Method for producing a polymer using poly(aryl ether sulfone) as a reactant

Abstract

A method for producing polyaryl ether sulfone "PAES" (P2) using a recycled polymer material, comprising heating a reaction medium (RM) containing a recycled polymer material containing polyaryl ether sulfone "PAES" (P1), at least one monomer (M), an alkali salt former (A), and a polar aprotic solvent (S) until a reaction temperature of at least 150 °C is reached to form PAES (P2), and separating the formed PAES (P2) from the reaction medium. The recycling rate of PAES (P1) may be from 100% by weight to 1% by weight. The recycled polymer material added to the reaction medium may further contain other polymers, solid fillers, and / or additives. The monomer (M) may be at least one aromatic diol monomer (AA) and / or at least one aromatic dihalomonomer (BB). The diol (AA) may include bisphenol A, bisphenol S, biphenol, 1,4:3,6-dianhydrohexitol sugar diol, and / or tetramethylbisphenol F, and the dihalo (BB) may include non-sulfonated and / or disulfonated dihalodiphenyl sulfone.

Description

Technical Field

[0001] Cross - reference to related applications This application claims priority based on Indian Patent Application No. 202221034350 filed on June 15, 2022 and European Patent Application No. 22194749.2 filed on September 9, 2022, and the entire contents of these applications are incorporated herein by reference for all purposes.

[0002] The present disclosure relates to a chemical recycling process that uses a source of recycled polyaryl ether sulfone as a reactant for producing sulfone polymers.

Background Art

[0003] Products made from plastics or products incorporating plastics are part of almost every workplace or household environment. Generally, the plastics used to create these products are formed from virgin plastic materials. That is, plastics are manufactured from petroleum and not from existing plastic materials. After exceeding their service life, products are usually sent to landfills or recycling plants.

[0004] Due to the popularity of plastics and the importance of environmental policies, the importance of recycled plastic materials is increasing. Replacing virgin polymer compositions is considered an important way to solve the global plastic waste problem, stop the depletion of limited natural resources, and promote a circular economy. Recycling is one of the most important measures aimed at reducing the use of fossil oil, carbon dioxide emissions, the risks associated with waste treatment, and the high rate of plastic pollution.

[0005] Recycling plastics has various advantages compared to forming virgin plastics from petroleum. Generally, the energy required to manufacture articles from recycled plastic materials obtained from post-consumer waste, post-industrial waste, and plastic scraps (collectively referred to herein as "waste plastic materials") is less than that required to manufacture from equivalent virgin plastics. By recycling plastic materials, there is no need to discard plastic materials or products.

[0006] Generally, there are two methods for plastic recycling: physical recycling and chemical recycling. Mechanical recycling, also known as secondary recycling that does not change the basic structure of the material, is a process of recovering waste plastic materials for reuse in the manufacture of plastic products by mechanical means. Compared with chemical recycling, when available in large quantities, clean single-species plastics are ideal for mechanical recycling, presenting a win-win situation from both environmental and economic perspectives. However, the availability of materials based on clean homopolymers that can be mechanically recycled is low. Chemical (tertiary) recycling refers to a term used to describe an advanced technical process that converts plastic materials into smaller molecules, usually liquids or gases, suitable for use as raw materials for the production of new petrochemical products and plastics. Therefore, most of the conventional methods of chemical recycling of polymer compositions involve depolymerizing the polymer into low-molecular-weight products that can only be used for purposes other than the original purpose and then reusing them for another purpose.

[0007] Considering the demand for improving sustainability and circular economy, it is highly desirable to recycle polymers back to the same use for which they were intended. Such recycling would be considered efficient resource utilization that generates no waste and circulates the polymer back to the same use as the one for which it first became waste (after its initial use). Such a recycling process would be environmentally friendly and highly efficient. This represents an improvement over existing technologies where polymers are recycled into less demanding uses and thus have limited end uses. The reuse of polymers in their original intended use is generally very limited.

[0008] Amorphous sulfone polymers have been successfully used in modern industries such as automotive, electronics, medical devices, and aerospace because they exhibit a unique property profile that includes not only the advantages of high strength and heat resistance but also inherent transparency in addition to other properties. As a result, they are particularly suitable for any application that replaces conventional materials such as glass and metal.

[0009] Examples of sulfone polymers manufactured using recycled polymer waste can be found in U.S. Patent Application Publication No. 2016 / 002431A1 (IBM), the paper by Hong et al. (Green Chemistry, 2017, vol. 19, pp. 3692 - 3706), and the paper by Jones et al. (PNAS, July 12, 2016, vol. 113(28), pp. 7722 - 7726). These references describe the use of polycarbonate as a source of bisphenol A for manufacturing sulfone polymers using difluorodiphenyl sulfone and carbonate. The resulting polymer is a polysulfone polymer that is structurally different from the base polycarbonate material PC used as a source of bisphenol A monomer.

[0010] U.S. Patent No. 2005 / 154,178 A1 (Xerox) discloses a method for producing highly branched poly(arylene ether) polymers from linear poly(arylene ether) polymers. Such a method involves feeding a reaction medium comprising (A) (i) an optional solvent, (ii) a polyfunctional phenol compound of the formula Ar(OH)x where x ≧ 3 and 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 attached to its aryl portion), and (iii) one or more linear poly(arylene ether) polymers. In Examples I - III, linear polysulfone (PSU) is depolymerized and repolymerized using a triol and cesium carbonate to obtain a highly branched polysulfone polymer, but the molecular weight of this polymer is significantly reduced compared to the original linear polysulfone (1 / 2.7 to 1 / 4.2 by MW), and its polydispersity (PDI), which is evidence of a much higher degree of branching in the polymer backbone, increases significantly. The resulting sulfone polymer is structurally different from its original linear polysulfone polymer. Further, this reference does not mention the recycling of polymer waste. SUMMARY OF THE INVENTION

[0011] The present invention is as set forth below and in the appended claims.

[0012] The present invention addresses the recyclability of sulfone polymers, effectively recycling polymers by a one-pot process that breaks down the repeating units of the polymer into a scrambled mixture and incorporates them into newly formed polymer chains from oligomers and monomers in a reaction medium. Since monomers can be added to the reaction medium, when the added monomer corresponds to the same monomer as the monomer from which the recycled sulfone polymer is derived, the type of sulfone polymer obtained after this process can have the same chemical structure and properties. On the other hand, when the monomer added to the reaction medium generates different types of sulfone repeating units, the resulting polymer contains not only repeating units derived from the recycled sulfone polymer but also other repeating units derived from the added monomer.

[0013] Another advantage is the ability to recycle unused polyarylether sulfone produced in the operation of a commercial plant or post-industrial polyarylether sulfone waste that does not meet certain product specifications, sometimes referred to as "off-spec" polyarylether sulfone (such as high yellowness, polymers that produce turbid solutions, or those with too low or too high Mw for specific applications like forming films or fibers for membrane use). This polyarylether sulfone waste that does not meet specific product specifications becomes unsellable and is therefore often landfilled. By using this methodology, a commercial plant for polyarylether sulfone production can achieve nearly 100% efficiency and reduce its environmental footprint while improving production economics.

[0014] A first aspect of the present invention is a method for producing polyarylether sulfone (P2) using a recycled polymer material containing polyarylether sulfone (P1) as a reactant, · adding a polar aprotic solvent (S) to a reaction vessel, · adding a recycled polymer material containing polyarylether sulfone (P1) to the reaction vessel, · Adding an alkali salt former (A) to a reaction vessel, · Adding at least one monomer (M) selected from the group consisting of at least one aromatic diol monomer (AA) and at least one aromatic dihalo monomer (BB) to the reaction vessel, whereby the addition step forms a reaction medium (RM) containing a recycled polymer material comprising polyarylethersulfone (P1), at least one monomer (M), an alkali salt former (A), and a polar aprotic solvent (S), · Heating the reaction medium to reach a reaction temperature of at least 150 °C to form polyarylethersulfone (P2), and · Separating the formed polyarylethersulfone (P2) from the reaction medium, comprising; The alkali salt former (A) is an alkali metal carbonate and / or an alkali metal hydroxide; A method is provided.

[0015] The aromatic diol monomer (AA) can be selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, isosorbide, isomannide, isoidide, tetramethylbisphenol F, hydroquinone, and any combination thereof, preferably selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, tetramethylbisphenol F, hydroquinone, and any combination thereof.

[0016] The aromatic dihalo monomer (BB) can be selected from the group consisting of 4,4'-difluorodiphenyl sulfone (DFDPS), 4,4'-dichlorodiphenyl sulfone (DCDPS), disulfonated DCDPS, disulfonated DFDPS, and any combination thereof, preferably selected from the group consisting of DCDPS, disulfonated DCDPS, and any combination thereof.

[0017] Polyarylether sulfone (P1) is derived by condensation from at least one aromatic diol monomer (AA’) and at least one aromatic dihalo monomer (BB’), · The aromatic diol monomer (AA) added may be the same as or different from the aromatic diol monomer (AA’); · The aromatic dihalo monomer (BB) added may be the same as or different from the aromatic dihalo monomer (BB’).

[0018] A second aspect of the present invention relates to PAES (P2) obtained by the method according to the present invention.

[0019] A third aspect of the present invention provides for the use of PAES (P2) for preparing an article (or a part thereof).

[0020] Another aspect of the present invention provides an article comprising PAES (P2) according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0021] In the present application: - Even if described in connection with a particular embodiment, any description is applicable to another embodiment of the present disclosure and is interchangeable therewith, and each embodiment so defined can be combined with another embodiment unless otherwise indicated or clearly incompatible; - If an element or component is said to be included in and / or selected from a list of recited elements or components, in the related embodiments explicitly contemplated herein, the element or component can be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly recited elements or components; it should be understood that any element or component listed in the list of elements or components can be omitted from such a list; - Any recitation in this specification of a numerical range by endpoints includes all numbers within the recited range and the endpoints and equivalents thereof; - The term "comprising" (or "includes") includes "consisting essentially of" and also "consisting of"; - The use of the singular form "a" or "one" in this specification includes the plural unless otherwise specified; - It should be understood that the elements, properties, and / or features of the (co)polymers, products or articles, processes, or uses described herein can be combined with other elements, properties, and / or features of the (co)polymers, products or articles, processes, or uses in any possible way, explicitly or implicitly, without departing from the scope of this specification.

[0022] The term "consisting essentially of" with respect to a composition, product, polymer, solution, process, method, etc. is intended to mean that any additional elements or features that may not be explicitly recited herein and that do not substantially affect the basic and novel properties of such composition, product, polymer, solution, process, method, etc. may be included in such embodiments. For example, when a composition, compound, product, polymer, or solution "consists essentially of" the required elements, it is generally understood that any additional elements may be present at 1 wt% or less based on the total weight of the composition, compound, product, polymer, solution, etc., or at 1 mol% or less based on the total number of moles of the composition, compound, product, polymer, or solution.

[0023] In the present disclosure, the term "recurring unit" represents the smallest unit of a PAES polymer that repeats within a chain and is composed of the condensation of a diol compound and a dihalo compound. The term "recurring unit" is synonymous with the terms "repeating unit" and "structural unit".

[0024] As used herein, the term "homopolymer" encompasses polymers having only one type of repeating unit.

[0025] As used herein, the term "copolymer" encompasses polymers that can have two or more different types of repeating units.

[0026] The term "solvent" is used herein in its ordinary sense. That is, it refers to a substance that can dissolve another substance (solute) to form a uniformly dispersed mixture at the molecular level. In the case of a polymer solute, it is common practice to refer to a solution of the polymer in the solvent when the resulting mixture is transparent and no phase separation is observed in the system. Phase separation is interpreted as the point, often called the "cloud point", at which the solution becomes turbid or cloudy due to the formation of polymer aggregates.

[0027] The term "membrane" is used herein in its ordinary sense. That is, a membrane means an individual, usually thin interface that moderates the penetration of chemical species in contact with the membrane. Membranes generally contain polymers. Examples of membranes are water purification membranes and hemodialysis membranes.

[0028] The term "post-consumer" polymer material (or article) refers to a finished product that has been used and then recycled, which can serve as a source of recycled polymer material usable in the methods of the present invention. Typical post-consumer polymer materials include, but are not limited to, packaging, membranes, compounds, automotive parts, electronic parts, consumer product parts (such as, but not limited to, plastic bottles, especially baby bottles, etc.), battery parts, or any used or end-of-life, three-dimensional injection-molded, extrusion-molded, or printed articles or parts thereof.

[0029] The term "post-industrial" polymer material (or article), also known as "pre-consumer" polymer material (or article), refers to waste resulting from the manufacturing process that forms the raw polymer material usable in the method of the present invention. For example, when a polymer is molded into a bottle, polymer scraps may be generated, which do not become the final bottle product. When these polymer scraps are ground, shredded, or repelletized and reused in manufacturing the same article or another article, they are called "post-industrial" polymer materials. Typical pre-consumer polymer materials include, but are not limited to, polymers products such as packaging, film, fiber, membrane, off-spec compound, or off-spec polyarylether sulfone, automotive parts, electronic parts, consumer product parts (such as, but not limited to, plastic bottles, especially baby bottles), battery parts, or three-dimensional injection molded, extrusion molded, or printed articles or parts thereof, in whole, in part, or their scraps.

[0030] In other words, post-consumer polymer materials (or articles or waste) refer to finished products, while post-industrial polymer materials (or articles or waste) refer to waste resulting from the manufacturing process of producing polymers or polymer-based articles.

[0031] The weight average molecular weight (M w ) and the number average molecular weight (M n ) can be estimated by gel permeation chromatography (GPC) calibrated with polystyrene standards. The mobile phase can be selected from any solvent for the polymers described herein, such as methylene chloride, N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone (NMP) and N-butyl-2-pyrrolidinone, dimethyl sulfoxide (DMSO), 1,3-dimethyl-2-imidazolidinone (DMI), tetramethylene sulfone (sulfolane), N,N'-dimethylacetamide (DMAc), or any mixture thereof. The polydispersity index (PDI) is, in this specification, the number average molecular weight (M n) as the ratio of the weight-average molecular weight (M w ) is expressed.

[0032] If the disclosure of any patent, patent application, and publication incorporated herein by reference renders the terms of this application unclear to the extent that it conflicts with the description of this application, the description shall prevail.

