 g / mol, preferably at most 8 000 g / mol, more preferably at most 7 000 g / mol.

[0214] In some embodiments, the PAES reactive macromer has a Mnfwhich is at least 60% less than the Mn1of the PAES polymer. A reduction of 60 to 90% in number average molecular weight is preferred. The reduction % is calculated by 100 (Mn1- Mnf) / Mn‘ .

[0215] In particular, the weight average molecular weight (Mwf) and number average molecular weight (Mnf) of PAES reactive macromer can be determined by gel permeation chromatography (GPC) using methylene chloride as a mobile phase and calibrated with polystyrene standards. The polydispersity index (PDIf) is hereby expressed as the ratio of weight average molecular weight (Mwf) to the number average molecular weight (Mnf).

[0216] In a particular embodiment, the PAES reactive macromer product contains a PES reactive macromer,- said PES reactive macromer having the recurring unit represented by the formula (K) in which i=0 which is described herein;- said PES reactive macromer comprising end groups being at least one halide end group X, one or more reactive end groups Refand at least one unreactive end group Ne,wherein- the at least one halide end group X is present in an amount of at least 0.5 mol% and up to 20 mol%;- the one or more reactive end group Refis present in an amount of at least 70 mol% and up to 99 mol%; and- the at least one unreactive end group Ne is present in an amount at least 0.5 mol% and up to 20 mol%, said mol% being based on the total amount of moles of end groups in the PAES reactive macromer. wherein said PES reactive macromer has a number-average molecular weight (Mnf) of at least 1 500 g / mol and at most 9 000 g / mol, preferably at least 2 000 g / mol and at most 8 000 g / mol, more preferably at least 3 000 g / mol and at most 7 000 g / mol, said Mnfbeing measured by Gel Permeation Chromatography using methylene chloride as mobile phase and polystyrene standards for calibration.

[0217] In yet another particular embodiment, the PAES reactive macromer product contains a PES reactive macromer,- said PES reactive macromer having the recurring unit represented by the formula (K) in which i=0 which is described herein;- said PES reactive macromer comprising end groups being at least one halide end group X, one or more reactive end groups Refand at least one unreactive end group Ne, wherein- the PES reactive macromer has a total reactive end group Refcontent of at least100 pEq / g, at least 120 pEq / g, at least 140 pEq / g, or at least 150 p.Eq / g and / or at most 600 p.Eq / g, at most 550 p.Eq / g, at most 500 pEq / g, or at most 450 pEq / g.- the PES reactive macromer has a total unreactive end group Ne content of at least 1 pEq / g and at most 50 p.Eq / g, at most 45 pEq / g, at most 40 p.Eq / g, or at most 35 pEq / g.- the PES reactive macromer has a total halide end group X content of at least 1 pEq / g and at most 50 p.Eq / g, at most 45 pEq / g, at most 40 pEq / g, or at most 35 pEq / g. wherein said PES reactive macromer has a number-average molecular weight (Mnf) of at least 1 500 g / mol and at most 9 000 g / mol, preferably at least 2 000 g / mol and at most 8 000 g / mol, more preferably at least 3 000 g / mol and at most 7 000 g / mol, said Mnfbeing measured by Gel Permeation Chromatography using methylene chloride as mobile phase and polystyrene standards for calibration.

[0218] Use of the PAES Reactive Macromer

[0219] The PAES reactive macromer product according to the present invention can be used in diverse applications as composites, adhesives, electronics, coatings, fibers, films, moldings, and extrusions.

[0220] The PAES reactive macromer product according to the present invention will most often be used in composite resin formulations in combination with high- strength filaments or fibers such as carbon (graphite), glass, silicon carbide and other ceramic fibers, alumina, titania, boron, aromatic polyamide or other organic reinforcing fibers, in the preparation of composites.

[0221] In particular, the PAES reactive macromer product according to the present invention may be used in combination with another resin such as epoxy, bismaleimide, cyanide ester, phenol-formaldehyde, urethane, polyester, vinyl ester, siloxane, cyclopentadiene and higher oligomers, acetylenic, and cyclic polycarbonate resins, or mixtures thereof.

[0222] Thus another aspect of the present invention provides the use of the PAES reactive macromer for preparing a composite (or a part thereof). In this application, the reactive functionalities in the end groups preferably improve the adhesion of a resin matrix to reinforcing fibers thereby improving performance.

[0223] The resin matrix of the composite may include an epoxy resin, a polyurethane resin or an unsaturated polyester resin.

[0224] The resin matrix preferably comprises the reactive PAES macromer product according to the present invention and an additional component which can, for example, be at least one epoxy component and / or a curing agent (for example polyalkylenepolyamines, such as ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and polyethylene polyamines (PEPA)).

