Graft Polyaryl Ether Copolymer

Abstract

The present invention relates to graft polyarylether ('PAE') copolymers (P1), a process for preparing the graft PAE copolymers (P1) from side-chain allyl / vinylene-functionalized PAE copolymers (P0) by free radical reaction with vinylpyrrolidone, and the use of the graft PAE copolymers (P1) in the preparation of articles, such as membranes or parts thereof. The graft PAE copolymers (P1) contain at least two types of repeat units, one of which has a side-chain grafted poly(vinylpyrrolidone). The present invention also relates to amorphous side-chain allyl / vinylene-functionalized polyaryletherketone copolymers (P0).

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Patent Application No. 63 / 409989, filed September 26, 2022, and European Patent Application No. 22211450.6, filed December 5, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present disclosure relates to a graft polyarylether copolymer (P1), to a process for producing the graft copolymer (P1) from an amorphous side-chain allyl / vinylene-functionalized polyarylether copolymer (P0), to an article, particularly a membrane, comprising such a copolymer (P1), and to the use of the copolymer (P1) for preparing such an article. The present disclosure also relates to the amorphous side-chain allyl / vinylene-functionalized polyaryletherketone copolymer (P0) and its corresponding graft polyaryletherketone copolymer (P1). [Background technology]

[0003] Poly(aryl ether sulfone) (PAES) polymers are also high-performance polymers with high mechanical strength and high thermal stability; they are used in a variety of industrial applications. Their chemical, thermal, and mechanical resistance, combined with their excellent hydrolytic stability and relatively low manufacturing costs, make them ideal for widespread use in the manufacture of membranes, particularly porous hollow fiber polymer membranes. Porous hollow fiber polymer membranes are used in many applications, including hemodialysis, ultrafiltration, nanofiltration, reverse osmosis, gas separation, microfiltration, desalination by membrane distillation, and pervaporation. For many of these applications, membranes with optimal selectivity and chemical, thermal, and mechanical stability are desirable.

[0004] While poly(aryl ether) polymers (PAEs) have many advantages and good physical properties, it may be desirable to tailor one or more properties to improve performance in a particular application (e.g., hemodialysis, bioseparation, or water filtration), such as being less susceptible to fouling, having increased hydrophilic properties, and / or having improved biocompatibility.

[0005] The inherent hydrophobicity of PAE polymers actually makes membranes manufactured therefrom prone to fouling, which adversely affects their performance. Fouling is caused by hydrophobic interactions between the membrane material and contaminants (e.g., microorganisms, proteins, or organic matter) originating from the fluid being processed through the membrane. In particular, fouling is initiated by the adsorption of contaminants onto the membrane surface and internal structure, resulting in pore blockage, cake layer formation, or biofilm formation. Membrane fouling not only reduces membrane permeability and overall lifespan, but also increases maintenance costs due to extensive and frequent cleaning to remove contaminants.

[0006] Since most of the commercially available pressure-driven membranes are made of hydrophobic polymers such as polyethersulfone (PES), polysulfone (PSU) and poly(ether ether ketone) (PEEK), improving the surface hydrophilicity can be achieved by increasing the density of hydrophilic groups on the membrane surface, and consequently, hydrophilic modification of the membrane surface reduces the organic fouling properties.

[0007] For example, PAEs can be blended with highly hydrophilic polymers such as polyvinylpyrrolidone to increase the hydrophilicity of PAE-based membranes, while PAEs can be blended with zwitterionic polymers to impart antifouling properties. While this approach may be simple, it has serious limitations because the two or more polymers that are typically blended are not compatible, which leads to gross macrophase separation in the final product. Furthermore, because these polymers are simply physical mixtures, the resulting product can change its composition and thus its performance due to the loss of one of the polymers by diffusion during membrane operation.

[0008] Another approach to avoid such behavior is to covalently bond the PAE homopolymer to other polymers so that the resulting material has a robust composition and does not change substantially during application.

[0009] Altering hydrophilicity can also be achieved by combining two homopolymers to produce a block copolymer with the unique combination of properties of each individual homopolymer. For example, in membrane applications, a PAES homopolymer can be covalently bonded to a hydrophilic homopolymer to synthesize a new PAES-hydrophilic block copolymer that retains the mechanically robust and amorphous pore structure of the PAES component while providing superior membrane performance due to the improved wettability provided by the hydrophilic component. This technique can sometimes compromise the mechanical performance of the final product due to the inherent low molecular weight of the PAES component.

[0010] Another technique reported in the literature involves covalent grafting as a means of modifying polyarylether polymer properties. Graft copolymerization is a reaction in which side-chain grafts derived from one or more vinyl monomers are covalently attached to a linear polymer backbone, resulting in the formation of a graft copolymer with new characteristics derived from two or more parent polymers. Grafting can involve the polymerization reaction of a functionalized base polymer with vinyl monomers, resulting in the formation of reactive groups on the base polymer. From an anti-fouling perspective, the large chain density of the grafted polymer closes the gaps between the polymer chains, making such gaps much smaller than the size of proteins and / or microbial cells. This makes their adsorption to the membrane surface through the membrane voids difficult.

[0011] Yang et al., "Cross-linked poly(aryl ether ketone) anion exchange membrane with high ion conduction by two different functional imidazole side chains," in Reactive and Functional Polymers, Vol. 151, pp. 104551 (June 2020), and Xu et al., "Afacile functionalized routine for the synthesis of side-chain sulfonated poly(arylene ether ketone sulfone) as proton exchange membranes," International Journal of Hydrogen Energy, Vol. 42(8), pp. 5295–5305 (February 2017), report the covalent attachment of vinyl monomers to polyaryl ether ketone and ketone sulfone polymers with side-chain allyl groups. In these examples, very short chains of monomers or dimers are attached to the polymers by free-radical grafting.

[0012] Korean Patent Application Publication No. 20170115697A relates to a permeation membrane having a support formed by reacting a functionalized polysulfone-based polymer (APSf) with a hydrophilic compound to provide hydrophilicity and thereby improved water permeability. The APSf polymer is a homopolymer having double bonds in the side chains and produced by polymerization of 2,2'-diallylbisphenol A and difluorodiphenyl sulfone in potassium carbonate. However, this reference does not disclose a solvent for producing APSf, and the APSf homopolymer is not characterized by molecular weight, glass transition temperature, etc. The hydrophilic compound has double bonds that react with the side chain double bonds of the APSf polymer. These double bonds can be activated by a radical initiator. In one example, APSf homopolymer (1 g) was mixed with traditional polysulfone (PSf) (1 g) and treated with a vinyl monomer (0.8 g N,N-dimethylaminoethyl methacrylate) in the presence of a radical initiator (0.1 g azobisisobutyronitrile) in 7 g N-methylpyrrolidone (NMP) at 60 °C for 3 hours. At the end of the radical reaction, the mixture was used "as is" to apply it to a polyethylene terephthalate nonwoven fabric attached to a glass plate. However, in this reference, the resulting PSf-based polymer was not isolated from the ungrafted vinyl polymer, unreacted monomer, and radical initiator. Furthermore, APSf homopolymer is very hydrophobic because it contains two allyl groups in every repeat unit, and this type of homopolymer would be difficult to prepare in polar aprotic solvents such as dimethyl sulfoxide or NMP. Summary of the Invention

[0013] The present invention provides an amorphous graft polyarylether (hereinafter "PAE") copolymer (P1) and a process for preparing such a copolymer (P1). An amorphous side-chain allyl / vinylene-functionalized polyarylether copolymer (P0) is grafted with a functional vinyl monomer to produce a graft copolymer (P1) in which the vinyl polymer is covalently attached to some of the side chains of the polyarylether copolymer backbone. This graft polyarylether copolymer (P1) incorporates the advantages of both polyarylether polymers and vinyl polymers for specific applications. This graft polyarylether copolymer (P1) contains a complex polymer structure useful for many different applications, such as preparing membranes.

[0014] The present invention provides a method for introducing functionality into PAE polymers by grafting vinyl polymers from reactive side chains.