[0033] One aspect of the present invention is a method for chemically recycling a polymer material containing polyarylether sulfone (P1) [hereinafter "PAES(P1)"], · adding a polar aprotic solvent (S) to a reaction vessel, · adding a recycled polymer material containing PAES(P1) to the reaction vessel, · adding an alkali salt former (A) to the reaction vessel, · adding at least one monomer (M) selected from the group consisting of at least one aromatic diol monomer (AA) and at least one aromatic dihalo monomer (BB) to the reaction vessel, whereby the addition step forms a reaction medium (RM) containing a polymer material comprising PAES(P1), at least one monomer (M), an alkali salt former (A), and a polar aprotic solvent (S), · heating the reaction medium to reach a reaction temperature of at least 150 °C to form polyarylether sulfone (P2) [hereinafter "PAES(P2)"], and · separating the formed PAES(P2) from the reaction medium, comprising; - such PAES(P1) is derived by the condensation of at least one aromatic diol monomer (AA') and at least one aromatic dihalo monomer (BB'), - the aromatic diol monomer (AA) is the same as or different from the aromatic diol monomer (AA'), - the aromatic dihalo monomer (BB) is the same as or different from the aromatic dihalo monomer (BB'), - The alkali salt-forming agent (A) is an alkali metal carbonate and / or an alkali metal hydroxide; relates to a method.

[0034] The aromatic diol monomer (AA) can be selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, isosorbide, isomannide, isoidide, tetramethylbisphenol F, hydroquinone, and any combination thereof, and preferably can be selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, tetramethylbisphenol F, hydroquinone, and any combination thereof.

[0035] The aromatic dihalo monomer (BB) can be selected from the group consisting of 4,4'-difluorodiphenyl sulfone (DFDPS), 4,4'-dichlorodiphenyl sulfone (DCDPS), disulfonated DCDPS, disulfonated DFDPS, and any combination thereof, and preferably can be selected from the group consisting of DCDPS, disulfonated DCDPS, and any combination thereof.

[0036] In a preferred embodiment, the polymeric material comprises at least one recycled material selected from the group consisting of post-consumer polymeric articles, post-industrial polymeric articles including scrap of the articles, off-spec polyarylether sulfone products, and any combination thereof. These products are preferably selected from the group consisting of membranes, automotive parts, electronic parts, consumer product parts (such as baby bottles), composite materials, battery parts, and any combination thereof.

[0037] Polyarylether sulfone (P1) The recycled polymeric material used as a reactant in the method of the present invention comprises at least one polyarylether sulfone (P1).

[0038] PAES(P1) may be a polymer containing 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% of at least one repeating unit selected from those of formulas (L), (L'), (M), (M'), (N), (N'), (O), (O'), (T), (T'), (U), (U'), (V), (V'), (W), (W'), based on the total number of moles of the repeating units of PAES(P1):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0039] The repeating units selected from those of formulas (U), (V), (W) are respectively of formulas (U*), (V*), (W*):

Chemical formula

[0040] PAES(P1) may be a homopolymer having one repeating unit selected from those of formulas (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), (T), (T’), (U), (U’), (V), (V’), (W), (W’), (U*), (V*), (W*), or may be a copolymer containing two or more repeating units selected from those of formulas (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), (T), (T’), (U), (U’), (V), (V’), (W), (W’), (U*), (V*), (W*). In some embodiments, each R in the repeating unit selected from those of the above formulas (L’), (N’), (O’), (Q’), (T’), (U’), (V’), and (W’) can be independently selected from the group consisting of alkali metal or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently selected from integers of 1 to 4.

[0041] In particular, PAES(P1) is at least 60 mol% based on the total number of moles of repeating units in PAES(P1) of · the repeating units of formulas (L) and (L’), · the repeating units of formulas (N) and (N’), · the repeating units of formulas (O) and (O’), · the repeating units of formulas (Q) and (Q’), · the repeating units of formulas (T) and (T’), · the repeating units of formulas (U) and (U’), · the repeating units of formulas (V) and (V’), or · the repeating units of formulas (W) and (W’), and may be a copolymer containing or consisting essentially of them. Each R in the repeating units of formulas (L’), (N’), (O’), (Q’), (T’), (U’), (V’), and (W’) can be independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently selected from integers of 1 to 4.

[0042] In a preferred embodiment of a method for producing polyaryl ether sulfone (P2) using a recycled polymer material containing polyaryl ether sulfone (P1) as a reactant, PAES (P1) preferably contains 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% of a sulfone polymer selected from the group consisting of the following, based on the total weight of PAES (P1): · PPSU, · PSU, · PES, · Sulfonated PSU (sPSU), · Sulfonated PES (sPES), · Sulfonated PPSU (sPPSU), · Any polymer derived from a diol monomer selected from isosorbide and / or tetramethylbisphenol F and a dihalo monomer selected from sulfonated dihalodiphenyl sulfone and / or dihalodiphenyl sulfone, · Any copolymer derived from at least two diols selected from biphenol, bisphenol A, bisphenol S, isosorbide, tetramethylbisphenol F, and / or hydroquinone and a dihalo monomer selected from sulfonated dihalodiphenyl sulfone and / or dihalodiphenyl sulfone, · A block polymer in the form of A-B or A-B-A, comprising at least one block having one repeating unit selected from those of formula (L), (L’), (N), (N’), (O), (O’), (Q), (Q’) and at least one block having one repeating unit selected from those of formula (T), (T’), (U), (U’), (V), (V’), (W), (W’), (U*), (V*), (W*), ·A block polymer in the form of A-B or A-B-A, having at least one block with a repeating unit selected from those of formula (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), and at least one polyalkylene oxide block or polyvinylpyrrolidone (PVP) block, such as a PEG block, a PPG block, or a PVP block, ·Any combination of two or more of these (The formulas (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), (T), (T’), (U), (U’), (V), (V’), (W), (W’), (U*), (V*), (W*) are as defined previously).

[0043] The polyethersulfone (PES) used herein contains at least 90 mol%, at least 95 mol%, or at least 98 mol% of the repeating unit of formula (O) (R PES ) or consists essentially of it, and the mol% is based on the total number of moles of repeating units in the PES polymer. PES can be prepared by known methods and is particularly available from Solvay Specialty Polymers USA, L.L.C. as VERADEL® PES.

[0044] The polysulfone (PSU) used herein contains at least 90 mol%, at least 95 mol%, or at least 98 mol% of the repeating unit of formula (L) (R PSU ) or consists essentially of it, and the mol% is based on the total number of moles of repeating units in the PSU polymer. PSU can be manufactured by known methods and is particularly available from Solvay Specialty Polymers USA, L.L.C. as Udel® PSU.

[0045] The polyphenylsulfone (PPSU) used herein contains at least 90 mol%, at least 95 mol%, or at least 98 mol% of the repeating unit of formula (Q) (R PPSUcomprises or consists essentially of, with the mole % based on the total number of moles of repeating units in the PPSU polymer. PPSU can be prepared by known methods and is particularly available from Solvay Specialty Polymers USA, L.L.C. as RADEL® PPSU.

[0046] As used herein, sulfonated polyethersulfone (sPES) comprises or consists essentially of 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 a combination of repeating units of formula (O) (R PES ) and repeating units of formula (O’) (R sPES ), with the mole % based on the total number of moles of repeating units in the sPES polymer. Each R in formula (O’) is independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently an integer from 1 to 4.

[0047] As used herein, sulfonated polysulfone (sPSU) comprises or consists essentially of 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 repeating units of formula (L) (R PSU ) and repeating unit R of formula (L’) sPSU ), with the mole % based on the total number of moles of repeating units in the sPSU polymer. Each R in formula (L’) is independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently an integer from 1 to 4.

[0048] As used herein, sulfonated polyphenylsulfone (sPPSU) is at least 60%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 98 mol% of repeating units of formula (Q) (R PPSU ) and repeating units of formula (Q’) (R sPPSUcomprising or consisting essentially of, with the mole % based on the total number of moles of repeating units in the sPPSU polymer, each R in formula (Q’) being independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i being independently an integer from 1 to 4.

[0049] When used, the block polymer in the form of A-B or A-B-A in PAES(P1) is ·at least one sulfone polymer block having at least one repeating unit selected from those of PPSU, sPPSU, PSU, sPSU, PES, sPES, and at least one block having repeating units produced from tetramethylbisphenol F and sulfonated or non-sulfonated dihalodiphenyl sulfone, or from 1,4:3,6-dianhydrohexitol sugar diol (e.g., isosorbide) and sulfonated or non-sulfonated dihalodiphenyl sulfone; or ·at least one block polymer having a repeating unit selected from those of PPSU, sPPSU, PSU, sPSU, PES, sPES and at least one polyalkylene oxide block or polyvinylpyrrolidone (PVP) block such as a PEG block, a PPG block, or a PVP block; may be included.

[0050] As used herein, the polyvinylpyrrolidone (PVP) block or polymer is at least 90 mole %, at least 95 mole %, or at least 98 mole % of the following formula, based on the total number of moles of repeating units in the PVP block or polymer:

Chemical formula

[0051] As used herein, "polyalkylene oxide" is understood to mean a polyalkylene oxide obtained by polymerizing alkylene oxides such as ethylene oxide and 1,2-propylene oxide. "Polyalkylene oxide" generally has the following formula: -[(CHR l ) y O] z -H (wherein R l is H or alkyl; y may be 1 to 3; z may be 2 to 500). Polyethylene glycol (PEG) and polypropylene glycol (PPG) are examples of polyalkylene oxides.

[0052] In a further preferred embodiment of a method for producing polyarylether sulfone (P2) using a recycled polymer material containing polyarylether sulfone (P1) as a reactant, PAES (P1) comprises, or consists of, 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% of a sulfone polymer selected from the group consisting of PPSU, PSU, PES, sPSU, sPES, sPPSU, and any combination thereof, and the wt% is based on the total weight of PAES (P1).

[0053] In an alternative embodiment of a method for producing polyarylether sulfone (P2) using a recycled polymer material containing polyarylether sulfone (P1) as a reactant, PAES (P1) can optionally consist of a blend of PES / PPSU, PES / PSU, PSU / PPSU, PES / PSU / PPSU, PES / sPES, PSU / sPSU, or PPSU / sPPSU.

[0054] The PAES(P1) polymer can be produced by various methods. PAES(P1) is preferably derived by polycondensation of at least one aromatic diol monomer (AA') and at least one aromatic dihalo monomer (BB').

[0055] For example, U.S. Patent Nos. 4,108,837 and 4,175,175 describe the preparation of polyaryl ethers, particularly polyaryl ether sulfones. Several one-step and two-step processes are described in these patents, which are hereby incorporated by reference in their entirety. In these processes, the double alkali metal salt of a dihydric phenol (aromatic diol AA') is reacted with a dihalobenzene compound (aromatic dihalo BB') in the presence of a polar aprotic solvent under substantially anhydrous conditions. In the two-step process, the aromatic diol AA' is first converted to an alkali metal salt derivative in the system by reaction with an alkali metal or an alkali metal compound in the presence of a solvent. The alkali metal salt is produced as a by-product of the polymerization.

[0056] For the production of PAES(P1), preferred starting aromatic diol monomers (AA') can be selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S (4,4'-dihydroxydiphenyl sulfone), 1,4:3,6-dianhydrohexitol sugar diols (such as isosorbide), tetramethylbisphenol F, hydroquinone, and any combination thereof.

[0057] For the production of PAES(P1), the preferred starting aromatic dihalomonomer (BB’) can be selected from the group consisting of 4,4'-dihalodiphenyl sulfone and its sulfonated derivatives, preferably 4,4'-difluorodiphenyl sulfone (DFDPS), 4,4'-dichlorodiphenyl sulfone (DCDPS), disulfonated DCDPS, and / or disulfonated DFDPS, and any combination thereof, more preferably can be selected from DCDPS and / or disulfonated DCDPS.

[0058] In some embodiments for the production of the PAES(P1) copolymer, the first aromatic diol monomer (AA’)1 can be selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, and hydroquinone, and the second aromatic diol monomer (AA’)2 can be selected from the group consisting of tetramethylbisphenol F, 1,4:3,6-dianhydrohexitol sugar diol (such as isosorbide), and any combination thereof.

[0059] The weight average molecular weight Mw of PAES(P1) can be 30,000 - 100,000 g / mol, for example 35,000 - 90,000 g / mol, or 40,000 - 85,000 g / mol. The weight average molecular weight (Mw) of PAES(P1) can be determined by gel permeation chromatography (GPC) using methylene chloride as the mobile phase, calibrated with a polystyrene standard solution (2×5μ mixed D column (with guard column) manufactured by Agilent Technologies; flow rate: 1.5 mL / min; injection volume: 20 μL of a 0.2 w / v% sample solution).

[0060] Polyarylether sulfone (P2) The method of the present invention forms polyarylether sulfone (P2).

[0061] PAES(P2) may be a polymer containing at least 50 mol% of at least one repeating unit selected from the formulas (L), (L'), (N), (N'), (O), (O'), (Q), (Q'), (T), (T'), (U), (U'), (V), (V'), (W), (W'), (U*), (V*), (W*) with respect to the total number of moles of the repeating units in PAES(P1). PAES(P2) may be a homopolymer having a repeating unit selected from the formulas (L), (L'), (N), (N'), (O), (O'), (Q), (Q'), (T), (T'), (U), (U'), (V), (V'), (W), (W'), (U*), (V*), (W*), or may be a copolymer containing two or more repeating units selected from the formulas (L), (L'), (N), (N'), (O), (O'), (Q), (Q'), (T), (T'), (U), (U'), (V), (V'), (W), (W'), (U*), (V*), (W*). In a preferred embodiment, each R in the repeating unit selected from the formulas (L'), (N'), (O'), (Q'), (T'), (U'), (V'), and (W') can be independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently selected from integers of 1 to 4.

[0062] In particular, PAES(P2) is at least 60 mol% of, based on the total number of moles of the repeating units of PAES(P2), · the repeating units of formulas (L) and (L'), · the repeating units of formulas (N) and (N'), · the repeating units of formulas (O) and (O'), · the repeating units of formulas (Q) and (Q'), · the repeating units of formulas (T) and (T'), · the repeating units of formulas (U) and (U'), · the repeating units of formulas (V) and (V'), or · the repeating units of formulas (W) and (W'). It may be a copolymer comprising or consisting essentially of, wherein each R in the repeating units of formula (L’), (N’), (O’), (Q’), (T’), (U’), (V’), and (W’) can be independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and each i is independently an integer from 1 to 4.

[0063] When PAES(P1) is added as a reactant of (RM) and contains repeating units selected from those of formula (L), (L’), (N), (N’), (O), (O’), (Q), (Q’), (T), (T’), (U), (U’), (V), (V’), (W), (W’), PAES(P2) also contains the same repeating units as PAES(P1). However, the molar % content of such repeating units in PAES(P2) based on the total molar number of repeating units in PAES(P2) may be different from the molar % content of this repeating unit in PAES(P1). For example, if PAES(P1) is PPSU consisting essentially of repeating units of formula (Q) and at least one monomer (M) added to the reaction consists of a combination of bisphenol and sulfonated DCDPS, the resulting PAES(P2) contains not only repeating units of formula (Q’) but also the same repeating units (Q), but its content in PAES(P2) is less than 100 mol% based on the total molar number of repeating units in PAES(P2).