[0225] The term “epoxy component” means a compound that contains more than one epoxy group, preferably two epoxy groups, per molecule. These epoxy compounds may be either saturated or unsaturated and aliphatic, cycloaliphatic, aromatic or heterocyclic and may also have hydroxyl groups. They are preferably glycidyl ethers which derive from polyhydric phenols, especially bisphenols or aminophenols and novolacs.

[0226] Yet another aspect of the present invention provides the use of a PAES reactive macromer which is self-crosslinking for preparing an article (or a part thereol). In such instance, the PAES reactive macromer contains reactive end groups that are self-reacting and which are preferably selected from phenyl ethynyl, ethynyl, cyano and / or allyl groups, more preferably selected from acetylene groups and / or phenyl acetylene groups. To induce crosslinking, the PAES reactive macromer is subjected to a thermal treatment at a high temperature, generally ranging from 320to 370 °C to form a cured article. The cured article using this technology generally has a high thermal performance. In this application, the PAES reactive macromer product is not used in combination with another resin.

[0227] The invention will be now described in more detail with reference to the following examples whose purpose is merely illustrative and not limitative of the scope of the invention.Examples

[0228] The invention will be now described in more detail with reference to the following examples whose purpose is merely illustrative and not limitative of the scope of the invention. As used in the Examples, “E” denotes an embodiment of the present invention.

[0229] Raw Materials

[0230] 2,2’ Diallyl BPA, available from Astatech

[0231] 4-aminophenol, 3-aminophenol, 4-(2-phenylethynyl)phenol, 3- hydroxyacetylene, 4-hydroxy benzoic acid, oxalic acid, hydrochloric acid, methanol, available from Sigma- Aldrich, U.S.A.

[0232] 4,4’-dichlorodiphenylsulfone (DCDPS) available from Solvay Specialty Polymers

[0233] K2CO3 (Potassium Carbonate), available from Armand products

[0234] Sulfolane, available from Chevron Phillips.

[0235] PES-1: Veradel® 3300 Premium, available from Solvay Specialty Polymers Characterisation of PES-1 Mw = 46,105 g / mol Mn = 18,349 g / mol PDI = 2.51Tg (DSC) = 225 °CTGA = 548 °C Td onsetEnd groups:(Titration) Hydroxyl (Sulfone) End groups = 4 micro equivalents / g(Titration) Chlorine End groups = 89 micro equivalents / g(1H NMR) Methoxy End groups = 17 micro equivalents / g

[0236] PES-2: Veradel® 3000MP, available from Solvay Specialty Polymers Characterisation of PES-2 Mw = 67,277 g / mol Mn = 20,312 g / mol PDI = 3.31Tg (DSC) = 230.2 °CTGA = 541.7 °CEnd groups:(Titration) Hydroxyl (Sulfone) End groups = 1.1 micro equivalents / g (Titration) Chlorine End groups = 38.98 micro equivalents / g ('H NMR) Methoxy End groups = 24.00 micro equivalents / g

[0237] PES-3: Hemodialysis fibers made of PES / PVP, available from Baxter Characterisation of PES-3 Mw = 62826 g / mol Mn = 26184 g / mol PDI = 2.39 Tg (DSC) = 226.34 °C TGA = 515.56 °C PVP Content = 3882 ppm End groups:(Titration) Hydroxyl (Sulfone) End groups = 9.9 micro equivalents / g (Titration) Chlorine End groups = 59.9 micro equivalents / g (1H NMR) Methoxy End groups = 1 micro equivalents / g

[0238] Test methods

[0239] GPC Method for measuring Afo / ect / far weights (Mn, Mw)

[0240] The molecular weights were measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5p mixed D columns with guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254nm was used to obtain the chromatogram. A flow rate of 1.5 ml / min and injection volume of 20 pL of a 0.2 w / v% solution in mobile phase was selected. Calibration was performed with 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.

[0241] Thermal gravimetric analysis (TGA)

[0242] 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.

[0243] !1HNMR

[0244] 11 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.

[0245] DSC

[0246] DSC was used to determine glass transition temperatures (Tg) and melting points (Tm)-if present. DSC experiments were carried out using a TA Instrument QI 00. DSC curves were recorded by heating, cooling, re-heating, and then re-cooling thesample 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 and Tm values were provided using the second heat curve unless otherwise noted.

[0247] HPLC-UV for measuring PVP content:

[0248] Size exclusion chromatography was performed, utilizing an Agilent 1100 series HPLC with a photodiode array (PDA) detector, for PVP detection and quantification. A PL Aquagel-OH 60 (8 pm x 300 mm x 7.5 mm) column was used as the stationary phase and an isocratic mobile phase consisting of 50 / 50 water / acetonitrile was implemented, with a total analysis time of 25 minutes. The flow rate was set to 1 mL min-1 at a column temperature of 60 °C and an injection volume of 20 pL. The PVP was detected and quantified utilizing the wavelength of 200 nm. The limit of detection, on a sample basis, for PVP is 100 ppm.