[0015] A first aspect of the present disclosure is directed to a grafted PAE copolymer (P1) comprising a grafted vinyl polymer covalently attached to some of the side chains of a PAE copolymer backbone. The copolymer (P1) comprises poly(aryl ether) (PAE) repeating units (R P1 ), and functionalized PAE repeat units (R*) grafted with vinyl polymer side chains. P1 ), more precisely, poly(aryl ether sulfone) (“PAES”) repeat units (R P1a ) and functionalized PAES repeating units (R*) grafted with vinyl polymer side chains. P1a ), or poly(aryl ether ketone) (“PAEK”) repeat units (R P1b ) and functionalized PAEK repeating units (R*) grafted with vinyl polymer side chains. P1b ).

[0016] A second aspect of the present invention is a polymer comprising a polymer having a total of at least 50 mol % of PAEK repeat units (R P1b ) and PAEK repeat units (R*) functionalized with reactive side chains containing allyl and / or carbon-carbon double bond-containing functional groups.P1b This study aimed to prepare amorphous side-chain allyl / vinylene-functionalized polyaryletherketone copolymers (P0) containing aryl groups.

[0017] A third aspect of the present invention is directed to a process for preparing a graft PAE copolymer (P1) from a side-chain allyl / vinylene functionalized PAE copolymer (P0) that contains functional groups containing allyl and / or carbon-carbon double bonds that are reactive and therefore can be used to efficiently modify the copolymer.

[0018] A fourth aspect of the present invention is directed to the use of the resulting grafted PAE copolymer (P1) in various applications, for example to prepare membranes.

[0019] A fifth aspect of the present invention is directed to an article comprising the grafted PAE copolymer (P1), said article preferably being a membrane or part thereof.

[0020] Another aspect of the present invention is particularly directed to solutions containing the grafted PAE copolymer (P1) that are used to form films, fibers or membranes.

[0021] A further aspect of the present invention may be directed to a purification process comprising at least a filtration step through a membrane, fiber or film comprising or made from the grafted PAE copolymer (P1) described herein. DETAILED DESCRIPTION OF THE INVENTION

[0022] In this application: - Any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure, and each embodiment so defined may be combined with other embodiments unless otherwise indicated or clearly incompatible; - When an element or component is said to be included in and / or selected from a list of enumerated elements or components, in related embodiments expressly contemplated herein, the element or component can also be any one of the individually enumerated elements or components, or can be selected from a group consisting of any two or more of the explicitly enumerated elements or components; it is to be understood that any element or component enumerated in a list of elements or components can be omitted from such list; - any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range, and equivalents thereof; - the term "comprises" (or "comprises") encompasses "consisting essentially of" (or "consisting essentially of") and also "consisting of" (or "consisting of"); - the use of the singular form "a" or "one" herein includes the plural form unless specifically stated otherwise; - it is to be understood that the elements, properties and / or characteristics of the (co)polymers, products or articles, processes or uses described herein may be combined in all possible ways, explicitly or implicitly, with other elements, properties and / or characteristics of the (co)polymers, products or articles, processes or uses, and this is done without departing from the scope of the present specification.

[0023] In this disclosure, the term "repeating unit" refers to the smallest unit of a PAE polymer that repeats in a chain and is composed of the condensation of an aromatic diol compound with an aromatic dihalo compound. The term "recurring unit" is synonymous with the terms "repeating unit" and "structural unit."

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

[0025] As used herein, the term "copolymer" includes polymers that may have two or more different types of repeat units.

[0026] The term "solvent" is used herein in its ordinary sense to refer to a substance capable of dissolving another substance (solute) to form a uniformly dispersed mixture at the molecular level. In the case of polymeric solutes, it generally refers to a solution of the polymer in the solvent when the resulting mixture is clear and no phase separation is observed in the system. Phase separation is understood to be the point at which the solution becomes turbid or cloudy due to the formation of polymer aggregates, often referred to as the "cloud point."

[0027] The term "membrane" is used herein in its ordinary sense, i.e., it refers to a discrete, generally thin, interface that resists penetration of chemical species in contact with it. This interface may be molecularly uniform, i.e., completely uniform in structure (dense membrane), or it may be chemically or physically heterogeneous, e.g., containing gaps, voids, or pores of finite dimensions (porous membrane). Membranes generally have an exterior surface with which chemical species contact and an interior surface within the pores.

[0028] Weight average molecular weight (M w ) and number average molecular weight (M n The M of the PAE copolymer (P1) can be estimated by gel permeation chromatography (GPC) using a mobile phase calibrated with polystyrene standards. The mobile phase can be selected from any solvent for the copolymers (P0), (P1) described herein, such as solvent S1 disclosed herein, such as methylene chloride, N-methyl-2-pyrrolidone (NMP), sulfolane, or N,N'-dimethylacetamide (DMAc). w and M n is preferably measured by GPC Method 1 provided in the Examples. w and M nis preferably measured by GPC Method 2 provided in the Examples. Polydispersity Index (PDI) is used herein to refer to the weight average molecular weight (M w ) logarithm average molecular weight (M n ) is expressed as a ratio of

[0029] The glass transition temperatures of the PAE copolymers (P1) and (P0) can be measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0030] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference conflicts with the statements of this application to the extent that a term may be unclear, the statements of this application shall control.

[0031] Graft PAE copolymer (P1) A first aspect of the present invention relates to a graft polyarylether copolymer (P1) comprising at least two types of repeating units, one type of repeating unit being functionalized by having a side-chain grafted vinyl polymer.

[0032] The functionality of the grafted PAE copolymer (P1) is inherent in the PAE copolymer backbone and results from a step-growth polymerization in the presence of at least one allyl-substituted diol monomer to form a side-chain allyl / vinylene-functionalized PAE copolymer (P0), which serves as the basis for producing the copolymer (P1). This advantageously makes the PAE copolymer backbone versatile, as the content of functional groups can be adjusted by varying the content of the allyl-substituted diol monomer relative to other diols in the reaction mixture when the base PAE copolymer (P0) is formed. The allyl-substituted monomer contains two pendant allyl group side chains, each containing 3 to 7 carbon atoms.

[0033] The grafted PAE copolymer (P1) of the present invention is in the form of a racemic product. Due to the presence of a base and high temperature during polymerization to form the base PAE copolymer (P0) from which the copolymer (P1) is formed, the allyl-substituted monomers usually racemize during polymerization so that the position of the double bond can vary along the side chain. This results in the formation of molecules that differ from each other due to the fact that the C=C double bond can be at the end of the side chain or at the carbon immediately preceding the end of the side chain. The amount of racemization depends on the reaction time and temperature.

[0034] The copolymer (P1) of the present invention is - at least 50 mol % in total of sulfone repeat units (R P1a ) and functionalized sulfone repeating units (R*) of formula (N1) P1a ) (the mole percentages are based on the total number of moles of repeating units in copolymer (P1)): [ka] or - at least 50 mol % in total of ketone repeat units (R P1b ) and functionalized ketone repeating units (R*) of formula (N2) P1b ) (the mole percentages are based on the total number of moles of repeating units in copolymer (P1)): [ka] Including, During the ceremony, - Repeating unit (R P1a ) / Repeating unit (R* P1a ) or repeating unit (R P1b ) / Repeating unit (R* P1b ) is at least 1 / 5 and at most 100 / 1; - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4, preferably i=0 or 1; - T is a bond, -C(CH3)2-; -SO2-; -CH2-; -O-; -S-; -C(O)-; -C(CF3)2-; -C(=CCl2)-; -C(CH3)(CH2CH2COOH)-; -N=N-; and -R a C=CR b -(where each R a and R b are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy, or C6-C18 aryl group; m is an integer of 1 to 6 (CH2) m -and-(CF2) m -; a linear or branched, aliphatic divalent radical of up to 6 carbon atoms; and combinations thereof; preferably T is selected from the group consisting of a bond, -C(CH3)2-, and -SO2-; -G N is expressed by the following formula (G N1 )~(G N10 ) and any combination thereof: [ka] (In the formula, - Group G N wherein W is selected from the group consisting of a bond, —SO—, —C(CH)—, and any combination thereof, preferably selected from —C(CH)— and / or —SO— or selected from —C(CH)— and / or a bond; - Group G N wherein each k is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2, or 3, more preferably k=0; groups G, which may be the same or different from one anotherN The two grafted polymers P2 in are grafted poly(vinylpyrrolidone) polymers ("PVP"); groups G, which may be the same or different from one another N The two I's in the formula represent fragments of a free radical initiator and / or fragments of a PVP polymer. is selected from the group consisting of:

[0035] The grafted PAE copolymer (P1) of the present invention comprises functionalized sulfone repeating units (R*) of formula (N1): P1a ) or consisting solely of functionalized ketone repeat units (R*) of formula (N2′) P1b ) are excluded.