[0064] PAES(P2) preferably contains 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% of a sulfone polymer selected from the following group based on the total weight of PAES(P1): ·PPSU; ·PSU; ·PES; ·Sulfonated PSU (sPSU); ·Sulfonated PES (sPES); ·Sulfonated PPSU (sPPSU); · A copolymer derived from a diol selected from 4,4'-biphenol, bisphenol A, bisphenol S, or hydroquinone, and two dihalomonomers selected from sulfonated DCDPS + DCDPS or DFDPS + sulfonated DFDPS; · A homopolymer derived from a diol selected from isosorbide or tetramethylbisphenol F, and a dihalomonomer selected from sulfonated DCDPS, DCDPS, DFDPS, or sulfonated DFDPS; and · A copolymer derived from two diols selected from 4,4'-biphenol, bisphenol A, bisphenol S, isosorbide, tetramethylbisphenol F, and hydroquinone, and a dihalomonomer selected from sulfonated DCDPS and / or DCDPS.

[0065] PAES(P2) preferably contains at least 50% by weight of a sulfone polymer selected from the group consisting of PPSU, PSU, PES, sPSU, sPES, sPPSU, and any combination thereof, and the % by weight is based on the total weight of PAES(P2).

[0066] PAES(P2) can have an Mw of at least 40 kDa, at least 50 kDa, or at least 55 kDa, and / or a maximum of 150 kDa, 130 kDa, 110 kDa, 100 kDa, or 90 kDa (P2) and the Mw (P2) is measured by GPC calibrated with polystyrene standards using methylene chloride as the mobile phase. The preferred range of Mw (P2) can be 50 kDa to 100 kDa, or 55 kDa to 90 kDa.

[0067] In some embodiments, PAES(P2) has an Mw (P1) within + / - 35% of the Mw (P2) of PAES(P1), and / or PAES(P2) has a PDI P1 value within + / - 35% of the PDI P2 value of PAES(P1).

[0068] In particular, the weight average molecular weight (Mw) and number average molecular weight (M n ) of PAES (P2) can be determined by gel permeation chromatography (GPC) using methylene chloride as the mobile phase, calibrated with a polystyrene standard solution (2×5μ mixed D column (with guard column) manufactured by Agilent Technologies; flow rate: 1.5 mL / min; injection volume: 20 μL of 0.2 w / v% sample solution).

[0069] The polydispersity index (PDI) is expressed herein as the ratio of the weight average molecular weight (M n ) to the number average molecular weight (M w ).

[0070] Recycled polymer material The recycled polymer material added to the reaction medium (RM) in the method of the present invention can be regarded as waste, such as end-of-life products or articles, industrial waste, and / or unsellable (e.g., off-specification, surplus) products or articles.

[0071] The polymer material preferably contains at least one recycled material selected from the group consisting of post-consumer polymer articles, post-industrial articles or parts thereof, off-specification polyarylether sulfone products, and any combination thereof.

[0072] The polymer material can include or consist of at least one recycled polymer article selected from the group consisting of membranes, automotive parts, electronic parts, consumer product parts, such as plastic bottles (e.g., baby bottles), composite materials, battery parts, any parts or scraps thereof, and any combination thereof.

[0073] The recycled polymer material may contain at least 50 weight percent (wt%) of PAES (P1) based on the total weight of the polymer material. The polymer material preferably contains 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% of PAES (P1) based on the total weight of the polymer material.

[0074] The recycled polymer material can consist essentially of PAES (P1).

[0075] In an alternative embodiment, the recycled polymer material includes PAES (P1) and at least one additional component such as other non-PAES polymers, fillers, and / or additives.

[0076] Optional other polymer (P3) in the polymer material The recycled polymer material may further include another polymer (P3) different from PAES (P1). The other polymer (P3) is preferably not a PAES and is also referred to as a "non-PAES polymer".

[0077] The other polymer (P3) in the recycled polymer material may preferably be a pore-forming polymer such as polyvinylpyrrolidone (PVP), polyalkylene oxide, or polyalkylene glycol (such as polyethylene glycol (PEG)), or any combination thereof.

[0078] When the recycled polymer material further includes another polymer (P3), the polymer material may include the following: · A blend of PAES (P1) and another polymer (P3), · A coating or layer of either polymer (P1) and (P3) on at least a portion of the solid surface made of another polymer, and / or ·A block copolymer comprising at least one block of PAES (P1) and at least another block of another polymer (P3).

[0079] For example, the recycled polymer material may include a blend of PAES (P1) and a pore-forming polymer such as polyvinylpyrrolidone (PVP), polyalkylene oxide, or polyalkylene glycol (e.g., PEG, PPG) having a molecular weight of at least 200, preferably 200 - 900, as the polymer (P3), or any combination thereof.

[0080] In another example, the recycled polymer material can include a block copolymer in the form of A - B or A - B - A, where blocks A and B represent at least one PAES (P1) block and at least one polyalkylene oxide block, such as PES:PEG, PPSU:PEG, or PSU:PEG block copolymers.

[0081] In another embodiment, the other polymer (P3) in the recycled polymer material may be polycarbonate (PC).

[0082] The recycled polymer material preferably contains up to 25 wt%, up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt% of the other polymer (P3) based on the total weight of the recycled polymer material.

[0083] Optional solid filler in the polymer material The recycled polymer material may further include a solid filler. The filler is preferably not a polymer. The filler may be a reinforcing filler. In fact, when it is desired to form a polymer molded article having high mechanical strength while being lightweight, the polymer material can be reinforced with a filler.

[0084] In such cases, the recycled polymer material preferably contains a filler in an amount of up to 60 wt%, up to 55 wt%, up to 50 wt%, up to 45 wt%, up to 40 wt%, up to 35 wt%, or up to 30 wt%, and / or at least 2 wt%, at least 4 wt%, at least 6 wt%, at least 8 wt%, or at least 10 wt%, based on the total weight of the recycled polymer material.

[0085] The filler may be in the form of a particulate filler, a non-fibrous filler, and a fibrous filler. The particulate reinforcing filler can be selected from inorganic fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, and magnesium carbonate) or glass beads (such as hollow glass microspheres). The fibrous reinforcing filler is considered herein to be a three-dimensional material having a length, width, and thickness such that the average length is significantly greater than both the width and the thickness. Typically, such fibrous materials have an aspect ratio defined as the ratio between the average length and the maximum of the average width and average thickness of at least 5, at least 10, at least 20, or at least 50. The fibrous reinforcing filler can 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 polymer-based fillers. A "non-fibrous" filler is considered herein to have a three-dimensional structure having a length, width, and thickness such that both the length and the width are significantly greater than the thickness. The non-fibrous reinforcing filler can include glass or carbon.

[0086] In a preferred embodiment, the recycled polymer material may further contain a non-polymer-based filler selected from inorganic fillers, carbon fibers, and / or glass fibers.

[0087] Optional Additives in the Polymer Material The recycled polymer material may further contain one or more additional additives selected from the group consisting of an ultraviolet stabilizer, a heat stabilizer, an acid scavenger (i.e., zinc oxide, magnesium oxide), an antioxidant, a pigment, a processing aid, a lubricant, a flame retardant, and / or a conductive additive (i.e., carbon black, carbon nanotubes, and carbon nanofibers).

[0088] In such a case, the recycled polymer material preferably contains one or more additional additives of up to 15 wt%, up to 10 wt%, up to 7.5 wt%, or up to 5 wt%, and / or one or more additional additives of at least 0.01 wt%, at least 0.05 wt%, at least 0.08 wt%, at least 0.1 wt%, or at least 1 wt%, based on the total weight of the recycled polymer material.

[0089] Monomer (M) in the reaction medium At least one monomer (M) selected from at least one aromatic diol monomer (AA) and / or at least one aromatic dihalo monomer (BB) is added to the reaction vessel before the polycondensation reaction is initiated.

[0090] Preferably, at least one monomer (M) contains at least one aromatic diol monomer (AA). At least one monomer (M) preferably contains at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of at least one aromatic diol monomer (AA) based on the total number of moles of monomer (M).

[0091] When the PAES (P1) recycling rate is 100 wt%, at least one monomer (M) preferably consists essentially of at least one aromatic diol monomer (AA).

[0092] Among the diol monomers (AA) suitable for use in the method of the present invention, the following compounds can be particularly mentioned: [Chem.] and / or three isomers of 1,4:3,6-dianhydrohexitol diol, namely isosorbide (1), isomannide (2), and isoidide (3): [Chem.]

[0093] The aromatic diol monomer (AA) can be selected from the group consisting of isosorbide (1), isomannide (2), and isoidide (3), and any combination thereof, or can be selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, hydroquinone, tetramethylbisphenol F, and any combination thereof.

[0094] The aromatic diol monomer (AA) is preferably selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, isosorbide (1), tetramethylbisphenol F, hydroquinone, and any combination thereof, and more preferably is selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, tetramethylbisphenol F, and any combination thereof.

[0095] When the added PAES (P1) is PSU and the intended PAES (P2) is a PSU homopolymer or copolymer, the selected aromatic diol monomer (AA) most preferably contains bisphenol A.

[0096] When the added PAES (P1) is PPSU and the intended PAES (P2) is a PPSU homopolymer or copolymer, the aromatic diol monomer (AA) most preferably contains 4,4'-biphenol.

[0097] When the added PAES (P1) is PES and the intended PAES (P2) is a PES homopolymer or copolymer, the aromatic diol monomer (AA) most preferably includes bisphenol S.

[0098] When the aromatic dihalo monomer (BB) is added to the reaction vessel, the aromatic dihalo monomer (BB) can be selected from the group consisting of 4,4'-difluorodiphenyl sulfone (DFDPS), 4,4'-dichlorodiphenyl sulfone (DCDPS), their disulfonated derivatives, and any combination thereof. More preferably, the aromatic dihalo monomer (BB) can be selected from the group consisting of DCDPS, disulfonated DCDPS, and any combination thereof.

[0099] Alkali salt former (A) in the reaction medium The alkali salt former (A) can be at least one base selected from the group consisting of potassium carbonate (K2CO3), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium tert-butoxide, and sodium tert-butoxide.

[0100] The alkali salt former (A) is preferably at least one base selected from the group consisting of potassium carbonate (K2CO3), sodium carbonate (Na2CO3), sodium hydroxide (NaOH), and potassium hydroxide (KOH), and more preferably at least one base selected from the group consisting of potassium carbonate (K2CO3), sodium carbonate (Na2CO3), and sodium hydroxide (NaOH).

[0101] The base functions to deprotonate the aromatic diol monomer to form an alkali salt of the diol.

[0102] Polar aprotic solvent (S) The condensation to prepare PAES (P2) is carried out in a reaction medium (RM) containing at least one polar aprotic solvent (S). The polar aprotic solvent (S) is preferably selected such that the PAES (P1) in the recycled polymer material dissolves in this solvent.

[0103] The polar aprotic solvent (S) can be selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (commonly called tetramethylene sulfone or sulfolane), N-alkyl-2-pyrrolidone, such as 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.

[0104] The polar aprotic solvent (S) is preferably selected from the group consisting of NMP, NBP, NEP, DMF, DMAc, DMI, DMSO, diphenyl sulfone, and sulfolane.

[0105] The polar aprotic solvent (S) is more preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, NMP, diphenyl sulfone, and any combination thereof; most preferably, it is selected from the group consisting of sulfolane, DMSO, DMAc, NMP, diphenyl sulfone, and any combination thereof.

[0106] Optional co-solvent The condensation reaction for preparing PAES(P2) can be carried out in a mixture of an aprotic polar solvent (S) and a cosolvent that forms an azeotrope with water. Examples of the cosolvent that forms an azeotrope with water include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene. The cosolvent is preferably toluene or monochlorobenzene (MCB). The azeotrope-forming cosolvent and the aprotic polar solvent (S) are typically used in a weight ratio of about 1:10 to about 1:1, preferably about 1:5 to about 1:1. Water is continuously removed from the reaction medium as an azeotrope together with the azeotrope-forming cosolvent, and as a result, substantially anhydrous conditions are maintained during the polymerization. The azeotrope-forming cosolvent, such as chlorobenzene or toluene, is typically removed from the reaction medium by distillation after the water formed in the reaction has been removed, leaving the formed PAES(P2) dissolved in the aprotic polar solvent (S).

[0107] Addition step in the method The various components of the reaction medium (RM) (i.e., the recycled polymer material, at least one monomer (M), the alkali salt former (A), and the aprotic polar solvent (S), optional components such as the aprotic polar solvent (S0), and / or the cosolvent) can be added simultaneously or sequentially.

[0108] In some embodiments, when at least one monomer (M) comprises at least one aromatic diol monomer (AA), the diol (AA) and the alkali salt former (A) can be added together to the reaction vessel in the form of an alkali salt (AAA) of the diol (AA). In such a case, the aromatic diol monomer (AA) is mixed with the alkali salt former (A) outside the system in a container (e.g., a supply tank) separate from the reaction vessel in a polar aprotic solvent (S0). To promote the reaction with the alkali salt former (A) to form phenoxide and / or bisphenoxide (before polycondensation) and produce an alkali salt of the diol (hereinafter referred to as (AAA)), it may be necessary to heat the mixture of aromatic diol (AA) + alkali salt former (A) + solvent (S0). The temperature of the mixture of diol (AA) + reagent (A) + solvent (S0) may be at least ambient temperature, but should not exceed the boiling point of the solvent (S0), and is preferably from 25°C to 300°C. Then, the alkali salt (AAA) of the diol (AA) is added to the reaction vessel. After the formation of (bis)phenoxide and before adding to the reaction vessel, the alkali salt (AAA) of the diol (AA) in the solvent (S0) may be dehydrated (to remove the water formed during (bis)phenoxide formation). Any of the solvents described herein for the polar aprotic solvent (S) is equally suitable for the solvent (S0) used for the phenoxide reaction outside the system. The polar aprotic solvent (S0) is preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, DMF, NMP, and combinations thereof. The polar aprotic solvent (S0) is preferably the same polar aprotic solvent (S) as that used for the reactor medium, but not necessarily so. When the polar aprotic solvents (S) and (S0) are the same, they are preferably selected from sulfolane, DMSO, DMI, DMAc, NMP, or any combination thereof.

[0109] In some cases, the recycled polymer material containing PAES (P1) may be added to the reaction vessel in solid form such as pellets, fibers, powders, flakes, fragments of shredded or ground articles, solidified solids (e.g., solidified polymer beads, particles, or prills), any other solid 3D object, or any mixture thereof. The pellets may be of any shape, such as cylindrical, spherical, or oval. In particular, when the recycled polymer material may contain industrial waste from a polyarylether sulfone manufacturing plant, such waste is obtained after the solidification step (in solidified form) and may not be dried before being recycled and used as a reactant in this method. The shape and size of the recycled polymer material are not important as long as the PAES (P1) in the recycled polymer material can be at least partially, preferably completely dissolved in the polar aprotic solvent.