[0249] Example 1: Synthesis of amine- terminated PES reactive macromer El from PES-1Scheme 1: Synthesis of low molecular weight amine-terminated PES macromer El from high molecular weight PES-1 polymer

[0250] Procedure: The reaction took place in a glass reactor vessel (250 mL) equipped with an overhead stirrer, nitrogen inlet and Dean-Stark trap. While purging with nitrogen, PES-1 (Veradel® 3300) pellets (40.00 g), 4-aminophenol (1.068 g), potassium carbonate (1.758 g), and sulfolane (93.33 g) were added to the vessel first, and the resulting mixture was heated from room temperature to 220 °C using a 10°C / mi heating ramp. The reaction medium was allowed to react for 4 hours at 220 °C, then cooled to room temperature, pressure filtered, and coagulated into methanol. The solid (coagulated) polymer obtained was washed with methanol 4 times and then dried at 110°C under vacuum for at least 12 hours.

[0251] Characterization of the PES reactive macromer ElGPC: Mw = 8,723 g / mol , Mn = 4,241 g / mol, PDI = 2.06

[0252] End group chemistry(Titration)Hydroxyl content: 262 microeq / g(Titration) Chlorine content: 4 microeq / g(Titration) Amine: 176 microeq / g('H NMR) Methoxy content: 17 microeq / g

[0253] Example 2: Synthesis of amine- terminated PES reactive macromer E2 from PES-1

[0254] The synthesis was carried out in a similar way as in Scheme 1, except that 4,4’- dichlorodiphenylsulfone was further added to the reaction medium.Scheme 2: Synthesis of low molecular weight amine-terminated PES macromer from high molecular weight PES polymer

[0255] Procedure: The reaction took place in a glass reactor vessel (250 mL) equipped with an overhead stirrer, nitrogen inlet and Dean-Stark trap. While purging with nitrogen, PES-1 (Veradel® 3300) pellets (40.00 g), 4-aminophenol (1.068 g), DCDPS (1.405g), potassium carbonate (1.758 g), and sulfolane (93.33 g) were added to the vessel first, and the resulting reaction medium was heated from room temperature to 220 °C using a 10°C / mi heating ramp. The reaction medium was allowed to react for 4 hours at 220 °C, then cooled to room temperature, pressure filtered, and coagulated into methanol. The solid (coagulated) polymer obtained was washed with methanol 4 times and then dried at 110°C under vacuum for at least 12 hours.

[0256] Characterization of the PES reactive macromer E2GPC: Mw = 19864 g / mol, Mn = 6727 g / mol, PDI = 2.95End groups:(Titration)Hydroxyl content: 26 microeq / g (Titration) Chlorine content: 5 microeq / g (Titration) Amine content: 131 microeq / g ('H NMR) Methoxy content: 17 microeq / g

[0257] Example 3: Synthesis of amine-terminated PES macromer E3 from PES-2Amine terminated PESScheme 3: Synthesis of low molecular weight amine-terminated PES macromer E3 from PES-2 (with m<n)

[0258] Procedure: The reaction took place in a glass reactor vessel (500 mL) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. PES-2 powder (100 g), 3-aminophenol (2.6 g), sulfolane (300 g) were added to the vessel first, and the reaction medium was heated from room temperature to 200 °C using a 130°C / hour heating ramp. Then potassium carbonate (3.98 g) was added all at once and the temperature of the reaction medium was maintained for 90 minutes under nitrogen atmosphere and stirring. The reaction medium was then cooled to room temperature and then coagulated into methanol. The solid polymer obtained was washed again with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0259] Characterization of the PES reactive macromer E3GPC: Mw = 10151 g / mol, Mn = 4814 g / mol, PDI = 2.11 DSC = 198 °C TGA(onset) = 399 °C End group chemistry (Titration)Hydroxyl content: n / a microeq / g (Titration) Chlorine content: 11.33 microeq / g (Titration) Amine content: 152 microeq / g ('H NMR) Methoxy content: 35.0 microeq / g

[0260] Example 4: Synthesis of the carboxylic acid-terminated PES reactive macromer E4 from PES-2

[0261] Procedure: The reaction took place in a glass reactor vessel (500 mL) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. PES-2 powder (100 g), 4-hydroxybenzoic acid (3.3 g), sulfolane (300 g) were added to the vessel first and the resulting reaction medium was heated from room temperature to 200 °C using a 130°C / hour heating ramp. Then potassium carbonate (7.8 g) was added all at once, and the temperature of the reaction medium was maintained for 90 minutes under nitrogen atmosphere and stirring. The reaction medium was then cooled to 80 °C. Solid oxalic acid (10.8 g) as protonating agent was carefully added to the reaction medium in small portions, and the reaction was allowed to stir for another 60 minutes and then cooled to room temperature and then coagulated into 2 liters of 0.1N HC1 solution. The solid polymer obtained was washed again with deionized water once and then with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0262] Characterization of the PES macromer E4GPC: Mw = 11164 g / mol, Mn = 5696 g / mol, PDI = 1.96Tg (DSC) = 193.8 °CTGA(onset) = 518.3 °CEnd group chemistry(Titration)Hydroxyl content: 130.6 microeq / g(Titration) Chlorine content: 19.94 microeq / g('H NMR) Methoxy content: 32.2 microeq / g('H NMR) Carboxylic acid : 241.11 microeq / g