[0036] Repeating unit (R P1a ) / Repeating unit (R* P1a ) or repeating unit (R P1b ) / Repeating unit (R* P1b The molar ratio of repeating units (R ) in the PAE copolymer (P1) may be at least 1 / 5, at least 1 / 4, at least 1 / 3, at least 1 / 2, or at least 1 / 1, and / or at most 100 / 1, at most 50 / 1, at most 25 / 1, or at most 22 / 1. P1a ) / Repeating unit (R* P1a ) or repeating unit (R P1b ) / Repeating unit (R* P1b ) may be from 1 / 4 to 50 / 1, preferably from 1 / 3 to 40 / 1 or from 1 / 3 to 30 / 1, more preferably from 1 / 2 to 30 / 1, from 1 / 2 to 25 / 1, or from 1 / 2 to 22 / 1.

[0037] The grafted PAE copolymer (P1) can be such that each R1 is independently selected from the group consisting of a C1-C12 moiety, optionally containing one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.

[0038] The grafted PAE copolymer (P1) may preferably be such that i is zero for each R1 (meaning that the phenyl ring is unsubstituted).

[0039] In another embodiment, the grafted PAE copolymer (P1) having sulfone repeating units of formulas (M1) and (N1) may be such that in some repeating units of formulas (M1) and (N1), some R1 are selected from sulfonic acid groups; alkali or alkaline earth metal sulfonate groups; and / or alkylsulfonate groups, and the corresponding i is 1, while in other sulfone repeating units of formulas (M1) and (N1), i=0 (i.e., the phenyl ring is not substituted). Such phenyl rings optionally substituted with R1 and having i=1 are preferably bonded to the -SO2- linking group of the sulfone repeating units.

[0040] Alternatively, the grafted PAE copolymer (P1) having ketone repeat units of formulae (M2) and (N2) may be such that in some ketone repeat units of formulae (M2) and (N2), some R1 are selected from sulfonic acid groups, alkali or alkaline earth metal sulfonate groups, and / or alkylsulfonate groups, and the corresponding i is 1, while in other ketone repeat units of formulae (M2) and (N2), i=0 (i.e., the phenyl is not substituted). Such phenyl rings optionally substituted with R1 and having i=1 are preferably bonded to the -C(O)- linking group of the ketone repeat units.

[0041] The grafted PAE copolymer (P1) is represented by the formula (G N1 )~(G N10 ) any group G N It may be such that k is zero in

[0042] In some embodiments, the grafted PAE copolymer (P1) has the formula (G N1 )~(G N10 ) any group G NIn the same grafted PAE copolymer (P1), W can be -C(CH3)2- and / or -SO2-. N can be -C(CH3)2-, while W can be any other group N However, preferably, in the same grafted PAE copolymer (P1), W is -SO2-. N and is either -C(CH3)2- or -SO2-.

[0043] In another embodiment of the graft PAEK copolymer (P1) having ketone repeat units of formula (M2) and (N2), N1 )~(G N10 ) any group G N In the same graft PAEK copolymer (P1), W can be a bond and / or -C(CH3)2-. N can be -C(CH3)2-, while W can be any other group G N However, preferably, in the same grafted PAEK copolymer (P1), W is a bond between all groups G N and is either -C(CH3)2- or a bond.

[0044] Repeating unit (R* P1a ) or (R* P1b ) in the formula (G N1 )~(G N10 ) any group G N Each of the grafted polymers P2 in the grafted polymer P2 comprises at least 50 mole %, based on the total number of moles of repeat units in the grafted polymer P2, of the formula (P); [ka] wherein n in formula (P) is an integer of at least 3, or at least 5, or at least 8, or at least 10, or at least 20, or at least 30, or at least 40, or at least 50, and at most 200, or at most 175, or at most 150, or at most 100. In the repeating unit Rp of formula (P), n is preferably 3 to 200, or 10 to 200, or 10 to 150, or 50 to 150, or 50 to 100, or 60 to 90, or 65 to 85.

[0045] Formula (G N1 )~(G N10 ) any group G N Each of the grafted polymers P2 in the formula (G) may contain, in total, at least 55 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% of repeating units Rp of formula (P), based on the total number of moles of repeating units in the grafted polymer P2. N1 )~(G N10 ) any group G N Each of the grafted polymers P2 in may preferably consist essentially of repeating units Rp of formula (P).

[0046] The grafted PAE copolymer (P1) is a copolymer of the group G N wherein I can be a fragment of a free radical initiator selected from the group consisting of 2,2'-azobis(2-methylpropionitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), benzoyl peroxide, hydroperoxide, and any combination thereof, and / or can be a fragment of a PVP polymer chain comprising at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% of repeating units Rp of formula (P), based on the total number of moles of repeating units in I. N When at least one of I is a fragment of a PVP polymer chain, the chain length or molecular weight (M n ) are preferably the same group G N The chain length or molecular weight (M n ) is less than

[0047] Preferably, the group G N If at least one of the two I's in is a fragment of a free radical initiator, then such I's are [ka] The group G can be a fragment of AIBN, such as N When at least one of the two I's in is a fragment of a PVP polymer chain, such I's preferably consist essentially of repeating units Rp of formula (P).

[0048] The graft PAE copolymer (P1) is preferably prepared by radical polymerization of a side-chain allyl / vinylene functionalized polyarylether copolymer (P0) containing side-chain carbon-carbon double bonds and no bound PVP with vinylpyrrolidone monomer and a free radical initiator.

[0049] The grafted PAE copolymer (P1) is preferably not crosslinked. During the preparation of the copolymer (P1) from the copolymer (P0), practically no observable crosslinking occurs within the PAE copolymer or within or between the vinyl polymer, as evidenced by the resulting very good solubility of the copolymer (P1) without the presence of any gel or undissolved mass, and by the glass transition temperature of the copolymer (P1) being similar (within ±15°C, preferably within ±11°C, more preferably within ±10°C or within ±8%, or within ±6%, or within ±5%) to that of the copolymer (P0) from which the copolymer (P1) is prepared. Tg and Tg 0 is preferably measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0050] In an alternative embodiment, the graft copolymer (P1) has a Tg 0 -10℃~Tg 0 +10°C, where Tg 0is the glass transition temperature of the side-chain allyl / vinylene functionalized PAE copolymer (P0) from which the copolymer (P1) is prepared. Tg and Tg 0 is preferably measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0051] The grafted PAE copolymer (P1) preferably contains less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.3% by weight or less than 0.1% by weight of free vinylpyrrolidone, based on the total weight of the grafted PAE polymer (P1). Detection of free vinylpyrrolidone can be carried out by Fourier transform infrared spectroscopy (FTIR).

[0052] The grafted PAE copolymer (P1) preferably contains less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. %, even more preferably less than 0.3 wt. % or less than 0.1 wt. % of free poly(vinylpyrrolidone), based on the total weight of the grafted PAE polymer (P1). Detection of free PVP can be carried out by Fourier transform infrared spectroscopy (FTIR).

[0053] The grafted PAE copolymer (P1) has the same polymer backbone as the base PAE copolymer (P0) from which the copolymer (P1) is produced. The difference between the grafted PAE copolymer (P1) and the side-chain allyl / vinylene-functionalized PAE copolymer (P0) is the presence of grafted polymer P2 grafted onto some side chains of the copolymer (P1), which is attached by way of reaction with the side-chain allyl / vinylene groups in its corresponding PAE copolymer (P0).