[0110] In some embodiments, the recycled polymer material containing PAES (P1) can be added directly to the reaction vessel in solid form, and at least a portion of the PAES (P1) is "pre-dissolved" in part or all of the polar aprotic solvent (S) before adding the other components (A) and (M) of the reaction medium (RM). Heating may be required during pre-dissolution to facilitate dissolution of the PAES (P1). Dissolution is preferably carried out at least at ambient temperature, but should not exceed the boiling point of the solvent (S), preferably 50°C to 150°C or 70°C to 130°C.

[0111] In another embodiment, the monomer (M) and the recycled polymer material containing PAES (P1) can be added directly to the reaction vessel in solid form, and at least a portion of the monomer (M) and the PAES (P1) is "pre-dissolved" in the polar aprotic solvent (S) before adding the component (A) to the reaction vessel. Heating may be required during pre-dissolution to facilitate dissolution of the monomer (M) and the PAES (P1). Dissolution is preferably carried out at least at ambient temperature, but should not exceed the boiling point of the solvent (S), preferably 50°C to 150°C or 70°C to 130°C.

[0112] In an alternative embodiment, the recycled polymer material containing PAES (P1) can be added to the reaction vessel in the form of a "pre-dissolved" solution or slurry outside the system, i.e., outside the reaction vessel, before at least a portion of the PAES (P1) is added to the reaction vessel. In such a case, the recycled polymer material can be mixed with an aprotic polar solvent (S0). It may be necessary to heat the mixture of recycled polymer material + solvent (S0) to facilitate the dissolution of PAES (P1) in the solvent (S0). The dissolution is preferably carried out at least at ambient temperature, but should not exceed the boiling point of the solvent (S0), preferably between 50°C and 150°C or between 70°C and 130°C. Such preliminary dissolution is preferably carried out in a container separate from the reaction vessel (e.g., a supply tank). If the resulting pre-dissolved material is in the form of a slurry containing solids such as insoluble fillers derived from the recycled polymer material, the solids can be removed (e.g., the slurry is filtered) to recover the PAES (P1) solution. The PAES (P1) solution is then added to the reaction vessel. The aprotic polar solvent (S0) in which PAES (P1) can be pre-dissolved is preferably the same aprotic polar solvent (S) used in the reactor medium, but this is not necessarily the case. Such an aprotic polar solvent (S0) is specifically selected for its ability to completely dissolve PAES (P1) and any optional monomer (M) when mixed with PAES (P1) outside the system. Any of the solvents described herein for the aprotic polar solvent (S) are equally suitable for pre-dissolving PAES (P1) and any optional monomer (M) before addition to the reaction vessel. The aprotic polar solvent (S0) is preferably selected from the group consisting of sulfolane, DMSO, DMAc, DMI, DMF, NMP, and combinations thereof. When the aprotic polar solvents (S) and (S0) are the same, they are preferably selected from sulfolane, DMSO, DMAc, NMP, or combinations thereof.

[0113] In certain embodiments, the various addition steps for preparing the reaction medium (RM) can be carried out as follows: · Place the recycled polymer material containing PAES (P1) into the reaction vessel together with the solvent (S), and preferably heat it from ambient temperature to a temperature below the boiling point of the solvent (S), preferably 50°C to 150°C or 70°C to 130°C, to dissolve PAES (P1) in the solvent (S); · Then, after PAES (P1) is dissolved, at least the monomer (M) and the alkali salt former (A) are added to the reaction vessel either simultaneously or sequentially. In some examples where at least the monomer (M) contains an aromatic diol (AA), the diol (AA) and the alkali salt former (A) may be added "as is", or they may be mixed and reacted outside the system (e.g., in another container such as a supply tank) to form (bis)phenoxide and generate the alkali salt (AAA) of the diol (AA). Then, the obtained alkali salt (AAA) of the diol (AA) is added to the reaction vessel. After (bis)phenoxide formation, the alkali salt (AAA) of the diol (AA) in the solvent (S0) may be dehydrated (to remove the water formed during (bis)phenoxide formation) and then added to the reaction vessel.

[0114] In an alternative embodiment, the various addition steps for preparing the reaction medium (RM) can be carried out as follows: · Dissolve PAES (P1) by pre-dissolving the recycled polymer material containing PAES (P1) outside the system (i.e., in a supply tank separate from the reaction vessel) with the solvent (S) [or solvent (S0) if different from the solvent (S)], preferably heating it from ambient temperature to a temperature below the boiling point of the solvent (S), preferably 50°C to 150°C or 70°C to 130°C, and optionally filtering after dissolution to remove solids; · Next, the pre-dissolved PAES (P1), at least monomer (M), alkali salt former (A), and optional solvent (S) [when solvent (S0) is used for pre-dissolving PAES (P1) and / or forming phenoxide] are added to the reaction vessel simultaneously or continuously. As described above, in some cases where at least monomer (M) contains aromatic diol (AA), the diol (AA) and alkali salt former (A) may be reacted (to form (bis)phenoxide) before polycondensation and then added to the reaction vessel in the form of an alkali salt (AAA) of diol (AA). After the formation of (bis)phenoxide, the alkali salt (AAA) of diol (AA) in solvent (S0) may be dehydrated before being added to the reaction vessel.

[0115] In yet another embodiment, the various addition steps for preparing the reaction medium (RM) can be carried out as follows: · Place a recycled polymer material containing at least monomer (M) and PAES (P1) into the reaction vessel together with solvent (S), and preferably heat it from ambient temperature to below the boiling point of solvent (S), preferably at a temperature of 50°C to 150°C or 70°C to 130°C, to dissolve monomer (M) and PAES (P1) in solvent (S); · Then, after monomer (M) and PAES (P1) are dissolved, add alkali salt former (A) to the reaction vessel.

[0116] Polycondensation reaction step Without wishing to be bound by theory, the chemistry of the transetherification reaction acts to scramble the ether bonds of the repeating units of the recycled polymer PAES (P1) with the polymer chains formed from the monomer / oligomer, thereby incorporating them into the final chains of the resulting polymer PAES (P2) formed by the method of the present invention.

[0117] In particular, when the recycling rate is 100% by weight, the ether exchange reaction breaks and mixes (scrambles) the ether bonds in the repeating units of the recycled PAES (P1). As a result, the resulting polymer PAES (P2) has substantially the same chemical structure (the same repeating units) as the virgin polymer produced from only monomers, and their properties are very similar. Consequently, there should be no restrictions on the use of the polymer PAES (P2).

[0118] Similarly, when the monomers added to the reaction medium (RM) to promote the formation of new polymer chains correspond to the same monomers as those from which the recycled PAES (P1) is derived, the resulting polymer PAES (P2) also has substantially the same chemical structure (the same repeating units) as the virgin polymer directly obtained from these added monomers, and their properties are very similar. For example, this process may involve using recycled PES waste, adding bisphenol S and DCDPS to the reaction vessel, and forming a new PES polymer (P2) having PES repeating units of formula (O).

[0119] On the other hand, when the monomers added to the reaction medium (RM) promote the formation of new polymer chains of a different type of sulfone polymer, the resulting polymer PAES (P2) will have a different chemical structure compared to the recycled PAES (P1) in that PAES (P2) contains the same repeating units as PAES (P1) but also different repeating units obtained from the condensation of the added monomers. In such cases, the resulting PAES (P2) may have some different properties when compared to the recycled PAES (P1), and also when compared to the virgin polymer obtained by adding monomers to the reaction medium (RM) without the recycled (P1). For example, the method may involve using recycled PES waste, adding biphenol and DCDPS to the reaction vessel, and forming a new copolymer having not only PES repeating units of formula (O) but also a plurality of PPSU repeating units of formula (Q).

[0120] The main advantage of the method according to the invention is that it involves a one-pot synthesis (within the same reaction vessel) from a recycled polymer material containing PAES (P1) used as a reactant. The polymer material containing PAES (P1) is preferably added to the reaction medium before the polycondensation is initiated.

[0121] Thus, the reaction medium (RM) in the reaction vessel contains a polymer recycling material containing PAES (P1), at least one monomer (M), an alkali salt former (A), and an aprotic polar solvent (S) before the polycondensation is initiated.

[0122] The reaction medium (RM) may further contain an aprotic polar solvent (S0) and / or an azeotrope-forming cosolvent used to pre-dissolve PAES (P1) as described above.

[0123] When at least one monomer (M) contains at least one aromatic diol monomer (AA), the reaction medium (RM) contains the following molar ratio of alkali salt former (A) to aromatic diol monomer (AA): · At least 0.95:1, at least 0.98:1, at least 0.99, at least 0.995, or at least 1:1; and / or · At most 2.5:1, at most 2.2:1, at most 2:1, at most 1.8:1, at most 1.6:1, at most 1.4:1, at most 1.35:1, or at most 1.3:1.

[0124] When at least one monomer (M) comprises at least one aromatic diol monomer (AA) and at least one aromatic dihalo monomer (BB), the reaction medium (RM) comprises a molar ratio of aromatic dihalo monomer (BB) / aromatic diol monomer (AA) of at least 0.9:1, at least 0.92:1, at least 0.95:1, at least 0.98:1, at least 0.99, at least 0.995, or at least 1:1, and / or at most 1.1:1, at most 1.08:1, at most 1.07:1, at most 1.06:1, at most 1.05:1, or at most 1.04:1. A preferred molar ratio of aromatic dihalo monomer (BB) / aromatic diol monomer (AA) is 0.95 to 1.05, or 0.98 to 1.02, or 0.99 to 1.01.

[0125] The reaction medium (RM) preferably comprises 5 to 40 wt%, 10 to 35 wt%, 5 to 40 wt%, 15 to 35 wt%, 20 to 35 wt%, or 20 to 30 wt% of PAE polymers (P1) and (P2) based on the total weight of the reaction medium during the reaction time.

[0126] The reaction time may be 2 hours to 20 hours, preferably 3 hours to 12 hours, more preferably 3 hours to 10 hours, still more preferably 3.5 hours to 8 hours, and most preferably 3.5 hours to 6 hours.

[0127] The reaction temperature for forming PAES (P2) 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. A preferred range 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.

[0128] Recycling rate The recycled polymer material containing PAES (P1) can be added to the reactor medium so as to achieve a PAES (P1) recycling rate of 100% by weight to 1% by weight, preferably 100% by weight to 5% by weight. Such a recycling rate is based on the ratio of the weight of the added PAES (P1) to the total weight of the maximum weight of the additional polymer that would theoretically be produced based on the equimolar stoichiometry of the polycondensation of the monomers (AA) and (BB) when both the diol monomer (AA) and the dihalo monomer (BB) are added to the reactor medium and the weight of the added PAES (P1).

[0129] For example, formula (Q):

Chemical formula

[0130] The same type of calculation can be used: · For PES produced from bisphenol S and DCDPS (as monomers AA and BB respectively), the molecular weight of the PES repeating unit is 464 g / mol, or · For PSU produced from bisphenol A and DCDPS (as monomers AA and BB respectively), the molecular weight of the PSU repeating unit is 442 g / mol.

[0131] In another method, the number of moles of monomers (AA) and (BB) added after the recycling rate is selected can be calculated. For example, if "m1" g of PAES (P1) is added to the medium (RM) and a predetermined recycling rate "z" (which is 0.01 - 1 used in 1 - 100 wt%) is desired, the amount of polymer "y" that can be produced from monomers AA and BB is calculated as follows: Y = (m1 - zm1) / z. When m1 = 400 g of PES is added and a recycling rate of 40 wt% (z = 0.4) is desired, 600 g of PES, i.e., 600 / 464 = 1.293 moles of PES can be produced. In that case, 1.293 moles of DCDPS is used, but more than 1.293 moles of bisphenol S may be used.

[0132] If the aromatic dihalo (BB) or aromatic diol (AA) is not added to the reaction medium, since one of the monomers (AA) and (BB) is absent from the reaction medium, there will be no possibility of forming new polymer chains from at least the monomer (M). In that case, the recycling rate of PAES (P1) in the process is 100 wt%.

[0133] Separation step in the process for recovering PAES (P2) At the end of the reaction, PAES (P2) is separated from the other components of the reaction medium. The separated PAES (P2) may be in the form of a PAES (P2) solution or in solid form (such as coagulation or drying).

[0134] Non-polymer components, such as sodium chloride or potassium chloride or excess base, and non-polymeric fillers derived from the starting recycled polymer material can be removed from the reaction medium by suitable methods such as dissolution and filtration, sieving, or extraction, either before or after the separation of PAES (P2).

[0135] The separated PAES (P2) can first be recovered in the form of a PAES (P2) solution. This step may include filtration of the reaction medium to remove solid components and recover the PAES (P2) solution. The PAES (P2) solution should contain the solvent (S) (used during the condensation) and PAES (P2) dissolved in an optional solvent (S0).

[0136] PAES (P2) is preferably recovered in solid form from the solvent (S) and an optional solvent (S0) (if used for the preliminary dissolution of PAES (P1)). This step may include filtration of the reaction medium to remove solid components (such as alkali salts and / or insoluble substances derived from the recycled polymer material) and recover the PAES (P2) solution. In some embodiments, when a 100% weight recycling rate is used, i.e., when the polymer chains of the resulting PAES (P2) grow from depolymerized PAES (P1), there should be little alkali salt formed during the reaction, and the filtration step can be omitted in the method of the present invention.

[0137] To recover PAES (P2) in solid form, the PAES (P2) solution can preferably be precipitated from the solvent by coagulation or devolatilization of the solvent from the PAES (P2) solution.

[0138] Solidification is based on the precipitation of PAES (P2) by a non-solvent or a poor solvent. This solidification step is preferably carried out by forming droplets of the PAES (P2) solution in a precipitation bath containing the non-solvent or the poor solvent to form polymer beads of PAES (P2). The non-solvent can be selected from C1-C5 alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, ethyl acetate, methyl acetate, acetone, butanone, water, or any mixture thereof. Preferred non-solvents include ethanol, methanol, water, or any mixture thereof. The poor solvent may be a mixture of the non-solvent and the solvent (S) and / or (S0). The non-solvent or the poor solvent may contain at least 50% by weight, preferably at least 60% by weight of water and / or C1-C5 alcohol such as methanol or ethanol.