[0263] Example 5: Synthesis of the phenyl acetylene terminated PES reactive macromer E5 from PES-2Scheme 5 : Synthesis of low molecular weight phenyl acetylene terminated PES reactive macromer E5 from PES-2 (with m<n)

[0264] Procedure: The reaction took place in a glass reactor vessel (500 mL) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. The Veradel 3000MP powder (100 g), 3-hydroxyphenylacetylene (2.8 g), sulfolane (300 g) were added to the reactor vessel, and the resulting reaction medium was heated from room temperature to 200 °C using a 130°C / hour heating ramp. Then potassium carbonate (2.15 g) was added all at once and the temperature of the reaction medium was maintained for 90 minutes under nitrogen atmosphere and stirring. The reaction medium was then cooled to room temperature and then coagulated into methanol and then washed with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0265] Characterization of the PES reactive macromer E5GPC: Mw = 12767 g / mol, Mn = 6485 g / mol, PDI = 1.97 Tg (DSC) = 209.7 °C TGA(onset) = 518.3 °C End group chemistry (Titration)Hydroxyl content: 115.1 microeq / g (Titration) Chlorine content: 31.05 microeq / g (JH NMR) Methoxy content: 29.3 microeq / g ( H NMR) Alkyne content: 98.17 microeq / g

[0266] Example 6: Synthesis of the phenol and allyl terminated PES reactive macromer E6 from PES-2

[0267] Procedure: The reaction took place in a glass reactor vessel (500 mL) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. PES-2 powder (100 g), 2,2’ diallyl BPA (7.4 g), sulfolane (300 g) were added to the vessel, and the resulting reaction medium was heated from room temperature to 200 °C using a 130°C / hour heating ramp. Then potassium carbonate (3.98 g) was added all at once, and the temperature of the reaction medium was maintained for 90 minutes under nitrogen atmosphere and stirring. The reaction medium was then cooled to 80 °C. Solid oxalic acid (10.8 g) as protonating agent was carefully added to the reaction medium in small portions, and the reaction was allowed to stir for another 60 minutes and then cooled to room temperature and then coagulated into 2 liters of 0.1N HC1 solution. The solid polymer obtained was washed with deionized water once and then with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0268] Characterization of the PES reactive macromer E6GPC: Mw = 9934 g / mol, Mn = 3415 g / mol, PDI = 2.91Tg (DSC) = 184.3 °CTGA (onset) = 414.3 °C fH NMR) Allyl content : 5.23 %End group chemistry(Titration)Hydroxyl content: 131 microeq / g(Titration) Chlorine content: 20 microeq / g( H NMR) Methoxy content: 34.4 microeq / g

[0269] Example 7: Synthesis of amine-terminated PES reactive macromer E7 from hemodialysis fibers PES-3Amine terminated PESScheme 7: Synthesis of low molecular weight amine terminated PES reactive macromer E7 from PES-3 (with m<n)

[0270] Procedure: The reaction took place in a glass reactor vessel (250 mL) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. PES-3 fibers (25 g), 3-aminophenol (650 mg), sulfolane (75 g) were added to the vessel, and the resulting reaction medium was heated from room temperature to 200 °C using a 130°C / hour heating ramp. Then potassium carbonate (1 g) was added all at once, and the temperature of the reaction medium was maintained for 90 minutes under nitrogen atmosphere and stirring. The reaction medium was then cooled to room temperature and then coagulated into methanol. The obtained solid (coagulated) polymer was washed with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0271] Characterization of the PES reactive macromer E 7GPC: Mw = 7907 g / mol, Mn = 2947 g / mol, PDI = 2.68 Tg (DSC) = 186.7 °C TGA (onset) = 366.7 °C PVP content: none detected End group chemistry(Titration)Hydroxyl content: 182 microeq / g (Titration) Chlorine content: 7.61 microeq / g ('H NMR)Methoxy content: 6.7 microeq / g ( H NMR)Amine: 134 microeq / g

[0272] Example 8: Synthesis of 2-phenylethynyl terminated PES reactive macromerE8 from hemodialysis fibers PES-3Scheme 8 : Synthesis of low molecular weight phenyl ethynyl terminated PES reactive macromer E8 from PES-3 (with m<n)

[0273] Procedure: The reaction took place in a glass reactor vessel (250 mL) fitted with an overhead stirrer, nitrogen inlet and an overhead distillation set-up. PES-3 fibers (25 g), 4-(2-phenylethynyl)phenol (1.45 g), sulfolane (75 g) were added to the vessel, and the resulting reaction medium was heated from room temperature to 200 °C using a 130°C / hour heating ramp. Then potassium carbonate (0.77 g) was added all at once, and the temperature of the reaction medium was maintained for 90 minutes under nitrogen atmosphere and stirring. The reaction medium was then cooled to room temperature and then coagulated into methanol. The solid (coagulated) polymer obtained was washed with methanol twice and then dried at 110°C under vacuum for at least 12 hours.