[0054] The grafted PAE copolymer (P1) has a weight average molecular weight M of at least 150 kDa, preferably at least 200 kDa, more preferably at least 250 kDa or at least 300 kDa. wThe graft PAE copolymer (P1) has a weight average molecular weight Mw of at most 1100 kDa, preferably at most 1000 kDa, more preferably at most 900 kDa or at most 700 kDa. The graft PAE copolymer (P1) may have a weight average molecular weight Mw of from 200 kDa to at most 1100 kDa, preferably from 250 kDa to at most 1000 kDa, more preferably from 300 kDa to at most 900 kDa, and even more preferably from 300 kDa to at most 700 kDa. The Mw of the PAE copolymer (P1) w is preferably measured by GPC Method 1 provided in the Examples.

[0055] The grafted PAE copolymer (P1) preferably has a PDI less than or equal to the PDI of the side-chain allyl / vinylene-functionalized PAE copolymer (P0) from which the grafted PAE copolymer (P1) is prepared. 0 =M w 0 / M n 0 PDI=M is ​​greater than w / M n The M of the PAE copolymer (P1) n and M w is preferably measured by GPC Method 1 provided in the Examples and is the M n 0 and M w 0 is preferably measured by GPC Method 2 provided in the Examples. Generally, the grafted PAE copolymer (P1) may have a PDI of at least 4, or at least 4.5, or at least 5, or at least 5.5, or at least 6, or at least 6.5.

[0056] The grafted PAE copolymer (P1) has a glass transition temperature Tg of the side-chain allyl / vinylene functionalized PAE copolymer (P0) from which the grafted PAE copolymer (P1) is prepared. 0The glass transition temperature Tg may be within ±15°C or ±11°C or within ±10%, preferably within ±8%, more preferably within ±6%, and even more preferably within ±5% of the Tg and Tg 0 is preferably measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0057] In an alternative embodiment, the grafted PAE copolymer (P1) has a Tg 0 -10℃~Tg 0 +10°C, where Tg 0 is the glass transition temperature of the side-chain allyl / vinylene functionalized PAE copolymer (P0) from which the copolymer (P1) is prepared. Tg and Tg 0 is preferably measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0058] The solubility of the grafted PAE copolymer (P1) in a particular solvent is the same as or higher than the solubility of the side-chain allyl / vinylene-functionalized PAE copolymer (P0) from which the copolymer (P1) is prepared. Preferred solvents in which the grafted PAE copolymer (P1) is soluble are 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), DMAc, tetramethylene sulfone (sulfolane), NMP, or any mixture thereof.

[0059] Graft PAES copolymer (P1) The grafted PAE copolymer (P1) has a repeating unit (R P1a ) and functionalized repeating units (R* P1a ), it can be referred to as a graft "PAES" copolymer (P1).

[0060] The grafted PAES copolymer (P1) preferably has a Tg in the range of 140 to 250°C, preferably 170 to 240°C, more preferably 180 to 220°C, as measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0061] The grafted PAES copolymer (P1) may comprise a total of at least 55 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units (R P1a ) and (R* P1a The graft PAES copolymer (P1) may preferably contain the repeating unit (R P1a ) and (R* P1a ) can consist essentially of

[0062] The repeating unit (R P1a ) / Repeating unit (R* P1a ) is the molar ratio of - at least 1 / 4, at least 1 / 3, at least 1 / 2, at least 1 / 1, and / or - Maximum 50 / 1, Maximum 40 / 1, Maximum 30 / 1, Maximum 25 / 1 or Maximum 22 / 1 It could be.

[0063] The repeating unit (R P1a ) / Repeating unit (R* P1a ) may be 1 / 4 to 50 / 1, preferably 1 / 3 to 40 / 1, more preferably 1 / 2 to 30 / 1 or 1 / 3 to 30 / 1, 1 / 2 to 25 / 1, 1 / 2 to 22 / 1, or 1 / 1 to 22 / 1.

[0064] The graft PAES copolymer (P1) has a repeating unit (R P1a), where T is selected from the group consisting of a bond, —SO—, —C(CH)—, and any combination thereof. The grafted PAES copolymer (P1) can, for example, have some repeating units (R P1a ) and other repeating units where T is -SO2- (R P1a ) may be included.

[0065] Preferred repeating units (R P1a ) is represented by formula (M1a), (M1b), or (M1c): [ka] (In the formula, - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4, preferably i=0 It can be of the following type.

[0066] The more preferred repeating units (R P1a ) has the formula (M1b') and / or (M1b"): [ka] (In the formula, each R1 is independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates; Each i is independently an integer from 1 to 4, preferably i=1. It can be of the following type.

[0067] Amorphous grafted PAEK copolymer (P1) The grafted PAE copolymer (P1) has a repeating unit (R P1b ) and functionalized repeating units (R* P1b ), it can be referred to as a graft "PAEK" copolymer (P1).

[0068] The grafted PAEK copolymer (P1) preferably has a Tg in the range of 100 to 200°C, preferably 105 to 150°C, more preferably 110 to 140°C, as measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0069] The graft "PAEK" copolymer (P1) is an amorphous polymer, meaning that the graft "PAEK" copolymer (P1) does not exhibit a melting point (Tm) as determined by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0070] The grafted PAEK copolymer (P1) may comprise a total of at least 55 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 repeat units (R P1b ) and (R* P1b The graft PAEK copolymer (P1) may preferably comprise the repeating unit (R P1b ) and (R* P1b ) can consist essentially of

[0071] The repeating unit (R P1b ) / Repeating unit (R* P1b ) is the molar ratio of - at least 1 / 4, at least 1 / 3, at least 1 / 2, or at least 1 / 1, and / or - Maximum 50 / 1, Maximum 40 / 1, Maximum 30 / 1, Maximum 25 / 1 or Maximum 22 / 1 It could be.

[0072] The repeating unit (R P1b ) / Repeating unit (R* P1b ) may be from 1 / 4 to 50 / 1, preferably from 1 / 3 to 40 / 1 or from 1 / 3 to 30 / 1, more preferably from 1 / 2 to 30 / 1, 1 / 2 to 25 / 1, or 1 / 2 to 22 / 1.

[0073] Preferred repeating units (R P1b ) is expressed as formula (M2a): [ka] It can be of the following type.

[0074] The graft PAEK copolymer (P1) is a copolymer of the repeating unit (R P1b ) and (R* P1b ) is different from one or more other repeating units (R' P1b ), for example, the following formula (M2b) or (M2b'): [ka] (In the formula, - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4 It may further include those such as those.

[0075] In such cases, the grafted PAEK copolymer (P1) may contain at most 20 mol %, at most 15 mol %, or at most 10 mol % of repeating units (R'), based on the total number of moles in the grafted PAEK copolymer (P1). P1bThe repeating unit (R') in the graft PAEK copolymer (P1) may be P1b The amount of ) should be such that the grafted PAEK copolymer (P1) retains its amorphous state and makes it soluble in polar aprotic solvents such as NMP, sulfolane, DMAc, and others described herein.

[0076] Preparation process of PAE copolymer (P1) The grafted PAE copolymer (P1) can be formed by a free radical reaction with vinylpyrrolidone monomer in the presence of a free radical initiator.

[0077] Therefore, a second aspect of the present invention is a process for the preparation of a grafted PAE copolymer (P1), comprising: - reacting, in a solvent S1, a side-chain allyl / vinylidene-functionalized polyarylether copolymer (P0) with vinylpyrrolidone monomer in the presence of at least one free radical initiator to form a graft polyarylether copolymer (P1); - removing any free poly(vinylpyrrolidone) and optionally any unreacted vinylpyrrolidone monomer and / or unreacted free radical initiator from the formed grafted PAE copolymer (P1) to produce a purified grafted PAE copolymer (P1); The present invention relates to a process including:

[0078] Side-chain allyl / vinylene functionalized PAE copolymer (P0) - sulfone repeating units (R P0a ) and functionalized repeating units (R* P0a ); or - Ketone repeating units (R P0b ) and functionalized repeating units (R* P0b ) Includes.

[0079] The functionalized repeating units (R*) in the PAE copolymer (P0) used in the reaction mixture P0a) or (R* P0b the number of moles of vinylpyrrolidone monomer used in the reaction mixture is n2, and the molar ratio n2 / n1 is at least 3, or at least 5, or at least 8, or at least 10, or at least 20, or at least 30, or at least 40, or at least 50, and at most 200, or at most 175, or at most 150, or at most 100. The molar ratio n2 / n1 is preferably 3 to 200, or 10 to 200, or 10 to 150, or 50 to 150, or 50 to 100, or 60 to 90, or 65 to 85.