[0139] The recovered solid PAES (P2) can be washed one or more times with a washing liquid to further remove salts or other components remaining in the polymer solid content. The washing liquid is preferably water and / or C1-C5 alcohol (such as methanol, ethanol, n-propanol, isopropanol). The washing liquid (such as water) is preferably at a temperature of at least 50 °C, or at least 60 °C, or at least 65 °C. The washing liquid needs to be at a temperature not exceeding its boiling point. The temperature of the washing liquid is preferably 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 60 °C - 80 °C, or 65 °C - 75 °C. Two or more washings using different washing liquids may be carried out, such as one or more washings with water first and then one or more washings with methanol.

[0140] The solid PAES (P2) can be dried at a temperature of usually about 50 °C - 120 °C, preferably about 80 °C - 120 °C, more preferably about 90 - 120 °C, and even more preferably about 90 - 110 °C, preferably under vacuum.

[0141] The dried PAES (P2) can be used in the manufacture of articles such as, but not limited to, fibers, sheets, films, or membranes.

[0142] Optional steps in the method The method according to the invention may further comprise at least one of the following steps between the reaction (condensation) step and the separation step: i. Cooling: a step of lowering the temperature of the reaction medium; ii. Quenching: a solvent (S q ) which may be the same as or different from the polar aprotic solvent (S) is added to quench the reaction medium, usually to stop the reaction, dilute the reaction medium and reduce its viscosity; and / or iii. End-capping: a step of adding an end-capping agent to convert the hydroxyl end groups of the formed PAES (P2) into less reactive end groups.

[0143] In some embodiments of the method according to the invention, only one optional step may be carried out.

[0144] Alternatively, at least two optional steps are carried out.

[0145] Step (i): Cooling can be carried out by stopping the heating of the reaction medium. Cooling can be carried out by directly adding an additional amount of polar aprotic solvent (S) or another solvent to the reaction medium at a temperature at least 50 °C lower, at least 60 °C lower, or at least 70 °C lower 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 carried out by passing a cooling fluid (without mixing with the reaction medium (RM)) through a cooling tube or by using a cooling jacket for the reaction vessel.

[0146] Step (ii): Quenching can be carried out at the end of the reaction to reduce the polymer content of the reaction medium to a value of 20% by weight or less based on the total weight of the reaction medium to be quenched. The solvent (S) added for quenchingq ) is preferably the same as the polar aprotic solvent (S) used during the reaction, but does not necessarily have to be. Solvent (S q ) 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 5% to 20% by weight, more preferably 10% to 15% by weight, based on the total weight of the quenched reaction medium.

[0147] The cooling and quenching steps (i) and (ii) may be carried out simultaneously by using a solvent (S q ) at a temperature lower than the reaction temperature of the reaction medium at the end of the reaction.

[0148] Step (iii): End-capping (also called termination) preferably converts the reactive hydroxyl end groups of the formed PAES (P2) into less reactive end groups. The end-capping agent is preferably methyl chloride (“MeCl”). Methyl chloride gas may be passed through the reaction medium. The end-capping step (iii) may be carried out before or after cooling of the reaction medium. Therefore, the end-capping step (iii) can be carried out at the reaction temperature or at a temperature lower than the reaction temperature at the end of the polycondensation reaction. If it is desired to obtain the final PAES (P2) product having reactive (-OH) end groups, the end-capping step (iii) is preferably omitted in the method of the present invention.

[0149] Use of PAES (P2) Another aspect of the present invention provides the use of PAES (P2) for manufacturing the article (or a part thereof) described herein.

[0150] Method for manufacturing an article Another aspect of the present invention provides a method for preparing or manufacturing an article (or a part thereof) comprising PAES (P2). The method for manufacturing an article may include using PAES (P2) for forming the article or a part thereof.

[0151] The article can be formed from a solution containing PAES (P2).

[0152] When the article is a membrane or a part thereof, the method may include a phase conversion occurring in a liquid phase (e.g., a precipitation bath) to form the membrane or a part thereof from a solution containing PAES (P2).

[0153] The method may include solution spinning techniques.

[0154] An article containing PAES (P2) Another aspect of the present invention provides an article (preferably a shaped article) containing PEAS (P2) according to the present invention.

[0155] The article may be an injection molded article, an extrusion molded article, a drawn molded article, or a solution processed article (e.g., solution cast).

[0156] The article containing PAES (P2) can be selected from the group consisting of a membrane (e.g., a solution cast membrane), a fiber, a sheet, a solution processed film (e.g., a porous film), and a solution processed monofilament.

[0157] PAES (P2) can be incorporated into an article having a polymer surface. The article can have a polymer surface, at least a part of which is in direct contact with an aqueous medium such as water, an aqueous solution, a biological fluid, and / or food in the intended use situation. The polymer surface can be the outer surface or the inner surface of the article. For example, a medical device has an outer surface intended to be in direct contact with a biological fluid such as blood, plasma, or serum. One of ordinary skill in the art will understand which surface is intended to be in contact with a biological fluid or food based on the intended use situation of the article.

[0158] As another example, the surface of the article can include a coating or film containing PAES (P2) disposed on a substrate therebelow. In such an embodiment, the substrate therebelow may be a structural element having a composition different from that of PAES (P2).

[0159] In embodiments where PAES (P2) is a film, the film can have an average thickness of from about 25 μm to about 1 mm.

[0160] PAES (P2) can be included in at least a portion of the surface of an article intended to come into contact with a biological fluid such as blood, plasma, or serum. Alternatively, PAES (P2) can form all or substantially all of the article.

[0161] The shaped article containing PAES (P2) is preferably a membrane or a part thereof selected from a proton exchange membrane, a membrane for bioprocesses (such as enzyme or cell culture filtration), a membrane for medical filtration (such as a hemodialysis membrane), a membrane for food and beverage treatment, a membrane for water purification, a membrane for wastewater treatment, and a membrane for industrial process separation containing an aqueous medium.

[0162] Among the membranes, PAES (P2) according to the present invention is particularly suitable for the production of membranes intended to come into contact with an aqueous medium. Examples of the aqueous medium include biological fluids such as blood and foods such as beverages (such as fruit juice, milk).

[0163] From a structural point of view, the membrane containing PAES (P2) can be provided in the form of a flat structure (such as a film or sheet), a corrugated structure (such as a corrugated sheet), a tubular structure, or a hollow fiber; with respect to the pore size, any type of membrane (non-porous and porous such as for microfiltration, ultrafiltration, nanofiltration, and reverse osmosis) can be advantageously produced using PAES (P2); and the pore distribution can be isotropic or anisotropic.

[0164] Among the uses for which it is used, healthcare uses, particularly medical uses, can be mentioned. Molded articles containing PAES (P2) can advantageously be used in single-use and reusable instruments and devices.

[0165] Among the uses, fuel cell uses in which PAES (P2) can be advantageously used for proton exchange membranes can be mentioned.

[0166] The article can contain PAES (P2) and another sulfone polymer different from the optional PAES (P2) in an amount in the range of 1 to 99% by weight, for example 2 to 98% by weight, 3 to 97% by weight, or 4 to 96% by weight, based on the total weight of the polymer. When the article contains PAES (P2) and another sulfone polymer such as virgin PSU, PES, and / or PPSU, the weight fraction of PAES (P2) based on the total weight of PAES (P2) and the other sulfone polymer in the article is at least 10% by weight, or at least 15% by weight, or at least 20% by weight, or at least 25% by weight, and / or at most 99% by weight, or at most 98% by weight, or at most 96% by weight, or at most 95% by weight, or at most 90% by weight.

[0167] Membrane or film (as an article) The article can be a film or a membrane, or a part thereof.

[0168] A particular embodiment of the article (preferably a molded article) relates to a membrane containing PAES (P2). The membrane can be used for proton exchange or for purifying water, food, or biological fluids (such as blood).

[0169] One embodiment of the membrane according to the present invention relates to a proton exchange membrane containing PAES (P2).

[0170] Another embodiment of the membrane according to the present invention relates to a purification membrane containing PAES (P2), such as for purifying water, food, or biological fluids (such as blood).

[0171] The membrane may be a microporous membrane that can be characterized by an average pore diameter and a porosity (i.e., the proportion of the porous part in the whole membrane).

[0172] The membrane can have a weight porosity of 20 - 90% (%) and contain pores, and at least 90% by volume of the pores have an average pore diameter of less than 5 μm. The weight porosity of the membrane is defined as the volume of the pores divided by the total volume of the membrane.

[0173] A membrane having a uniform structure throughout its thickness is generally known as a symmetric membrane, and a membrane in which pores are not uniformly distributed throughout its thickness is generally known as an asymmetric membrane. An asymmetric membrane is characterized by a thin selective layer (thickness 0.1 - 1 μm) and a thick highly porous layer (thickness 100 - 200 μm) that serves as a support and has little influence on the separation characteristics of this membrane.

[0174] The membrane may be in the form of a flat sheet or a tube.

[0175] The membrane may be formed using a plurality of films or fibers.

[0176] Based on its dimensions, a tubular membrane is classified into a tubular membrane having a diameter of more than 3 mm; a capillary membrane having a diameter included in 0.5 mm - 3 mm; and a hollow fiber having a diameter of less than 0.5 mm. A capillary membrane is also called a hollow fiber.

[0177] Hollow fibers are particularly advantageous for applications where a compact module with a large surface area is required.

[0178] The membrane, fiber, or film according to the present invention can be manufactured using any conventionally known manufacturing method for a membrane, fiber, or film. For example, a film manufacturing method can use a solution casting method.

[0179] The membrane or film according to the present invention can be produced by a phase inversion method carried out in a liquid phase, and the method includes a step of preparing a polymer solution containing PAES (P2) described herein and a polar solvent, a step of processing the polymer solution into a film, and a step of bringing the film into contact with a non-solvent bath.

[0180] Here, the present invention will be described in more detail in connection with the following examples, but the purpose is merely illustrative and not intended to limit the scope of the present invention.

Example

[0181] Here, the present invention will be described in more detail in connection with the following examples, but the purpose is merely illustrative and not intended to limit the scope of the present invention. "E" used in this example means an embodiment of the present invention, and "CE" means a comparative example.

[0182] GPC method ("Sulfone GPC method #1") for measuring Mn and Mw The molecular weight was measured by gel permeation chromatography (GPC) using methylene chloride as the mobile phase. Two 5-μm mixed D columns with a guard column from Agilent Technologies were used for separation. A UV detector at 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml / min and an injection volume of 20 μL of a 0.2 w / v% solution in the mobile phase were selected. Calibration was performed using 10 or 12 narrow molecular weight polystyrene standards. The number average molecular weight Mn and the weight average molecular weight Mw were reported, and PDI = Mw / Mn was calculated.

[0183] Example 1: PES Recycling Raw materials for samples E1 - E2, CE3, CE4, E5 Na2CO3 (sodium carbonate), available from Solvay France DCDPS (4,4'-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers DHDPS (4,4'-dihydroxydiphenyl sulfone or bisphenol S), available from Sigma-Aldrich Sulfolane, available from Chevron Phillips Chemicals Methyl chloride, available from Matheson Gas Methanol, available from Sigma-Aldrich PES1: Veradel® 3000MP PES, manufactured by Solvay Specialty Polymers, Mw = 64,145; Mn = 19,145; PDI = 3.35

[0184] Synthesis of PES samples E1 - E2: A PES polymerization process in which 20 wt% added PES is used as a reactant To a 1.0 L glass reaction vessel equipped with an overhead stirrer and a nitrogen inlet, to prepare PES samples E1 and E2, monomer DHDPS and DCDPS with a 1 mol% excess (i.e., a DCDPS / DHDPS molar ratio of 1.01) relative to the amount of DHDPS and Veradel® 3000MP (PES1) were first added. Then, sodium carbonate was added in an 18% molar excess relative to the amount of DHDPS (i.e., with a Na2CO3 / DHDPS molar ratio of 1.18). The reaction medium was heated from room temperature to 227 + / - 2 °C over 90 minutes. The polymerization temperature of the reaction medium was maintained for approximately 3.6 - 4.1 hours depending on the viscosity of the solution. Polymerization was carried out at a polymer concentration of 26.4 wt% in the reaction medium. The reaction was terminated by adding methyl chloride (at about 1 g / min) and end-capping the polymer at 227 ± 2 °C for an additional 30 minutes. The reaction medium was quenched by diluting with sulfolane to achieve a 15 wt% polymer content. The quenching was carried out at the polymerization temperature (227 °C) and then further quenched with additional sulfolane. After quenching, the reaction medium was filtered through a 2.7 μm glass fiber filter pad under nitrogen pressure and coagulated in water at a polymer solution / water volume ratio of 1:5 using a high-speed waring blender. The coagulated polymer was then washed 5 times with hot water (70 °C) and vacuum dried overnight in an oven at 110 °C.

[0185] The difference between Samples E1 and E2 was that the polymerization of Sample E1 (3.6 hours) was completed earlier than that of Sample E2 (4.1 hours).

[0186] Synthesis of Sample CE3 (Comparative Example) - PES Polymerization Process (without using PES as a reactant) For Sample CE3, polymerization was carried out in the same manner as described above for Samples E1 and E2, except that PES was not added to the reaction medium and the reaction time was 4.6 hours.

[0187] The Mw, Mn, and PDI (by sulfone GPC method) of the PES polymers obtained after coagulation and drying of Samples E1, E2, and CE3 are reported in Table 1.

[0188] It was observed that the polymer obtained by adding 20 wt% of PES1 as a reactant to Sample E2 had Mw and Mn values similar to those of CE3 without the PES1 reactant when the reaction time was the same.

[0189] For Sample E2, Mw decreased slightly (-7%) compared to the control sample CE3. This is in contrast to the 35% decrease in Mw when the reaction time of Sample E1 was shorter compared to the control CE3.

[0190] Also, a decrease in the PDI value was observed for Samples E1 (-25%) and E2 (-18%) compared to the control sample CE3.

[0191] Synthesis of Sample E4: PES Polymerization Process Using 10 wt% PES1 Recycling Polymerization of Sample E4 was carried out in the same manner as described for Sample E2, except that the coagulated polymer of Sample E4 was washed 5 times with hot water (70 °C) and then further washed once with methanol. Furthermore, to form Sample E4, only 10 wt% of PES1 was used (compared to 20 wt% of PES1 in Samples E1 and E2).

[0192] Synthesis of Sample CE5 (Comparative Example) - PES Polymerization Process (without PES addition) The polymerization to form Sample CE5 was carried out in the same manner as described for Sample CE3, except that the coagulated polymer was washed 5 times with hot water (70 °C) and then further washed once with methanol to obtain the PES sample CE5.

[0193] The Mw, Mn, and PDI (by sulfone GPC method) of the PES polymers obtained after coagulation and drying in Samples CE4 and E5 are also reported in Table 1.

[0194]

Table 1

[0195] It was observed that the PES obtained in Sample E4 with 10 wt% PES1 added as a reactant had Mw and Mn values similar to those of Sample CE5 without PES1 addition when the reaction conditions (including reaction time) were similar.