[0274] Characterization of the PES reactive macromer E8GPC: Mw = 14125 g / mol, Mn = 6254 g / mol, PDI = 2.26Tg (DSC) = 211.0 °CTGA(onset) = 495.3 °CPVP content: not detectedEnd group chemistry(Titration) Chlorine content: 7.49 microeq / g(JH NMR )Hydroxyl content: 159.0 microeq / g('H NMR)Methoxy content: 1.15 microeq / g( H NMR)Phenylethynyl content: 124 microeq / g

[0275] The molar equivalents of the components in the reaction medium for synthezing the PES reactive macromer samples E1-E8 are shown in Table 2.

[0276] Table 2* DCDPS = 4,4-dichlorodiphenyl sulfone

[0277] The Mw, Mn, and PDI (via the GPC method) of the starting PES materials PES-1, PES-2, PES-3 and the PES macromer Samples E1-E8 resulting after coagulation and drying, as well as the calculated % reduction in Mn are reported in Table 3.

[0278] Table 3* protonating agent** GPC method using methylene chloride as mobile phase

[0279] It was observed that the resulting PE macromers in El to E8 had a significantly reduced Mw and Mn compared to their respective starting PES materials.

[0280] It was observed that the resulting PE macromers in El to E8 had a lower Tg and a lower TGA value compared to the Tg (DSC) and TGA values of their respective starting PES material.

[0281] The end groups analysis of the starting PES materials PES-1, PES-2, PES-3 and the PES macromers in Samples E1-E8 are reported in Table 4.

[0282] Table 4

[0283] It can be seen from Table 4 that the starting PES materials only had 3 types of end groups: the Cl end group, the reactive OH end group Re1, and the unreactive end group Ne (methoxy), although the reactive OH end group Re1in the starting PES materials PES-1, PES-2 and PES-3 did not exceed 10 microEq / g polymer. The Cl endgrougs were predominant in the starting PES materials. On the other end, the reactive OH end group Refin the PES reactive macromer samples E1-E8 significantly increased when compared to their respective starting PES material. The content of Cl endgrougs were signifantly reduced in the reactive macromer samples E1-E8. It can also be seen from Table 4 that the reactive macromer samples E1-E8 had a total reactive end group Refcontent of from 157 to 438 pEq / g macromer.

[0284] Table 5 provides the relative mol% of each type of end groups in the starting PES polymers and the PES reactive macromer samples E1-E8.

[0285] Table 5

[0286] It can be seen from Table 5 that the Cl end groups from the PES starting materials (PES-1, PES-2, PES-3) were above 60 mol% of all end groups, while the reactive -OH end groups Re1did not exceed 15 mol% and the unreactive (methoxy) end groups Ne did not exceed 40 mol%, such mol% being based on the total number of moles of end groups in each of the starting materials.

[0287] The relative amount (mol%) of OH end groups Refin the PES reactive macromer samples E1-E8 were much higher than the -OH end groups Re1in their respective PES starting material.

[0288] Example 9- Thermal crosslinking

[0289] In order to check whether the incorporation of the acetylene end groups in the reactive macromer E5 with a total of 78 mol% reactive end groups would result in thermal crosslinking, a sample of the reactive macromer E5 resin as a powder was heated in an air circulated oven for 2 hours at 320 °C. The heat treated material E9 was analyzed by DSC and TGA.

[0290] Characterization of the crosslinked material E9 from macromer E5

[0291] Crosslinked TGA: 484.8 °C

[0292] Crosslinked DSC: 228.4 °C

[0293] The DSC result showed that the glass transition temperature increased from 209.7 °C (E5) to 228.4 °C (E9), an increase of 18.7 °C in Tg, indicative of thermal crosslinking. Furthermore, this heat treated material E9 was insoluble in NMP at room temperature (based on a solubility test carried out over a period of 3 weeks).

[0294] Example 10 - Thermal crosslinking

[0295] In order to confirm that the incorporation of the phenyl acetylene end groups in the reactive macromer E8 with a total of 97 mol% reactive end groups would result in thermal crosslinking, a sample of the reactive macromer E8 resin as a powder was heated in an air circulated oven for 2 hours at 370 °C. The heat treated material E10 was analyzed by DSC and TGA.