[0080] The reacting step is preferably carried out in a reaction mixture comprising vinylpyrrolidone monomer and solvent S1. A free radical initiator may be added to the reaction mixture to start the reaction.

[0081] For the reaction process, the copolymer (P0) and vinylpyrrolidone monomer may be first added to a reaction vessel, then dissolved in solvent S1 and heated at a suitable reaction temperature.

[0082] Alternatively, the copolymer (P0) can be first formed into an article and then contacted with a reaction mixture comprising vinylpyrrolidone monomer, a free radical initiator and a solvent S1 and heated at a suitable reaction temperature.

[0083] The reaction mixture is preferably purged with a non-oxidizing gas or atmosphere (such as nitrogen) after which a free radical initiator is added to start the free radical reaction. The time for purging can vary from 10 to 120 minutes, although 20 to 60 minutes is generally sufficient.

[0084] The free radical reaction may generally be carried out for at least 1 hour and at most 48 hours, preferably at least 3 hours and at most 24 hours, more preferably at least 6 hours and at most 18 hours, and even more preferably at least 8 hours and at most 16 hours.

[0085] The reaction process for preparing the grafted PAE copolymer (P1) is carried out under the following reaction conditions i) to iv): i) in the presence of a solvent; ii) in the presence of at least one free radical initiator; iii) at a reaction temperature of 10°C to 200°C; iv) in the absence of cross-linking conditions It may be carried out under at least one of the following conditions:

[0086] Reaction conditions (i): When the reaction for preparing the grafted PAE copolymer (P1) is carried out in a solvent S1, the solvent S1 may be any of 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO), diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (commonly called tetramethylene sulfone or sulfolane), N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropanol, ... The polar aprotic solvent is selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO), N-butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropyleneurea (DMPU), dimethylformamide (DMF), sulfolane, and mixtures thereof. The polar aprotic solvent S1 is preferably selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), sulfolane, and mixtures thereof. Solvent S1 may also contain chloroform or dichloromethane (DCM). The reaction for preparing the grafted PAE copolymer (P1) is more preferably carried out in sulfolane, DMAc, DMI, DMSO, and / or NMP.

[0087] The solvent S1 used to prepare the grafted PAE copolymer (P1) may be the same as the solvent S0 used to prepare the copolymer (P0).

[0088] The solvent S1 used to prepare the copolymer (P1) may be different from the solvent S0 used to prepare the copolymer (P0). For example, the solvent S1 used to prepare the copolymer (P1) may include or be NMP, and the solvent S0 used to prepare the copolymer (P0) may include or be sulfolane, DMSO, DMI, or DMAc, or vice versa.

[0089] Reaction condition (ii): The at least one free radical initiator is a thermal initiator that can initiate the polymerization of vinyl monomers, and can be a phenyl free radical initiator and / or an isobutyronitrile or isoheptyrinitrile free radical initiator. The free radical initiator can be selected from the group consisting of 2,2'-azobis(2-methylpropionitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), benzoyl peroxide, hydroperoxide, and any combination thereof. The at least one free radical initiator is preferably AIBN or ADVN, more preferably AIBN. For example, when AIBN is used as the free radical initiator, AIBN decomposes partially due to the strong N-N triple bond formed and partially due to the relatively stable radicals that are generated: [ka]

[0090] Typically, about 0.1 to 1 wt. % of the free radical initiator (e.g., AIBN) is used, based on the weight of the vinyl monomer. Generally, a larger amount of the free radical initiator (e.g., AIBN) relative to the weight of the vinyl monomer will decrease the molecular weight of the resulting PVP polymer P2. Therefore, up to 10 wt. % of the free radical initiator (e.g., AIBN) can be used to produce short polymer chains of the PVP polymer P2.

[0091] It is preferred to use all of the free radical initiator at once to start the reaction, however, the free radical initiator can also be fed gradually to the reaction system as needed.

[0092] Reaction conditions (iii): The temperature of the reaction for preparing the grafted PAE copolymer (P1) preferably varies from room temperature to 150°C, or more preferably from 35°C to 100°C, and even more preferably from 50°C to 80°C.

[0093] Reaction condition (iv): "Crosslinking" in the context of reaction condition (iv) refers to crosslinking between different molecules of PAE copolymer (P1) and / or (P0), between different molecules of vinyl polymer P2 and / or between molecules of PAE copolymer and molecules of vinyl polymer P2. The absence of crosslinking conditions preferably includes the absence of a crosslinking agent, the absence of the use of radiation during the reaction and / or the absence of a radiation initiator.

[0094] To avoid crosslinking during the reaction, the reaction is preferably carried out in the absence of a crosslinking agent, such as a polyfunctional vinyl compound containing at least two C=C double bonds. Alternatively or additionally, the reaction may exclude the use of high-energy radiation such as gamma rays and electron beams, or low-energy radiation such as UV and plasma radiation. The reaction preferably excludes the use of any radiation initiator, such as a UV radiation initiator.

[0095] The amount of grafted PAE copolymer (P1) at the end of the free radical reaction may be at least 10 wt. %, for example at least 15 wt. %, at least 20 wt. %, or at least 30 wt. %, based on the total weight of grafted PAE copolymer (P1) and solvent S1.

[0096] At the end of the free radical reaction, the reaction mixture may be cooled to terminate the free radical reaction.

[0097] After the reaction mixture has cooled, most of the solvent S1 can be distilled off from the reaction mixture under subatmospheric pressure, for example, at least 50 wt. %, preferably at least 60 wt. %, and more preferably 70 wt. % to about 80 wt. % of the solvent S1 present in the cooled reaction mixture at the end of the reaction is removed by distillation.

[0098] The grafted PAE copolymer (P1) is separated from other components of the reaction mixture (e.g., free poly(vinylpyrrolidone), unreacted radical initiator, fragments of the radical initiator, unreacted vinylpyrrolidone) to obtain a purified copolymer (P1). Separation preferably includes coagulation and one or more washings.

[0099] Coagulation can be used to precipitate the grafted PAE copolymer (P1) in a non-solvent or anti-solvent, thus forming solid particles of the grafted PAE copolymer (P1), to separate it from other components that remain in solution with the remainder of the solvent S1. The non-solvent or anti-solvent can comprise at least 50% by weight, preferably at least 60% by weight, of ethyl acetate, methyl acetate, acetone, butanone, and / or a C1-C5 alcohol. The non-solvent or anti-solvent can consist of ethyl acetate, methyl acetate, acetone, butanone, and / or a C1-C5 alcohol, such as methanol, ethanol, n-propanol, isopropanol, or butanol.

[0100] The precipitate of grafted PAE copolymer (P1) can be subjected to one or more washes with a wash liquid to further remove free (or unbound) PVP and / or unreacted vinylpyrrolidone monomer and / or free radical initiator. The wash liquid is preferably water and / or a C1-C5 alcohol (e.g., methanol, ethanol, n-propanol, isopropanol). The wash liquid (e.g., water) is preferably at a temperature of at least 50°C, or at least 60°C, or at least 65°C. The wash liquid should be at a temperature not exceeding its boiling point. The temperature of the wash liquid is preferably at most 90°C, or at most 85°C, or at most 80°C, or at most 75°C. The wash liquid is more preferably water at a temperature of 60°C to 80°C, or at most 65°C to 75°C. The presence of free PVP can be monitored by FTIR in the used wash liquid after each wash, and the wash process is repeated until free PVP is no longer detected in the used wash liquid.

[0101] The purified copolymer (P1) can then be dried, preferably under vacuum, generally at a temperature of about 50°C to 120°C, preferably about 80°C to 120°C, more preferably about 90°C to 120°C, and even more preferably about 90°C to 110°C.

[0102] The dried purified grafted PAE copolymer (P1) can be used to prepare articles as described herein, such as fibers, films or membranes.