[0196] For Sample E4, a slight decrease (-10%) in Mw was observed compared to the control sample CE5, and a slight decrease (-8%) in the PDI value was also observed compared to the control sample CE5.

[0197] Example 2 - Recycling of PES GPC method for measuring Mn and Mw The same sulfone GPC method #1 as described above was used.

[0198] Raw materials for Samples E6 - E12 and CE13 Na2CO3 (sodium carbonate), available from Solvay DCDPS (4,4'-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers DHDPS (4,4'-dihydroxydiphenyl sulfone or bisphenol S), available from Sigma-Aldrich Sulfolane, available from Chevron Phillips Chemicals PES2: Veradel® 3300PES from Solvay Specialty Polymers, Mw = 45249; Mn = 15244; PDI = 2.97; powder form PES3: Veradel® 3000MP PES from Solvay Specialty Polymers, Mw = 67559; Mn = 18013; PDI = 3.75; powder form PES4: Veradel® 3300PES from Solvay Specialty Polymers, Mw = 45735; Mn = 14785; PDI = 3.09; pellet form

[0199] Synthesis of PES sample E6 - Production of PES using 100 wt% recycled PES powder PES2 powder (Mw = 45249) (232 g) was placed in a 1.25 - liter glass polymerization reactor together with 460 ml of sulfolane. The reaction medium was heated under stirring conditions of 50 RPM while continuously flowing nitrogen. After the polymer was partially dissolved at about 100 °C, 4,4'-dihydroxydiphenyl sulfone (DHDPS) (2.5 g, 0.01 mol) and sodium carbonate (6.0 g, 0.0566 mol) were added to the reaction medium. The stirring speed was increased to 200 RPM. The reaction medium was heated at 227 °C for 3.5 - 4 hours. The molecular weight growth of the polymerization was tracked by GPC. The polymerization reaction was quenched by adding 250 ml of sulfolane. Then, methyl chloride was passed through the reaction medium for purging, and the polymer chains were end - capped for 30 minutes. The reaction medium was coagulated in 1.5 liters of deionized water in a Waring blender to obtain the coagulated polymer. The coagulated polymer was washed with cold and hot water in an Ace Glass Instatherm® extraction kettle until the residual solvent amount decreased to about 0.3 wt%. The obtained washed polymer powder was dried at 120 °C for 24 hours. 212 g of dry PES polymer (sample E6) was obtained with a yield of about 91%.

[0200] Synthesis of PES Sample E7 - Production of PES using 30 wt% PES powder recycling DCDPS (102.459 g, 0.357 mol), DHDPS (87.5 g, 0.35 mol), and PES3 powder (Mw = 67559) (69.6 g) were placed in a 1.25 - liter glass polymerization reactor together with 460 ml of sulfolane. While continuously flowing nitrogen, the reaction medium was heated under stirring conditions of 200 RPM. After the monomers were dissolved at about 70 °C, sodium carbonate (47.908 g, 0.413 mol) was added to the reaction medium. The reaction medium was heated at 227 °C for 4 hours. The molecular weight growth of the polymerization was tracked by GPC. The polymerization reaction was quenched by adding 250 ml of sulfolane. Then, methyl chloride was passed through the reaction medium for purging, and the polymer chains were end - capped for 30 minutes. Next, using an Advantec filtration system, the reaction medium was pressure - filtered through a 2.7 - micron glass fiber filter pad. The filtered reaction medium was coagulated in 1.5 liters of deionized water in a Waring blender to obtain the coagulated polymer. The coagulated polymer was washed with cold water and hot water in an Ace Glass Instatherm (registered trademark) extraction kettle until the residual solvent amount decreased to about 0.3 wt%. The obtained washed polymer solid was dried at 120 °C for 24 hours. 189 g of dry PES polymer powder (Sample E7) was obtained in a yield of about 81%.

[0201] Synthesis of PES Samples E8a and E8b - Production of PES using 50 wt% chemical recycling of PES powder DCDPS (73.185 g, 0.255 mol) and DHDPS (62.5 g, 0.25 mol), PES3 powder (Mw = 67559) (116 g) were placed in a 1.25 - liter glass polymerization reactor together with 460 ml of sulfolane. While stirring at 200 RPM in a continuous flow of nitrogen, the reaction medium was heated. After the monomers were dissolved at about 70 °C, sodium carbonate (31.27 g, 0.295 mol) was added to the reaction medium. By performing the same remaining procedures as in Example 6, 196 g of dry PES polymer (Sample E8a) was obtained in a yield of about 84%.

[0202] Another dried PES sample E8b was produced by repeating the procedure under the same conditions as described above, except using slightly different reaction times.

[0203] Synthesis of PES Samples E9a and E9b - Production of PES Using 70 wt% PES Powder Chemical Recycling DCDPS (43.911 g, 0.153 mol), DHDPS (37.5 g, 0.15 mol), and PES3 powder (Mw = 67559) (162.4 g) were placed into a 1.25 - liter glass polymerization reactor together with 460 ml of sulfolane. By performing the remaining procedure similar to Example 6, 186 g of a dried PES polymer (sample E9a) was obtained in a yield of approximately 80%.

[0204] Another dried PES sample E9b was produced by repeating the procedure under the same conditions as described for sample E9a, except using slightly different reaction times.

[0205] Synthesis of PES Samples E10a and E10b - Production of PES Using 90 wt% PES Powder Chemical Recycling DCDPS (14.637 g, 0.051 mol) and DHDPS (12.5 g, 0.05 mol), PES3 powder (Mw = 67559) (208.8 g) were placed into a 1.25 - liter glass polymerization reactor together with 460 ml of sulfolane. While continuously flowing nitrogen, the reaction medium was heated under stirring conditions of 50 RPM. After dissolving the monomers and PES3 powder at approximately 90°C, sodium carbonate (6.254 g, 0.059 mol) was added to the reaction medium. The stirring speed was increased to 200 RPM. The reaction medium was heated at 217°C for 3 - 4 hours. The molecular weight growth of the polymerization was tracked by GPC. By performing the remaining procedure similar to Example 7, 208 g of a dried PES polymer, sample E10a, was obtained in a yield of approximately 89%.

[0206] Another dried PES sample E10b was produced by repeating the procedure under the same conditions as described above, except using slightly different reaction times.

[0207] Synthesis of PES Sample E11 - Production of PES Using 95 wt% Chemically Recycled PES Powder DCDPS (7.318 g, 0.0255 mol), DHDPS (6.25 g, 0.025 mol), and PES3 powder (Mw = 67559) (208.8 g) were placed into a 1.25 - liter glass polymerization reactor together with 460 ml of sulfolane. While continuously flowing nitrogen, the reaction medium was heated under stirring conditions of 50 RPM. After dissolving the monomers and PES3 powder at approximately 90 °C, sodium carbonate (6.254 g, 0.059 mol) was added to the reaction medium. By performing the remaining procedures similar to Example 7, 206 g of dry PES polymer (Sample E11) was obtained at a yield of approximately 88%.

[0208] Synthesis of PES Sample E12 - Production of PES Using 100 wt% Chemically Recycled PES Pellets PES4 pellets (Mw = 45735) (232 g) were placed into a 1.25 - liter glass polymerization reactor together with 460 ml of sulfolane. While continuously flowing nitrogen, the reaction medium was heated under stirring conditions of 20 RPM. After partially dissolving the PES4 pellets at approximately 130 °C, DHDPS (2.5 g, 0.01 mol) and sodium carbonate (6.0 g, 0.0566 mol) were added to the reaction medium. The stirring speed was slowly increased to 200 RPM. The reaction medium was heated at 227 °C for 3 - 4 hours. The molecular weight growth of the polymerization was tracked by GPC. The polymerization reaction was quenched by adding 250 ml of sulfolane. Then, methyl chloride was passed through the reaction medium for purging, and the polymer chains were end - capped for 30 minutes. The reaction medium was coagulated in 1.5 liters of deionized water in a Waring blender to obtain the coagulated polymer. The coagulated polymer was washed with cold water (30 °C) and hot water (80 °C) in an Ace Glass Instatherm® extraction kettle until the residual solvent amount decreased to approximately 0.3 wt%. The obtained washed polymer solid was dried at 120 °C for 24 hours. 208 g of dry PES sample E12 was obtained at a yield of approximately 89%.

[0209] Synthesis of PES sample CE13 (Comparative Example) - PES production without PES recycling DCDPS (146.37 g, 0.51 mol) and DHDPS (125 g, 0.50 mol) were placed in a 1.25-liter glass polymerization reactor together with 460 ml of sulfolane. While continuously flowing nitrogen, the reaction medium was heated under stirring conditions of 50 RPM. After the monomers were dissolved at about 70 o °C, sodium carbonate (63 g, 0.59 mol) was added to the reaction medium. The stirring speed was increased to 200 RPM. The reaction medium was heated at 227 °C for 3 - 4 hours. By performing the remaining procedures similar to those in Example 7, 197 g of dry PES sample CE13 was obtained at a yield of about 84.9%.

[0210] The Mw, Mn, and PDI (by the above sulfone GPC method #1) of the PES samples E6 - E12 and CE13 obtained after coagulation and drying are reported in Table 2.

[0211]

Table 2

[0212] For PES samples E7 - E12, there were only slight changes in Mw (-4.2% to 7.1%) compared to the control sample CE13. Also, the PDI value increased slightly from 2.4% to 9.9% compared to the control sample CE13.

[0213] Example 3: Recycling of PES GPC method for measuring Mn and Mw The same sulfone GPC method #1 as described above was used.

[0214] Raw materials for samples E14 and E15 Na2CO3 (sodium carbonate), available from Solvay DHDPS (4,4'-dihydroxydiphenyl sulfone or bisphenol S), available from Sigma-Aldrich Sulfolane, available from Chevron Phillips Chemicals PES5: Ultrason® E020PES, manufactured by BASF, Mw = 66842 g / mol; Mn = 20205 g / mol; PDI = 3.3, in flake form

[0215] Synthesis of Sample E14 - PES production using 100 wt% PES pellet recycle 40 g of PES5 powder (Mw = 66842) was slowly added to a 250 ml four-necked round-bottom flask containing 80 ml of sulfolane. The reaction medium was heated under stirring conditions of 50 RPM while continuously flowing nitrogen. After the PES5 polymer was completely dissolved, the stirring speed was increased to 200 RPM. After the reaction temperature reached 220 °C, 4,4'-dihydroxydiphenyl sulfone (DHDPS) (0.431 g, 1.7 mmol) and sodium carbonate (0.91 g, 8.5 mmol) were added to the reaction medium. The reaction medium was heated at 227 °C for about 3.5 hours. The molecular weight growth of the polymerization was tracked by GPC (using methylene chloride as the mobile phase). First, the PES5 polymer was depolymerized from Mw: 66842 Da to Mw: 34490 Da, and then repolymerized to a molecular weight Mw of 44258 Da. The polymerization reaction was quenched by adding about 45 ml of sulfolane. Then, MeCl was passed through the reaction medium to purge, and the polymer chains were end-capped for 30 minutes. The reaction mass was coagulated in 1.2 L of deionized (MilliQ) water in a Waring blender. The obtained polyaryl ether polymer powder was extracted with cold water and hot water in an Ace Glass Instatherm® extraction kettle until the residual solvent amount decreased to less than about 0.3 wt%. The polymer powder was dried at 120 °C for 24 hours.

[0216] The Mw, Mn, and PDI of the PES polymer sample E14 obtained after coagulation and drying were compared with the starting PES material: The PES5 added to the reaction medium to produce sample E14 is reported in Table 3.

[0217]

Table 3

[0218] In sample E14 with nearly 100% PES recycling, the Mw decreased (-34%) compared to the initial PES5 polymer. Also, a slight increase in the PDI value of 3% was observed compared to the PES5 polymer.

[0219] Example 4: Recycling of PES mesangial fibers GPC method for measuring Mn and Mw The same sulfone GPC method #1 as described above was used.

[0220] Raw materials for sample E15 Na2CO3 (sodium carbonate), available from Solvay DHDPS (4,4'-dihydroxydiphenyl sulfone or bisphenol S), available from Sigma-Aldrich Sulfolane, available from Chevron Phillips Chemicals PES6: Hollow fiber dialysis device Dora B-13PF based on PES (Mw = 66619, Mn = 21277, PDI = 3.13) of Bain medical equipment (Guangzhou) Co., LTD. Elemental analysis was performed using an Elementar Vario Micro cube CHNS analyzer. The PVP content in the PES mesangial fibers was found to be approximately 5 wt%.

[0221] Synthesis of sample E15 - Production of PES using a hemodialysis membrane filter based on PES (100% recycling) The hemodialysis PES6 membrane fiber (MW = 66619 Da) was used as the reactant for Sample E15. The fiber (42 g) was cut into small pieces and slowly added to a 250 mL four-neck round-bottom flask containing 80 mL of sulfolane. Then, 4,4'-dichlorodiphenyl sulfone (DCDPS) (1.25 g, 4.38 mmol) and 4,4'-dihydroxydiphenyl sulfone (DHDPS) (1.075 g, 4.3 mmol) were added to the reactor. While continuously flowing nitrogen, the reaction medium was heated at 180 °C under stirring conditions of 50 RPM. After the fiber and monomers were completely dissolved, the stirring speed was increased to 200 RPM. After the reaction temperature reached 220 °C, sodium carbonate (2.32 g, 21.9 mmol) was added to the reaction medium. The reaction medium was heated at 227 °C for about 4.5 hours. The molecular weight growth of the polymerization was tracked by GPC. First, the polymer was depolymerized from Mw: 66619 Da to Mw: 22865 Da, and then repolymerized to the desired molecular weight of 45500 Da.

[0222] The polymerization reaction was quenched by adding about 45 mL of sulfolane. Then, MeCl was passed through the reaction medium to purge it, and the polymer chains were end-capped for 30 minutes. The reaction mass was coagulated in 1.2 L of deionized (MilliQ) water in a Waring blender. The polymer powder was extracted with cold water and hot water in an Ace Glass Instatherm® extraction kettle until the residual solvent amount decreased to less than about 0.3 wt%. The polymer powder was dried at 120 °C for 24 hours.

[0223] The Mw, Mn, and PDI of the PES polymer Sample E15 obtained after coagulation and drying are reported in Table 4 and compared with the starting PES material: the PES6 material added to the reaction medium to produce Sample E15.

[0224]

Table 4

[0225] For the 100 wt% PES6 recycled sample E15, the Mw decreased (-30%) compared to the initial PES6 polymer. Also, a very slight increase of 1.6% in the PDI value was observed compared to the recycled PES6 polymer.

[0226] Example 5: PSU Recycling and PSU / PVP Recycling

[0227] Test Methods GPC method for measuring Mn and Mw The same sulfone GPC method #1 as described above was used.