[0296] Characterization of the crosslinked material E10 from macromer E8

[0297] Crosslinked TGA: 502 °C

[0298] Crosslinked DSC: 256 °C

[0299] The DSC results showed that the glass transition temperature increased from 211.0 °C to 256 °C, which represents a 45 °C increase in Tg, indicative of thermal crosslinking. Furthermore, this material E10 was insoluble in NMP at room temperature (based on a solubility test carried out over a period of 3 weeks).

[0300] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention.

[0301] What is claimed is:

Claims

Claims1. A process for upcy cling a polymeric waste material comprising at least one polyarylethersulfone to generate a reactive macromer product, comprising:• in a reaction medium containing a polar aprotic solvent, a functional phenolic nucleophile, an alkali salt-forming carbonate agent, and a polymeric waste material comprising at least one polyarylethersulfone (“PAES polymer”) having an initial number-average molecular weight (Mn1), depolymerizing said PAES polymer at a reaction temperature of at least 150°C to obtain a PAES reactive macromer having a lower number-average molecular weight (Mnf);• optionally adding a protonating agent during or at the end of the depolymerization, wherein the protonating agent is different than the functional phenolic nucleophile, and• recovering the PAES reactive macromer to obtain a reactive macromer product; wherein said PAES polymer comprises at least one recurring unit represented by formula (K) :in which- in the formula (K), each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, sulfonic acid (-SO3H), alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and- in the formula (K), each i is independently zero or an integer of 1 to 4; wherein the content of the functional phenolic nucleophile in the reaction medium is from 0.2 to 0.02 molar Equivalent, said molar Equivalents being relative to 1 molar Equivalent of recurring units in the PAES polymer; wherein said PAES polymer comprises end groups being at least one halide group X, at least one reactive end group Re1and at least one unreactive end group Ne, with the proviso that the at least one reactive end group Re1is present in less than 20 mol%, preferably less than 15 mol%, based on the total amount of moles of end groups in the PAES polymer;wherein said PAES reactive macromer comprises the same recurring unit represented by the formula (K); wherein said PAES reactive macromer comprises end groups being at least one halide group X, one or more reactive end groups Refand at least one unreactive end group Ne, with the proviso that the one or more reactive end groups Refare present in more than 50 mol%, preferably more than 60 mol%, based on the total amount of moles of end groups in the PAES reactive macromer; wherein said functional phenolic nucleophile is selected from the group consisting of: monophenols with at least one functional group complementary to epoxy reactions, such a functional group being selected from aromatic monocarboxylic or dicarboxylic acids, primary alcohols, and / or aliphatic carboxylic acids, monophenols with at least one thermally-induced self-reacting functional group, such a functional group being selected from phenyl ethynyl, ethynyl, cyano and / or allyl groups; phenols with multifunctional groups capable of reacting with epoxy resins and in free radical reactions, such multifunctional groups being selected from a combination of allyl and phenol groups and / or a combination of vinylene & carboxylic acid, and wherein said alkali salt-forming carbonate agent comprises, or consists of, an alkali metal carbonate, preferably potassium carbonate and / or sodium carbonate, more preferably potassium carbonate; and wherein said at least one halide group X is selected from Cl and / or F, preferably is Cl; said at least one reactive end group Re1is an -OH end group; and said one or more reactive end groups Refare selected from hydroxy groups, aliphatic or aromatic carboxylic acids, alcohols, phenylethynyl groups, ethynyl groups, cyano groups, allyl groups, primary amine groups, secondary amine groups, tertiary amine groups, multifunctional groups, or any combination thereof, said multifunctional group being selected from a combination of allyl and phenol groups and / or a combination of vinylene and carboxylic acid groups; and said at least one unreactive end group Ne is selected from phenoxy groups, alkoxy groups, or combination thereof, preferably is an alkoxy group, more preferably is a methoxy group.

2. The process of Claim 1, wherein the PAES polymer further contains another recurring unit represented by formula (K’),in which, in the formulae (K’),- T is a bond or -C(CHs)2-;- each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, sulfonic acid (-SO3H), alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and- each i is independently zero or an integer of 1 to 4.

3. The process of any one of Claims 1 to 2, wherein said unreactive end group Ne in the PAES reactive macromer is an alkoxy group, preferably a methoxy group.

4. The process of any one of Claims 1 to 3, wherein the at least one reactive end group Refin the PAES reactive macromer comprises at least one hydroxy group and another group selected from aliphatic or aromatic carboxylic acids, alcohols, phenylethynyl groups, ethynyl groups, cyano groups, allyl groups, primary amine groups, secondary amine groups, tertiary amine groups, multifunctional groups and any combination thereof, such a multifunctional group being selected from a combination of allyl and phenol groups and / or a combination of vinylene and carboxylic acid groups.