[0103] In an alternative embodiment, the grafting reaction can be carried out as a finishing technique for shaped articles, such as films, membranes, sheets, and / or fabrics, containing the PAE copolymer (P0). In such cases, there can be an initial step of forming an article containing the PAE copolymer (P0). The article can be made essentially of the PAE copolymer (P0), or it can contain the PAE copolymer (P0) and other polymers different from the PAE copolymer (P0) as described herein. The method can then include contacting the shaped article with a solution of vinylpyrrolidone monomer and a free radical initiator to allow controlled modification of the PAE copolymer (P0) in the shaped article by covalent immobilization of the grafted PVP polymer P2 to a desired level. After the grafting reaction is complete, the article is subjected to washing to remove free PVP polymer and, if any, unreacted vinyl monomer and / or unreacted free radical initiator. This method embodiment may avoid possible film formation problems with the grafted copolymer (P1) and may allow for the removal of unreacted monomers / radicals or unbound PVP from a shaped article now containing the grafted PAE copolymer (P1) with the grafted PVP polymer P2.

[0104] Side-chain allyl / vinylene-functionalized polyarylether copolymer (P0) Side-chain allyl / vinylene functionalized polyarylether copolymers (P0) consist of two types of repeating units (R P0 ) and (R* P0 ), one type contains a functionalized repeating unit (R*) with two pendant allyl / vinylene side chains that are reactive. P0 )

[0105] PAE copolymer (P0) - at least 50 mol % in total of sulfone repeat units (R P0a ) and functionalized sulfone repeating units (R*) of formula (N0) P0a ): [ka] Or, - at least 50 mol % in total of ketone repeat units (R P0b ) and functionalized ketone repeating units (R*) of formula (N0′) P0b ): [ka] Including, During the ceremony, - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4, preferably i=0; - in formula (M1), T represents a bond, -C(CH3)2-; -SO2-; -CH2-; -O-; -S-; -C(O)-; -C(CF3)2-; -C(=CCl2)-; -C(CH3)(CH2CH2COOH)-; -N=N-; and -R a C=CR b -(where each R a and R b are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy, or C6-C18 aryl group; m is an integer of 1 to 6; -(CH2) m -and-(CF2) m -; a linear or branched, aliphatic divalent radical of up to 6 carbon atoms; and combinations thereof; T is preferably selected from the group consisting of a bond, -C(CH3)2-, and -SO2-; - G P is expressed by the following formula (G P1 ), (G P2 ) and (G P3 ): [ka] (In the formula, - Group G Pwherein W is selected from the group consisting of a bond, —SO—, —C(CH)—, and any combination thereof, preferably selected from —C(CH)— and / or —SO— or selected from —C(CH)— and / or a bond; - Group G P wherein each k is independently 0 or an integer of 1 to 4, preferably k=0, 1, 2, or 3, more preferably k=0. selected from the group consisting of at least one of: where the sulfone repeating unit (R P0a ) / Repeating unit (R* P0a ) or ketone repeating units (R P0b ) / Repeating unit (R* P0b ) is at least 1 / 5 and at most 100 / 1.

[0106] The PAE copolymer (P0) comprises functionalized sulfone repeating units (R*) of formula (N0): P0a ) or consisting solely of functionalized ketone repeat units (R*) of formula (N0′) P0b ) are excluded.

[0107] A particular embodiment of the present invention is a compound having a total of at least 50 mole % of ketone repeat units (R P0b ) and functionalized ketone repeating units (R*) of formula (N0′) P0b ) and amorphous PAEK copolymer (P0).

[0108] Sulfone repeating unit (R P0a ) / Repeating unit (R* P0a ) or ketone repeating units (R P0b ) / Repeating unit (R* P0b The molar ratio of sulfone repeat units (R ) can be at least 1 / 5, at least 1 / 4, at least 1 / 3, at least 1 / 2, or at least 1 / 1. P0a ) / Repeating unit (R* P0a ) or ketone repeating units (R P0b ) / Repeating unit (R* P0bThe molar ratio of sulfone repeat units (R ) in the PAE copolymer (P0) can be at most 100 / 1, at most 50 / 1, at most 30 / 1, at most 25 / 1, or at most 22 / 1. P0a ) / Repeating unit (R* P0a ) or ketone repeating units (R P0b ) / Repeating unit (R* P0b ) may be preferably 1 / 4 to 50 / 1, more preferably 1 / 3 to 40 / 1 or 1 / 3 to 30 / 1, more preferably 1 / 2 to 30 / 1, 1 / 2 to 25 / 1, 1 / 2 to 22 / 1, or 1 / 1 to 22 / 1.

[0109] The PAE copolymer (P0) is a copolymer in which k is a group G P may be such that it is zero at

[0110] In some embodiments, the PAES copolymer (P0) having sulfone repeat units of formula (M1) and (N0) may further comprise a group G P In the same PAES copolymer (P0), W can be -C(CH3)2- and / or -SO2-. P may be -C(CH3)2- in some of the groups G P However, preferably, in the same PAES copolymer (P0), W is -SO2- in all groups G P and is either -SO2- or -C(CH3)2-.

[0111] In another embodiment of the PAEK copolymer (P0) having ketone repeat units of formula (M2) and (N0′), P1 )~(G P3 ) any group G P In the same PAEK copolymer (P0), W is preferably a bond and / or —C(CH3)2—. P may be -C(CH3)2- in some of the groups G PHowever, preferably, in the same PAEK copolymer (P0), W is a bond between all groups G P and is either a bond or -C(CH3)2-.

[0112] The PAE copolymer (P0) can be such that each R1 is independently selected from the group consisting of a C1-C12 moiety optionally containing one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.

[0113] In the PAE copolymer (P0), i is preferably zero for each R1 (meaning that the phenyl ring is unsubstituted).

[0114] In another embodiment, the PAES copolymer (P0) having sulfone repeat units of formulae (M1) and (N0) may be such that in some of the sulfone repeat units of formulae (M1) and (N0), some R1 are selected from sulfonic acid groups; alkali or alkaline earth metal sulfonate groups; and / or alkylsulfonate groups, and the corresponding i is 1, while in other sulfone repeat units of formulae (M1) and (N0), i=0 (i.e., the phenyl ring is not substituted). Such phenyl rings optionally substituted with R1 and for which i=1 are preferably linked to the -SO2 linking group of the sulfone repeat unit.

[0115] Alternatively, the PAEK copolymer (P0) having ketone repeat units of formulae (M2) and (N0′) may be such that in some ketone repeat units of formulae (M2) and (N0′), some R1 are selected from sulfonic acid groups; alkali or alkaline earth metal sulfonate groups; and / or alkylsulfonate groups, and the corresponding i is 1, while in other ketone repeat units of formulae (M2) and (N0′), i=0 (i.e., the phenyl ring is unsubstituted). Such phenyl rings optionally substituted with R1 and for which i=1 are preferably linked to the —C(O)— linking group of the ketone repeat units.

[0116] The PAE copolymer (P0) has a weight average molecular weight M of at least 20 kDa, preferably at least 30 kDa or at least 35 kDa, more preferably at least 40 kDa or at least 45 kDa, and even more preferably at least 50 kDa. w The copolymer (P0) has a weight average molecular weight M of at most 200 kDa, preferably at most 180 kDa or at most 160 kDa, more preferably at most 140 kDa or at most 120 kDa, even more preferably at most 100 kDa. w The copolymer (P0) has a weight average molecular weight M of from 20 kDa to a maximum of 200 kDa, preferably from 30 kDa to a maximum of 160 kDa, more preferably from 60 kDa to a maximum of 100 kDa. w The M of the PAE copolymer (PO) w is preferably measured by GPC Method 2 provided in the Examples.

[0117] The PAE copolymer (P0) is soluble in polar aprotic solvents, preferably solvent S1 described herein, and more preferably soluble in NMP, DMAc, DMI, DMSO, sulfolane, or mixtures thereof.

[0118] Amorphous PAES copolymer (P0) PAE copolymer (P0) is a sulfone-based repeating unit (R P0a) and functionalized repeating units (R* P0a ), it can be referred to as a "PAES" copolymer (P0).