[0228] Thermogravimetric Analysis (TGA) The TGA experiments were carried out using a TA Instrument TGA Q500. The TGA measurements were obtained by heating the samples from 20 °C to 800 °C at a heating rate of 10 °C / min under nitrogen.

[0229] DSC When present, DSC was used to measure the glass transition temperature (Tg) and the melting point (Tm). The DSC experiments were carried out using a TA Instrument Q100. The DSC curves were recorded by heating, cooling, reheating, and then recooling the samples from 25 °C to 320 °C at a heating and cooling rate of 20 °C / min. All DSC measurements were obtained while purging with nitrogen. The reported Tg values (and Tm values if present) were defined using the second heating curve unless otherwise specified.

[0230] Elemental Analysis The elemental composition of some polymer samples was determined using a Perkin Elmer 2400CHN elemental analyzer. The polymer samples were combusted based on the classical Pregl-Dumas method. The resulting combustion gases were completely decomposed into CO2, H2O, N2, and SO2. The gases were then separated by frontal chromatography. They were measured with a thermal conductivity detector as they eluted to determine the quantitative values of carbon, hydrogen, nitrogen, and sulfur.

[0231] H Quantification of PVP by NMR analysis The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane. All samples were run on a Bruker 400 MHz NMR with D1 set to 15 s and 64 scans. Data were processed using MestReNova software. Integration of the relevant peaks was performed, and the weight percentage (wt%) of PVP in the sample was determined using the following equation:

Equation

[0232] Raw materials for samples CE16 - E21 N-methylpyrrolidone (NMP), available from Sigma-Aldrich; K2CO3 (potassium carbonate), available from Armand Products Bisphenol A "BPA" (4,4'-dihydroxydiphenyl sulfone), available from Covestro DCDPS (4,4'-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers Methyl chloride, available from Matheson gas Methanol, available from Sigma-Aldrich PSU1: Udel® P-3500 pellets (lot number P060467C), manufactured by Solvay Specialty Polymers USA, Mw = 78213 g / mol; Mn = 21996 g / mol; PDI = 3.55, measured by sulfone GPC method #1 DSC = 190.14 °C TGA = 505.5 °C PSU2: Udel® P-3500 (Lot No. 1901009833), pellet form, manufactured by Solvay Specialty Polymers USA, Mw = 77267 g / mol; Mn = 22542 g / mol; PDI = 3.42 DSC = 190.72 °C TGA = 501.2 °C PSU3: Fibers based on D. Braun's PSU-PVP for hemodialysis devices Mw = 82969 g / mol, Mn = 22907 g / mol, PDI = 3.6 DSC = 186.7 °C TGA = 516.1 °C PVP content: H 3.89 wt% by NMR C: 71.97% H; 5.15% N: 0.45% PVP (Polyvinylpyrrolidone), available from Alf Aesar, Mw = 371165 g / mol, Mn = 139881 g / mol, PDI = 2.65, determined by the following GPC method #3: A Viscotek GPC Max (autosampler, pump, and degasser) equipped with a TDA302 triple detector array consisting of RALS (right angle light scattering), RI (refractive index), and viscosity detectors was used. Samples were prepared at approximately 2 mg / mL in DMAc / LiBr. A series of three columns: a guard column (with an exclusion limit of CLM1019 - 20 kDa), a high Mw column (CLM1013 exclusion of 10 MM daltons relative to polystyrene), and a low Mw column (exclusion limit of 20 k daltons relative to CLM1011 - PS) were used to run the samples at 65 °C at 1.0 mL / min in NMP with 0.2 wt / wt% LiBr. Calibration was performed using only one monodisperse polystyrene standard of approximately 100 kDa. The light scattering, RI, and viscosity detectors were calibrated based on a series of input data provided using the standard. Samples were prepared at approximately 2 mg / mL in NMP / LiBr. Viscotek’s OMNISec v4.6.1 software was used for data analysis.

[0233] PVP had a DSC value of 174.48 °C (Tg) and a decomposition onset temperature of 401 °C (by TGA).

[0234] Synthesis of Sample CE16 (comparative example): Production of baseline PSU in NMP A 1L four-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, a thermocouple, and a Dean-Stark trap with a condenser was charged with bisphenol A = BPA (182.63 g), DCDPS (229.72 g), K2CO3 (120.5 g), and NMP (532 g). The respective weights of the components used in the reaction medium are shown in Table 5. The DCDPS / BPA molar ratio used in the reaction was 1.096, and the K2CO3 / BPA molar ratio was 1.09. To mix the materials, the reactor was slowly heated and a slow stirrer rpm was used. The heating rate was about 2.5 - 3 °C / min up to 190 °C. The water condensed when the temperature reached 190 °C was collected in the Dean-Stark trap. After reaching a predetermined torque or polymerization time, the reaction was stopped by passing excess methyl chloride. The cooled reaction medium was then filtered to remove KCl salt, then coagulated in methanol, and the coagulated polymer was washed with hot water (70 °C) and methanol, and then dried in a vacuum oven at 110 °C for 12 hours.

[0235] By this method, a baseline PSU sample CE16 was obtained. Its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (by DSC) are shown in Table 6.

[0236] Synthesis of Sample E17: Production of PSU using 25 wt% PSU recycle in NMP Synthesis was carried out using the same method as described for CE16, except that Udel® PSU P-3500 pellets (PSU1) were additionally added to a 1L four-necked resin kettle to achieve a 25 wt% PSU recycle rate. The respective weights of the components are shown in Table 5. The DCDPS / BPA molar ratio used in the reaction was 1.096, and the K2CO3 / BPA molar ratio was 1.09. By this, PSU sample E17 was obtained. Its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (by DSC) are shown in Table 6.

[0237] Elemental analysis of Sample E17: C = 72.43%, H = 4.88%, N < 0.05%

[0238] Synthesis of Sample E18: Production of PSU using a 75 wt% PSU recycling rate in NMP Synthesis was carried out using the same method as described for CE16, except that Udel® PSU P-3500 pellets (PSU1) were additionally added to a 1 L four-necked resin kettle to achieve a 75 wt% PSU recycling rate. The respective weights of the components are shown in Table 5. The DCDPS / BPA molar ratio used in the reaction was 1.096, and the K2CO3 / BPA molar ratio was 1.09. As a result, PSU sample E18 was obtained. Its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (by DSC) are shown in Table 6.

[0239] Elemental analysis of Sample E18: C = 72.63%, H = 5.09%, N < 0.05%

[0240] Synthesis of Sample E19: Production of PSU containing 5 wt% PVP using 25 wt% PSU recycling in NMP Synthesis was carried out using the same method as described for CE16, except that Udel® PSU P-3500 pellets (PSU1) and PVP were additionally added to a 1 L four-necked resin kettle to achieve a 25 wt% PSU recycling rate. The respective weights of the components are shown in Table 5. The DCDPS / BPA molar ratio used in the reaction was 1.096, and the K2CO3 / BPA molar ratio was 1.09. As a result, PSU sample E19 was obtained. Its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (by DSC) are shown in Table 6.

[0241] Elemental analysis of sample E19 (C = 72.4%, H = 5.13%, N = 0.09%) confirmed the presence of PVP in the obtained PSU sample E19. PVP was present in the final PSU sample E19 as PVP physically and chemically bonded to the PSU polymer matrix.

[0242] Synthesis of sample E20: Preparation of PSU / PVP containing 5 wt% PVP using 75 wt% PSU recycling in NMP Synthesis was carried out using the same method as described for CE16, except that Udel® PSU P-3500 pellets (PSU2) and PVP were additionally added to a 1 L four-necked resin kettle to achieve a 75 wt% PSU recycling rate. The respective weights of the components are shown in Table 5. The DCDPS / BPA molar ratio used in the reaction was 1.096, and the K2CO3 / BPA molar ratio was 1.09. Thereby, PSU sample E20 was obtained. Its Mw, Mn, PDI (using GPC sulfone method), TGA data, and Tg (by DSC) are shown in Table 6.

[0243] Elemental analysis of sample E20 (C = 72.2%, H = 5.08%, N = 0.28%) confirmed the presence of PVP in the obtained PSU sample E20. PVP was present in the final PSU sample E20 as PVP physically and chemically bonded to the PSU polymer matrix.

[0244] Synthesis of sample E21: Preparation of PSU using 25% Braun dialysis unit fibers in NMP Synthesis was carried out using the same method as described for CE16, except that fibers (PSU3) from a Braun dialysis device were additionally placed into a 1 L four-necked resin kettle to achieve a 25 wt% PSU recycling rate. The respective weights of the components are shown in Table 5. The DCDPS / BPA molar ratio used in the reaction was 1.096, and the K2CO3 / BPA molar ratio was 1.09. Thereby, PSU sample E21 was obtained. Its Mw, Mn, PDI (using the GPC sulfone method), TGA data, and Tg (by DSC) are shown in Table 6.

[0245]

Table 5

[0246]

Table 6

[0247] Elemental analysis of sample E21: C = 72.53%, H = 5.31%, N = 0.11% confirmed the presence of PVP in the obtained PSU sample E21. PVP was present in the final PSU sample E21 as PVP physically and chemically bonded to the PSU polymer matrix.

[0248] Example 6: Recycling of PPSU GPC method (sulfone GPC method #2) for measuring Mn and Mw The following sulfone GPC method #2 was used for Samples E22 - E25. Molecular weights were measured by gel permeation chromatography (GPC) using methylene chloride as the mobile phase. Two 5-μm mixed D columns with a guard column from Agilent Technologies were used for separation. A UV detector at 254 nm was used to obtain chromatograms. A flow rate of 1.5 ml / min and an injection volume of 15 μL of a 0.2 w / v% solution in the mobile phase were selected. Calibration was performed using a 10-point narrow molecular weight polystyrene standard. The injection volume of the calibration standard was 75 μL. The number average molecular weight Mn and the weight average molecular weight Mw were reported, and PDI = Mw / Mn was calculated.

[0249] Raw materials for Samples E22 - E25 Sulfolane anhydrous, available from ChevronPhillips Chemicals DMI (1,3-dimethyl-2-imidazolidinone), available from TCI Americas NMP (N-methylpyrrolidone), available from Sigma Aldrich Potassium carbonate anhydrous (K2CO3) with an average particle size of 30 - 40 μm, available from Armand Products Biphenol (4,4’-biphenol), available from Sigma-Aldrich DCDPS (4,4’-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers USA Methyl chloride, available from Matheson Gas MCB (methylchlorobenzene), available from Sigma-Aldrich Methanol, available from Sigma Aldrich PPSU1: Coagulated form of PPSU from Solvay Speciality Polymers USA, Mw = 60,925 g / mol, Mn = 28,501 g / mol, PDI = 2.14 PPSU2: Radel R-5600 P NT PPSU in the form of a ground powder, available from Solvay Speciality Polymers USA, Mw = 46,720 g / mol, Mn = 20,104 g / mol, PDI = 2.32. PPSU3: PPSU in the solidified form, manufactured by Solvay Speciality Polymers USA, Mw = 79,859 g / mol, Mn = 34,451 g / mol, PDI = 2.32. PPSU4: PPSU in the solidified form, manufactured by Solvay Speciality Polymers USA, Mw = 69,652 g / mol, Mn = 31,259 g / mol, PDI = 2.23 PPSU5: PPSU in the solidified form, manufactured by Solvay Speciality Polymers USA, Mw = 69,420 g / mol, Mn = 31,334 g / mol, PDI = 2.22

[0250] Synthesis method of PPSU1 130.34 g (0.70 mol) of bisphenol, 203.02 g (0.707 mol) of DCDPS, and 101.58 g (0.735 mol) of potassium carbonate anhydrous were placed in a 1 L four-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, a thermocouple, and a Dean-Stark trap with a condenser. 420.48 g of DMI was added to the reactor. The reaction medium was stirred and heated to an internal temperature of 200 °C over about 90 minutes using an external oil bath. The water of reaction was collected in the Dean-Stark trap during heating. After reaching a predetermined torque, the reaction medium was bubbled with gaseous methyl chloride for 30 minutes (about 1 g / min). 323 g of NMP was added to dilute the reaction medium. The salts were removed by pressure filtering the reaction medium through a 2.7 μm glass fiber filter pad. The polymer solution was coagulated in methanol at a polymer-to-methanol ratio of 1:5 using a Waring high-speed blender. The coagulated polymer was washed 5 times with methanol. The solidified form was dried in a vacuum oven at 120 °C for 12 - 20 hours and analyzed for Mw, Mn, and PSI. In this example, the solidified form was used.

[0251] Synthesis methods of PPSU4 and PPSU5 Into a 1 L four-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, a thermocouple, and a Dean-Stark trap with a condenser, 83.80 g (0.45 mol) of bisphenol, 131.17 g (0.4568 mol) of DCDPS, and 71.52 g (0.5175 mol) of potassium carbonate anhydrous were added. The contents were degassed / purged three times using a vacuum / nitrogen cycle. 420.48 g of sulfolane was added to the reactor. The reaction medium was stirred and heated to an internal temperature of 210 °C over about 90 minutes using an external oil bath. The water of reaction was collected in the Dean-Stark trap during heating. After reaching a predetermined torque, the reaction medium was bubbled with gaseous methyl chloride for 30 minutes (about 1 g / min). 723.6 g of MCB and 61.92 g of sulfolane were added to dilute the reaction medium. The salts were removed by pressure filtering the reaction medium through a 2.7 μm glass fiber filter pad. The polymer solution was coagulated in methanol at a polymer-to-methanol ratio of 1:5 using a Waring high-speed blender. The coagulated polymer was washed five times with methanol and then dried in a vacuum oven at 120 °C for 12 - 20 hours.

[0252] Synthesis method of PPSU3 Sulfolane was placed in a 60 gallon Hastelloy reaction vessel, followed by the addition of bisphenol, potassium carbonate, and DCDPS. A molar ratio of DCDPS / bisphenol of 1.015 was used with 11 mol% excess potassium carbonate relative to bisphenol. Sulfolane was added to achieve a polymer concentration of 30 wt%. Polymerization was carried out at 210 °C until the target polymerization end point was reached. MCB was added to quench the reaction, and then MeCl was added to terminate / end-cap the polymerization. The reaction mixture was diluted with MCB and sulfolane to a polymer concentration of 10%. Approximately 1 liter of the reaction mixture sample was pressure filtered to remove salts and coagulated / dried as described above.