5. The process of any one of Claims 1 to 4, wherein the at least one reactive end group Refin the PAES reactive macromer is at least one end group which is connected to an -Argroup and selected from -OH, -NH2 , -COOH, -C=CH, and / or -C=C-Ar, and / or an - OH end group connected to a -Ara'-W-Ara- group, in which Ar is a divalent aryl group, Arais a divalent allyl-substituted aryl group, and W is a single bond, -C(CHs)2- or -SO2-, preferably -C(CHs)2-.

6. The process of any one of Claims 1 to 5, wherein the number-average molecular weight (Mnf) of the PAES reactive macromer is at least 1 500 g / mol and at most 9 000 g / mol, preferably at least 2 000 g / mol and at most 8 000 g / mol, more preferably at least 3 000 g / mol and at most 7 000 g / mol, said Mnfbeing measured by Gel PermeationChromatography using methylene chloride as mobile phase and polystyrene standards for calibration.

7. The process of any one of Claims 1 to 6, wherein the number-average molecular weight (Mn1) of the PAES polymer is from at least 15 000 g / mol to at most 50 000 g / mol, preferably from at least 16 000 g / mol to at most 45 000 g / mol, more preferably from at least 17 000 g / mol to at most 40 000 g / mol, yet more preferably from at least 18 000 g / mol to at most 35 000 g / mol, said Mn1being measured by Gel Permeation Chromatography using methylene chloride as mobile phase and polystyrene standards for calibration.

8. The process of any one of Claims 1 to 7, wherein the reaction mixture further comprises a dihalo aromatic sulfone compound, such as 4,4 ’-di chlorodiphenylsulfone (DCDPS), 4,4’ -difluorodiphenylsulfone, and / or monochloro-monofluoro diphenylsulfone, preferably DCDPS.

9. The process of any one of Claims 1 to 8, wherein said functional phenolic nucleophile is selected from the group consisting of: monophenols with at least one functional group selected from aminophenols, aromatic monocarboxylic acids and / or dicarboxylic acids, preferably 3- aminophenol, 4-aminophenol, or hydroxybenzoic acid; monophenols with at least one thermally-induced self-reacting functional group selected from phenylethynyl groups and / or ethynyl groups, preferably 4- hydroxyphenylacetylene or 4-(2-phenylethynyl)phenol; phenols with multifunctional groups being allyl and phenol groups, preferably 2,2’ - diallyl bisphenol A, 2,2’ -diallyl bisphenol S, or 2,2’ -diallyl biphenol; more preferably 2,2’-diallyl bisphenol A.

10. The process of any one of Claims 1 to 9, wherein said functional phenolic nucleophile further comprises a diphenol selected from the group consisting of bisphenol A, bisphenol S, 4,4’ -biphenol, hydroquinone, resorcinol, and any combination thereof.

11. The process of any one of Claims 1 to 10, wherein the polymeric waste material further comprises at least one additive.

12. The process of Claim 11, wherein the at least one additive in the polymeric waste material is selected from the group consisting of :• at least one PVP,• at least one PEG,• at least one PPG,• at least one solid filler,• at least one colorant, and• any combination thereof; preferably selected from the group consisting of:• at least one PVP,• at least one PEG,• at least one glass filler, at least one carbon filler, and / or at least one mineral filler, in the form of fibers and / or particles,• at least one inorganic pigment,• at least one organic dye, and• any combination thereof; more preferably selected from the group consisting of:• at least one PVP.

13. The process of any one of Claims 1 to 12, wherein the polar aprotic solvent in the reaction medium is selected from the group consisting of N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-butylpyrrolidinone (NBP), tetramethylene sulfone (sulfolane), dimethyl sulfoxide (DMSO), l,3-dimethyl-2-imidazolidinone (DMI), N,N dimethylacetamide (DMAc), diphenyl sulfone (DPS), and any combination thereof.

14. The process of any one of Claims 1 to 13, wherein the alkali salt-forming carbonate agent comprises potassium carbonate.

15. The process of any one of Claims 1 to 14, wherein the contents of the functional phenolic nucleophile and of the alkali salt-forming carbonate agent in the reaction mixture are : from 0.04 to 0.06 molar Equivalent of the functional phenolic nucleophile, and from 0.03 to 0.08 molar Equivalent of the alkali salt-forming carbonate agent, said molar Equivalents being relative to 1 molar Equivalent of recurring unit of formula (K).

16. The process of any one of Claims 1 to 15, wherein the depolymerizing step comprises the step of heating the reaction medium to reach a reaction temperature of at least 160°C, or at least 170°C, or at least 180°C or at least 190°C and / or at most 240°C, or at most 230°C.

17. The process of any one of Claims 1 to 16, further comprising adding a carboxylic acid as protonating agent, preferably oxalic acid or acetic acid, more preferably oxalic acid, at the end of depolymerisation.