[0119] The PAES copolymer (P0) may have a Tg in the range of 130 to 260°C, preferably 160 to 250°C, more preferably 170 to 240°C, as measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0120] The PAES copolymer (P0) may comprise a total of at least 55 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 repeat units (R P0a ) and (R* P0a The PAES copolymer (P0) may contain the repeating unit (R P0a ) and (R* P0a ) can consist essentially of

[0121] The repeating unit (R P0a ) / Repeating unit (R* P0a ) is the molar ratio of - at least 1 / 4, at least 1 / 3, at least 1 / 2, at least 1 / 1, and / or - Maximum 50 / 1, Maximum 40 / 1, Maximum 30 / 1, Maximum 25 / 1 or Maximum 22 / 1 It could be.

[0122] The repeating unit (R P0a ) / Repeating unit (R* P0a ) may be 1 / 4 to 50 / 1, preferably 1 / 3 to 40 / 1 or 1 / 3 to 30 / 1, more preferably 1 / 2 to 30 / 1, 1 / 2 to 25 / 1, 1 / 2 to 22 / 1, or 1 / 1 to 22 / 1.

[0123] The PAES copolymer (P0) is a copolymer of repeating units (R P0a ), T may be selected from the group consisting of a bond, —SO—, —C(CH)—, and any combination thereof. The PAES copolymer (P0) may, for example, have a repeating unit (R P0a ) and other repeating units where T is -SO2- (R P0a ) may be included.

[0124] Preferred repeating units (R P0a ) is a repeating unit (R P1a and may be of formula (M1a), (M1b), or (M1c), as shown above for - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; Each i is independently 0 or an integer from 1 to 4, preferably i=0.

[0125] The PAES copolymer (P0) is a copolymer of repeating units (R P0a ) is a repeating unit (R P1a ) and may be as shown above for formula (M1b').

[0126] Amorphous PAEK copolymer (P0) Another aspect of the present invention is that the PAE copolymer (P0) comprises a total of at least 55 mole % of ketone-based repeat units (R 2 ) of formula (M2), as defined above, based on the total number of moles of repeat units in the PAEK copolymer (P0). P0b ) and functionalized ketone-based repeating units (R*) of formula (N0′) P0b ), it is a "PAEK" copolymer (P0).

[0127] The PAEK copolymer (P0) may comprise a total of at least 55 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% of repeat units (R P0b ) and (R* P0b The PAEK copolymer (P0) may preferably comprise the repeating unit (R P0b ) and (R* P0b ) can consist essentially of

[0128] The PAEK copolymer (P0) is an amorphous polymer, meaning that the PAEK copolymer (P0) does not exhibit a melting point (Tm) as determined by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0129] The PAEK copolymer (P0) may have a Tg in the range of 90°C to 200°C, preferably 95°C to 160°C, more preferably 100°C to 150°C, as measured by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0130] The repeating unit (R P0b ) / Repeating unit (R* P0b ) is the molar ratio of - at least 1 / 4, at least 1 / 3, at least 1 / 2, at least 1 / 1, and / or - Maximum 50 / 1, Maximum 40 / 1, Maximum 30 / 1, Maximum 25 / 1 or Maximum 22 / 1 is.

[0131] The repeating unit (R P0b ) / Repeating unit (R* P0b ) may be 1 / 4 to 50 / 1, preferably 1 / 3 to 40 / 1, more preferably 1 / 3 to 30 / 1, 1 / 2 to 30 / 1, 1 / 2 to 25 / 1, or 1 / 2 to 22 / 1.

[0132] The preferred ketone repeating units (R P0b ) is a repeating unit (R P1b ) and may be of formula (M2a)

[0133] Preferred ketone repeat units (R*) in PAEK copolymer (P0) P0b ) is of formula (N0′), where i is 0 for each R1.

[0134] In some embodiments relating to a PAEK copolymer (P0) having ketone repeat units of formula (M2) and (N0′), P1 )~(G P3 ) any group G P In the same PAEK copolymer (P0), W is preferably a bond and / or —C(CH3)2—. P may be -C(CH3)2- in some of the groups G P However, preferably, in the same PAEK copolymer (P0), W is a bond between all groups G P and is either a bond or -C(CH3)2-.

[0135] PAEK copolymer (P0) consists of repeating units (R' P1b Other repeating units (R') such as those of the following formula (M2b) or (M2b') shown above for P0b In such cases, the PAEK copolymer (P0) may further comprise at most 20 mol %, at most 15 mol %, or at most 10 mol % of repeat units (R'), based on the total number of moles in the PEAK copolymer (P0). P0b The repeating unit (R') in the PAEK copolymer (P0) may be P0b The amount of ) should be such that the PAEK copolymer (P0) retains its amorphous state.

[0136] Preparation process of side-chain allyl / vinylene functionalized PAE copolymer (P0) The allyl / vinylene-functionalized PAE copolymer (P0) can be prepared by condensing at least one aromatic dihydroxy monomer (a1), at least one aromatic sulfone or ketone monomer (a2) containing at least two halogen substituents, and at least one allyl-substituted aromatic dihydroxy monomer (a3). The reaction mixture preferably contains at least the monomers (a1), (a2), and (a3). When the aromatic monomer (a2) is a dihalosulfone monomer, the PAE copolymer (P0) can be referred to as a "PAES" copolymer (P0). When the aromatic monomer (a2) is a dihaloketone monomer, the PAE copolymer (P0) can be referred to as a "PAEK" copolymer (P0).

[0137] The condensation to prepare the copolymer (P0) is preferably carried out in a reaction mixture comprising the monomers (a1), (a2), and (a3) ​​and at least one solvent S0. The solvent (S0) is, for example, a polar aprotic solvent 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-methyl-2-pyrrolidone (NMP), N-butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropyleneurea (DMPU), dimethylformamide (DMF), tetrahydrothiophene-1-monoxide, and mixtures thereof. The polar aprotic solvent SO is preferably selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), sulfolane, and mixtures thereof. Solvent SO may also include chloroform or dichloromethane (DCM). The reaction for preparing the PAE copolymer (PO) is more preferably carried out in sulfolane, DMI, DMSO, DMAc, and / or NMP.

[0138] The condensation to prepare the PAE copolymer (P0) can be carried out in the presence of at least one base selected from the group consisting of potassium carbonate (K2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), and sodium tert-butoxide. The base serves to deprotonate components (a1) and (a3) ​​during the condensation reaction.

[0139] The condensation to prepare the PAE copolymer (P0) may be carried out at a molar ratio [(a1)+(a3)] / (a2) of 0.9 to 1.1, for example 0.92 to 1.08 or 0.95 to 1.05.

[0140] The monomers (a3) ​​are at least 50% by weight, based on the total weight of the monomers (a3), of the following formula (G M1 ), (G M2 ) and (G M3 ): [ka] (In the formula, G M wherein W is selected from the group consisting of a bond, —C(CH3)2—, —SO2—, and any combination thereof, preferably selected from —C(CH3)2— and / or —SO2— or selected from —C(CH3)2— and / or a bond; G M wherein each k is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2, or 3, more preferably k=0. 2,2'-diallyldiol "G" selected from the group consisting of M " includes or consists of ".

[0141] The monomers (a3) ​​preferably represent at least 50% by weight, based on the total weight of the monomers (a3), of the following formula (G M4 ): [ka] (In the formula, the formula (G M4 ) in which W is a bond, -C(CH3)2- or -SO2-, and G M4 means that the compound is 2,2'-diallylbiphenol (daBP), 2,2'-diallylbisphenol A (daBPA), or 2,2'-diallylbisphenol S (daBPS). In a preferred embodiment, the compound of formula (G M4) in which W can be -C(CH3)2- or -SO2-, and G M4 is daBPA or daBPS. M4 ) W can be —C(CH3)2— or a bond, and G M4 is daBPA or daBP.

[0142] Monomer (a3) ​​may, for example, be at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or at least 99% by weight, based on the total weight of monomer (a3), of a compound of formula (G M1 ), (G M2 ), (G M3 ) and (G M4 ) 2,2'-diallyldiol G M In preferred embodiments, monomer (a3) ​​comprises at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of daBP, or daBPA, or daBPS, based on the total weight of monomer (a3).