[0253] General synthesis of PPSU samples E22 - E25: A 1L four-necked resin kettle equipped with an overhead stirrer, a nitrogen inlet, a thermocouple, and a Dean-Stark trap with a condenser was charged with biphenol, DCDPS, PPSU material (as reactants), K2CO3, and sulfolane. The molar ratio of DCDPS / biphenol was set to 1 or 1.015 (for E23), and the molar ratio of K2CO3 / biphenol was set to 1.15. The target polymer content in the reaction medium was 30 wt%. Then, the reactor was slowly heated (by an external controlled oil bath), and the reaction medium was mixed using stirring. The reaction medium was heated to 210 °C over about 90 minutes. After reaching a predetermined torque or polymerization time, gaseous MeCl was blown into the reaction medium at about 1 g / min for 30 minutes to end-cap. A mixture of 859 g of monochlorobenzene and 42 g of sulfolane was added to the polymerization mixture. Then, the cooled reaction medium was pressure-filtered to remove the formed KCl and unreacted K2CO3 salts, and then coagulated in methanol at a polymer-to-methanol ratio of 1:5 using a Waring high-speed blender. The coagulated polymer was washed 5 times with methanol and then dried in a vacuum oven at 120 for d - 20 hours.

[0254] The respective weights of the components of PPSU samples E22 - E25 are shown in Table 7.

[0255]

Table 7

[0256] The Mw, Mn, and PDI (using GPC sulfone method #2) of the obtained PPSU samples E22 - E25 are reported in Table 8.

[0257]

Table 8

[0258] Example 7: Production of PSU using a PSU recycle rate of 10 wt% or 50 wt% GPC method for measuring Mn and Mw In this example, the GPC sulfone method #1 was used.

[0259] Raw materials for samples CE27 - CE29 and E30 - E32 DMSO (dimethyl sulfoxide), available from Fisher - Scientific NaOH (sodium hydroxide), available from Fisher - Scientific Bisphenol A "BPA" (4,4’ - dihydroxydiphenyl sulfone), available from Hexion DCDPS (4,4’ - dichlorodiphenyl sulfone), available from Solvay Speciality Polymers USA MeCl (methyl chloride), available from Matheson Gas PSU7: Udel® P - 3500 PSU in pellet form available from Solvay Speciality Polymers USA, Mw = 78385 g / mol, Mn = 22755 g / mol, PDI = 3.44.

[0260] Strong alkali synthesis of samples CE27 - CE29 and E30 - E32 Into a 1L four - necked resin kettle (reactor) equipped with an overhead stirrer, a nitrogen inlet, a thermocouple, a barrette trap, and a reflux condenser, PSU pellets (reactants) and a blend of DMSO + MCB (319 g) were placed. A pressure - equalizing funnel containing a caustic solution was attached to the head of the kettle. The reactor was purged with nitrogen until the PSU pellets were dissolved. For samples produced with a 10 wt% PSU recycle rate, the PSU pellets were dissolved at room temperature, and for samples produced with a 50 wt% PSU recycle rate, the PSU pellets were dissolved at 40 °C. After dissolution, bisphenol A was added to the kettle, the reaction medium was purged for 15 minutes, then heated to reflux, during which caustic alkali was added to the reaction medium. After reflux, the reaction medium was dehydrated by removing the water / MCB mixture. During dehydration, an MCB solution of DCDPS (129 g) was prepared in a heated pressure - equalizing funnel. After all the water added and generated during the reaction was removed, the DCDPS solution was added to the kettle.

[0261] After reaching the specified torque or polymerization time, the mixture was diluted with 400 g of MCB, and gaseous MeCl was blown into the reaction medium at about 1 g / min for 30 minutes for end-capping. After cooling, the reaction medium was further diluted with 400 g of MCB, and the formed NaCl salt was removed by pressure filtration. Subsequently, the filtered polymer solution was coagulated in methanol at a polymer-to-methanol ratio of 1:5 using a Waring blender. The coagulated polymer was washed 5 times with methanol and then dried in a vacuum oven at 120 °C for 12 - 20 hours.

[0262] The respective weights of the components of PSU samples CE27 - CE29 and E30 - E32 are shown in Table 10.

[0263]

Table 9

[0264] The Mw, Mn, and PDI of the obtained PSU samples CE27 - CE29 and E30 - E32 are reported in Table 11.

[0265]

Table 10

[0266] Accordingly, the scope of protection is not limited by the above description but only by the following claims. Each and every claim is incorporated herein as an embodiment of the present invention. Accordingly, the claims are a further description and an addition to the preferred embodiments of the present invention.

Claims

1. A method for producing polyaryl ethersulfone (P2) using a recycled polymer material containing polyaryl ethersulfone (P1) as a reactant, - Add a polar aprotic solvent (S) to the reaction vessel. - Add a recycled polymer material containing polyaryl ether sulfone (P1) to the reaction vessel. - Add alkali salt forming agent (A) to the reaction vessel. - Add at least one monomer (M) selected from the group consisting of at least one aromatic diol monomer (AA) and at least one aromatic dihalo monomer (BB) to the reaction vessel. The addition step thereby forms a reaction medium (RM) containing the recycled polymer material, which includes a polyaryl ether sulfone (P1), at least one monomer (M), an alkali salt forming agent (A), and a polar aprotic solvent (S). - Heat the reaction medium to reach a reaction temperature of at least 150°C and a maximum of 290°C to form polyaryl ether sulfone (P2), and - Separating the formed polyaryl ether sulfone (P2) from the reaction medium, Including; The alkali salt forming agent (A) is an alkali metal carbonate and / or alkali metal hydroxide; The polyaryl ether sulfone (P1) is present in an amount of at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or at least 95% by weight, based on the total weight of the PAES (P1): ・PPSU, PSU, PES, - Sulfonated PSU (sPSU), - Sulfonated PES (sPES), • Sulfonated PPSU (sPPSU), Any polymer derived from a diol monomer selected from isosorbide and / or tetramethylbisphenol F and a dihalomonomer selected from sulfonated dihalodiphenyl sulfone and / or dihalodiphenyl sulfone, Any copolymer derived from at least two diols selected from biphenol, bisphenol A, bisphenol S, isosorbide, tetramethylbisphenol F, and / or hydroquinone, and a dihalomonomer selected from sulfonated dihalodiphenyl sulfone and / or dihalodiphenyl sulfone, - A block polymer in the form of A-B or A-B-A, comprising at least one block having one repeating unit selected from formulas (L), (L'), (N), (N'), (O), (O'), (Q), (Q'), and at least one block having one repeating unit selected from formulas (T), (T'), (U), (U'), (V), (V'), (W), (W'), (U*), (V*), (W*), - Block polymers in the form of A-B or A-B-A, comprising at least one block having one repeating unit selected from formula (L), (L'), (N), (N'), (O), (O'), (Q), (Q'), and at least one polyalkylene oxide block or polyvinylpyrrolidone (PVP) block, such as a PEG block, a PPG block, or a PVP block, and a block copolymer. Any combination of two or more of these, It comprises a sulfone polymer selected from the group consisting of, Formulas (L), (L'), (N), (N'), (O), (O'), (Q), (Q'), (T), (T'), (U), (U'), (V), (V'), (W), (W'), (U*), (V*), (W*) are: 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 And in these formulas, Each R is independently selected from the group consisting of halogens, alkyls, alkenyls, alkynyls, aryls, ethers, thioethers, carboxylic acids, esters, amides, imides, alkali or alkaline earth metal sulfonates, alkyl sulfonates, alkali or alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds. A method in which each i is an independent integer between 1 and 4.

2. - The aromatic diol monomer (AA) is selected from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, isosorbide, isomannide, isoidide, tetramethylbisphenol F, hydroquinone, and any combination thereof, preferably from the group consisting of 4,4'-biphenol, bisphenol A, bisphenol S, tetramethylbisphenol F, hydroquinone, and any combination thereof, and / or - The aromatic dihalomonomer (BB) is preferably selected from the group consisting of 4,4'-difluorodiphenyl sulfone (DFDPS), 4,4'-dichlorodiphenyl sulfone (DCDPS), disulfonated DCDPS, disulfonated DFDPS, and any combination thereof, and / or The polar aprotic solvent (S) is selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (commonly called tetramethylene sulfone or sulfolane), N-alkyl-2-pyrrolidone, for example N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropylene urea (DMPU), dimethylformamide (DMF), tetrahydrothiophene-1-monoxide, and any combination thereof. The method according to claim 1.

3. The polyaryl ether sulfone (P1) is derived from the condensation of at least one aromatic diol monomer (AA') and at least one aromatic dihalo monomer (BB'), - The added aromatic diol monomer (AA) is the same as or different from the aromatic diol monomer (AA'); and / or - The added aromatic dihalomonomer (BB) is the same as or different from the aromatic dihalomonomer (BB'); The method according to claim 1.

4. The aforementioned polyaryl ether sulfone (P1) ・PPSU, PSU, PES, - Sulfonated PSU (sPSU), - Sulfonated PES (sPES), • Sulfonated PPSU (sPPSU), Any polymer derived from a diol monomer selected from isosorbide and / or tetramethylbisphenol F and a dihalomonomer selected from sulfonated dihalodiphenyl sulfone and / or dihalodiphenyl sulfone, Any copolymer derived from at least two diols selected from biphenol, bisphenol A, bisphenol S, isosorbide, tetramethylbisphenol F, and / or hydroquinone, and a dihalomonomer selected from sulfonated dihalodiphenyl sulfone and / or dihalodiphenyl sulfone, - A block polymer in the form of A-B or A-B-A, comprising at least one sulfone polymer block having one repeating unit selected from PPSU, sPPSU, PSU, sPSU, PES, sPES, and at least one block having one repeating unit produced from tetramethylbisphenol F and sulfonated or unsulfonated dihalodiphenyl sulfone, or from 1,4:3,6-dianhydrohexitol sugar diol and sulfonated or unsulfonated dihalodiphenyl sulfone, - Block copolymers in the form of A-B or A-B-A, comprising at least one block polymer having one repeating unit selected from PPSU, sPPSU, PSU, sPSU, PES, sPES, and at least one polyalkylene oxide block or polyvinylpyrrolidone (PVP) block such as a PEG block, PPG block, or PVP block, and Any combination of two or more of these, The method according to claim 1, selected from the group consisting of the following.

5. The recycled polymer material further comprises a pore-forming polymer (P3) different from polyaryl ether sulfone (P1), preferably polyvinylpyrrolidone (PVP), polyalkylene oxide (PEG, etc.), or any combination thereof, and The aforementioned recycled polymer material - A blend of the polyaryl ether sulfone (P1) and the other polymer (P3), and / or - A block copolymer comprising at least one block of the polyaryl ether sulfone (P1) and at least one block of the other polymer (P3), including, or The method according to claim 1, wherein the recycled polymer material further comprises a non-polymeric filler such as particulate inorganic filler, carbon fiber, and / or glass fiber.

6. The method according to claim 1, wherein the recycled polymer material comprises at least one material selected from the group consisting of post-consumer polymer articles, post-industrial polymer articles including article scrap, off-spec polyaryl ethersulfone products, and any combination thereof, and the article is preferably selected from the group consisting of membranes, automotive parts, electronic components, consumer product parts (such as baby bottles), composite materials, battery components, and any combination thereof.

7. - The added polyaryl ether sulfone (P1) is PES, the formed polyaryl ether sulfone (P2) is a PES homopolymer or copolymer, and the at least one monomer (M) added to the reaction vessel is bisphenol S; or - The added polyaryl ether sulfone (P1) is PSU, the formed polyaryl ether sulfone (P2) is a PSU homopolymer or copolymer, and the at least one monomer (M) added to the reaction vessel is bisphenol A; or - The added polyaryl ether sulfone (P1) is PPSU, the formed polyaryl ether sulfone (P2) is a PPSU homopolymer or copolymer, and the at least one monomer (M) added to the reaction vessel is 4,4'-biphenol; The method according to claim 1.

8. - The polyaryl ether sulfone (P2) is the Mw of the polyaryl ether sulfone (P1) （Ｐ１） Mw within + / - 35% （Ｐ２） Having, the Mw （Ｐ１） and Mw （Ｐ２） However, it is measured by a GPC method using methylene chloride as the mobile phase and calibrated with a polystyrene standard; and / or - The polyaryl ether sulfone (P2) is the PDI of the polyaryl ether sulfone (P1). Ｐ１ PDI within + / - 35% of the value Ｐ２ The PDI has a value, where PDI is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), and Mw and Mn are measured by GPC, respectively, using methylene chloride as the mobile phase and calibrated with a polystyrene standard; The method according to claim 1.

9. The polyaryl ether sulfone (P2) has a Mw of at least 40 kDa, preferably at least 50 kDa, more preferably 50 kDa to 100 kDa or 55 kDa to 90 kDa. （Ｐ２） Having, the Mw （Ｐ２） The method according to claim 1, wherein the measurement is performed by a GPC method calibrated with a polystyrene standard using methylene chloride as the mobile phase.

10. The method according to claim 1, wherein the recycled polymer material containing the polyaryl ether sulfone (P1) is added to the reaction vessel in the form of a solid, such as pellets, fibers, flakes, powder, fragments of shredded or crushed articles, solidified particles, or any other solid 3D object, or in the form of a solution or slurry in which at least a portion of the polyaryl ether sulfone (P1) is dissolved before being added to the reaction vessel.

11. The separation step includes the coagulation of the polyaryl ether sulfone (P2); and / or Between the reaction step and the separation step, - A step of cooling the reaction medium, ・ A step of quenching the reaction medium by adding a solvent (S ｑ ), which may be the same as or different from the polar aprotic solvent (S), and / or - A step of adding an end capping agent to convert the hydroxyl terminal group of the formed polyaryl ether sulfone (P2) into a less reactive terminal group. Further including at least one of the following: The method according to claim 1.

12. The method according to claim 1, wherein the recycling rate of the polyaryl ether sulfone (P1) in the reaction medium is 100% to 1% by weight, and the recycling rate is calculated as the ratio of the weight of the added polyaryl ether sulfone (P1) to the maximum weight of the PAES polymer that would theoretically be produced based on the equimolar stoichiometric amount of polycondensation of monomers (AA) and (BB) when both diol monomer (AA) and dihalo monomer (BB) are added to the reaction medium, and the total weight of the added polyaryl ether sulfone (P1).

13. The at least one monomer (M) comprises at least one aromatic diol monomer (AA), - The condensation reaction is carried out with a molar ratio of the alkali salt-forming salt to the diol monomer (AA) of at least 1 and at most 2, and / or - The diol (AA) and the alkali salt forming agent (A) are added to the reaction vessel in the form of an alkali salt (AAA) of the diol (AA). The method according to claim 1.

14. The reaction temperature is, - 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 - Maximum temperature is 285°C, 280°C, 275°C, 270°C, 265°C, or 260°C; The method according to claim 1.

15. A polyaryl ether sulfone (P2) obtained by the method according to any one of claims 1 to 14.

16. An article comprising the polyaryl ether sulfone (P2) according to claim 15, preferably selected from the group consisting of films, fibers, sheets, solution-processed films, solution-processed monofilaments, and any combination thereof.

Images