18. The process of any one of Claims 1 to 17, wherein the PAES polymer in the polymeric waste material is selected from the group consisting of PES and sulfonated PES, preferably PES.

19. The process of any one of Claims 1 to 18, wherein the polymeric waste material is in solid form, such as pellets, fibers, flakes, powder, pieces of shredded or ground articles, coagulated particles, or any other solid 3-D objects, or in form of a solution or slurry in which at least part of the PAES polymer is dissolved before being subjected to the depolymerizing step.

20. The process of any one of Claims 1 to 19, wherein the polymeric waste material comprises at least one material selected from the group consisting of post-consumer and post-industrial polymeric articles, polymeric scraps, off-specification PAES polymer products; and any combination thereof, said polymeric articles preferably being selected from the group consisting of membranes, automotive components, electronic components, consumer product components such as baby bottles, composites, battery components, plumbing parts, animal cages, and any combinations thereof.

21. The process of any of Claims 1 to 20, wherein the recovery step comprises- mixing the PAES reactive macromer in a non-solvent to form a precipitate which contains the PAES reactive macromer and a liquid phase;- separating, preferably by filtration, said liquid phase from the precipitate; and- drying said precipitate to recover the PAES reactive macromer product in solid form.

22. The process of any one of Claims 1 to 21, wherein the polymeric waste material comprises polyvinylpyrrolidone (PVP), and wherein the reactive macromer product has no detectable PVP content after recovery.

23. A PAES reactive macromer product obtained by the process of any one of claims 1 to 22.

24. A PAES reactive macromer product containing a PAES reactive macromer,said PAES reactive macromer comprising at least one recurring unit represented by formula (K); said PAES reactive macromer comprising 3 types of end groups being at least one halide end group X, one or more reactive end groups Refand at least one unreactive end group Ne, with the proviso that the one or more reactive end group Refis / are present in more than 50 mol%, preferably more than 60 mol%, based on the total amount of moles of end groups in the PAES reactive macromer; said PAES reactive macromer having a number-average molecular weight (Mnf) of at least 1 500 g / mol and at most 9 000 g / mol, preferably at least 2 000 g / mol and at most 8 000 g / mol, more preferably at least 3 000 g / mol and at most 7 000 g / mol, said Mnfbeing measured by Gel Permeation Chromatography using methylene chloride as mobile phase and polystyrene standards for calibration;- wherein the formula (K) of the recurring unit is as follows:in which- in the formula (K), each R is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, sulfonic acid (-SO3H), alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and- in the formula (K), each i is independently zero or an integer of 1 to 4.

25. The PAES reactive macromer product of Claim 23 or 24, wherein : the at least one halide end group X is present in an amount of at least 0.5 mol% and up to 25 mol%; the one or more reactive end groups Refare present in an amount of at least 70 mol% and up to 99 mol%; and the at least one unreactive end group Ne is present in an amount at least 0.5 mol% and up to 15 mol%, said mol% being based on the total amount of moles of end groups in the PAES reactive macromer.

26. The PAES reactive macromer product of Claim 23 or 24, having: a total reactive end group Refcontent of at least 100 pEq / g, at least 120 pEq / g, at least 140 pEq / g, or at least 150 pEq / g and / or at most 600 pEq / g, at most 550 pEq / g, at most 500 pEq / g, or at most 450 pEq / g; and / ora total unreactive end group Ne content of at least 1 pEq / g and at most 50, at most 45, at most 40, or at most 35 pEq / g; and / or a total halide end group X content of at least 1 pEq / g and at most 50 pEq / g, at most 45 pEq / g, at most 40 pEq / g, or at most 35 pEq / g.

27. The PAES reactive macromer product of any one of Claims 23 to 26, wherein : the at least one halide end group X is Cl; the one or more reactive end groups Refare at least one end group connected to an -Ar- group and which is selected from -OH, -NH2 , -COOH, -C=CH, and / or -C=C-Ar, and / or an -OH end group connected to a -Ara'-W-Ara- group, in which Ar is a divalent aryl group, Arais a divalent allyl-substituted aryl group, and W is a single bond, -C(CHs)2- or -SO2-; and the at least one unreactive end group Ne is an alkoxy group, preferably a methoxy group.

28. The PAES reactive macromer product of any one of Claims 23 to 27, being selfcrosslinking.

29. The PAES reactive macromer product of claim 28, wherein at least one reactive end group Refis selected from phenyl ethynyl groups, ethynyl groups, cyano groups, allyl groups, and any combination thereof, preferably selected from acetylene groups and / or phenyl acetylene groups.

30. A composite comprising a resin matrix, reinforcing fibers and the PAES reactive macromer product of any one of Claims 23 to 29.

31. An article made from the PAES reactive macromer product of any one of Claims 28 and 29 which is self-crosslinked by thermal treatment.