[0143] To prepare the PAES copolymer (P0), monomer (a1) comprises at least 50% by weight of at least one diol selected from the group consisting of 4,4'-dihydroxybiphenyl (biphenol), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 4,4'-dihydroxydiphenyl sulfone (bisphenol S), and any combination thereof, based on the total weight of monomer (a1). Monomer (a1) may comprise, for example, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of at least one diol selected from 4,4'-biphenol, bisphenol A, or bisphenol S, based on the total weight of monomer (a1). Monomer (a1) preferably consists essentially of at least one diol selected from 4,4'-biphenol, bisphenol A, or bisphenol S.

[0144] To prepare the PAES copolymer (P0), the monomer (a2) is at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight, based on the total weight of the monomers (a2), of the following formula: [ka] (In the formula, - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4, preferably i=0 or 1; X and X' are independently a halogen selected from the group consisting of Cl and F, preferably X and X' are both Cl. The compound contains at least one 4,4-dihalodiphenol sulfone.

[0145] In some embodiments, at least one R 1 in the 4,4-dihalodiphenylsulfone is selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and its corresponding i is equal to 1.

[0146] For preparing the PAES copolymer (P0), the monomer (a2) preferably comprises 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, at least 95% by weight, or at least 99% by weight, based on the total weight of the monomers (a2), of 4,4'-dichlorodiphenyl sulfone (DCDPS), disulfonated 4,4'-dichlorodiphenyl sulfone (sDCDPS), 4,4'-difluorodiphenyl sulfone (DFDPS), or disulfonated 4,4'-difluorodiphenyl sulfone (sDFDPS), more preferably DCDPS and / or sulfonated disodium DCDPS, such as: [ka] Sulfonated DCDPS disodium [bis(4-chloro-3-sulfophenyl)sulfone disodium] Includes:

[0147] In some embodiments for preparing the PAES copolymer (P0), the monomer (a2) may comprise two or more 4,4-dihalodiphenyl sulfones. In particular, the monomer (a2) may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of a 4,4-dihalodiphenyl sulfone represented by the following formula: [ka] (In the formula, - in one dihalodiphenylsulfone, both X and X' are Cl or F, preferably X=X'=Cl and both i's are equal to 0; - in other dihalodiphenylsulfones, X and X' are both Cl or F, preferably X = X' = Cl; both i's are 1, and each R1 can be independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates. The compound may contain two kinds of 4,4-dihalodiphenyl sulfones:

[0148] Furthermore, in more specific embodiments for preparing the amorphous PAES copolymer (P0), monomer (a2) can comprise or consist essentially of at least 90% by weight or at least 95% by weight of a mixture of DCDPS and disulfonated DCDPS (sDCDPS), based on the total weight of monomer (a2). In such cases, monomer (a2) preferably contains more than 50 mol%, more than 60 mol%, more than 70 mol%, or more than 80 mol% DCDPS, based on the total number of moles of DCDPS and sDCDPS in monomer (a2).

[0149] To prepare the amorphous PAES copolymer (P0), the monomers (a1), (a2) and (a3) ​​of the reaction mixture are generally reacted simultaneously. The reaction is preferably carried out in one step. This means that the deprotonation of the monomers (a1) and (a3) ​​and the condensation reaction between the monomers (a1) + (a3) ​​and (a2) are carried out in a single reaction step without isolation of intermediate products.

[0150] To prepare the amorphous PAEK copolymer (P0), the monomer (a1) is 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, at least 95% by weight, or at least 99% by weight, based on the total weight of the monomers (a1), of the following formula: [ka] wherein each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; and each i is independently 0 or an integer from 1 to 4, preferably i=0 or 1. Contains diols.

[0151] Monomer (a1) for preparing PAEK copolymer (P0) may, for example, comprise at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% resorcinol, based on the total weight of monomer (a1). Monomer (a1) for preparing PAEK copolymer (P0) may preferably consist essentially of resorcinol.

[0152] To prepare the amorphous PAEK copolymer (P0), the monomer (a2) is 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, at least 95% by weight, or at least 99% by weight, based on the total weight of the monomers (a2), of the following formula: [ka] (In the formula, - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently 0 or an integer from 1 to 4, preferably i=0 or 1 Difluorodiphenyl ketones of the formula:

[0153] In some embodiments for preparing a PAEK copolymer (P0), the monomer (a2) may comprise two or more difluoroketones. In particular, the monomer (a2) may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of a difluoroketone represented by the following formula: [ka] (In the formula, - in one of 4,4'-difluorodiphenyl ketones, both i's are equal to 0; - other 4,4'-difluorodiphenyl ketones, where both i=1 and each R1 is independently selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates. The compound may contain two kinds of 4,4'-difluorodiphenyl ketones.

[0154] In an alternative embodiment for preparing the PAEK copolymer (P0), each R1 in 4,4'-difluorodiphenyl ketone is selected from the group consisting of alkali or alkaline earth metal sulfonates and alkyl sulfonates, and its corresponding i is equal to 1. In such a case, the monomer (a2) is preferably sulfonated 4,4'-difluorodiphenyl ketone disodium.

[0155] To prepare the amorphous PAEK copolymer (P0), the monomer (a2) preferably comprises or consists of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% of 4,4'-difluorobenzophenone (DFBP) and / or disulfonated 4,4'-difluorobenzophenone (sDFBP), based on the total weight of the monomer (a2). When the monomer (a2) comprises both DFBP and sDFBP, the monomer (a2) preferably contains more than 50 mol% of DFBP, based on the total number of moles of DFBP and sDFBP in the monomer (a2). The monomer (a2) preferably consists essentially of DFBP.

[0156] To prepare the PAE copolymer (P0), the monomers (a1), (a2) and (a3) ​​of the reaction mixture are generally reacted simultaneously. The reaction is preferably carried out in one step. This means that the deprotonation of the monomers (a1) and (a3) ​​and the condensation reaction between the monomers (a1) + (a3) ​​and (a2) are carried out in a single reaction step without isolation of intermediate products.

[0157] The condensation reaction can be carried out in a mixture of a polar aprotic solvent S0 and a cosolvent that forms an azeotrope with water. Examples of cosolvents that form azeotropes with water include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene. The cosolvent is preferably toluene or chlorobenzene. The azeotrope-forming cosolvent and the polar aprotic solvent S0 are typically used in a weight ratio of about 1:100 to about 1:1, preferably about 1:10 to about 1:1, and more preferably about 1:5 to about 1:1. Water is continuously removed from the reaction mass as an azeotrope with the azeotrope-forming cosolvent, thereby maintaining substantially anhydrous conditions during polymerization. The azeotrope-forming cosolvent, e.g., chlorobenzene or toluene, is typically removed from the reaction mixture by distillation, leaving the copolymer (P0) dissolved in the polar aprotic solvent after the water formed in the reaction has been removed.

[0158] The temperature of the reaction mixture for preparing the PAE copolymer (P0) is maintained at about 150°C to about 250°C, preferably about 165°C to about 250°C, for about 1 to 15 hours. When NMP or sulfolane is used as solvent S0, the preferred temperature of the reaction mixture can be about 180°C to about 220°C. When DMAc is used as solvent S0, the preferred temperature of the reaction mixture can be about 150°C to about 170°C.

[0159] Inorganic constituents, such as sodium chloride or potassium chloride or excess base, can be removed before or after isolation of the copolymer (P0) by suitable methods such as dissolution and filtration, sieving or extraction.

[0160] At the end of the condensation, the amount of copolymer (P0) is at least 30% by weight, for example at least 35% by weight or at least or at least 37% by weight or at least 40% by weight, based on the total weight of copolymer (P0) and polar aprotic solvent S0.

[0161] At the end of the condensation reaction, the copolymer (P0) is separated from the other components (salt, base, ...) to obtain a solution. For example, filtration can be used to separate the copolymer (P0) from the other components.

[0162] The solution containing the PAE copolymer (P0) can then be used directly in the process of the present invention to react the PAE copolymer (P0) with vinylpyrrolidone monomer to produce the graft PAE copolymer (P1) according to the present invention and described herein. Alternatively, the PAE copolymer (P0) can be recovered in solid form from the solvent S0 (used during condensation), for example, by coagulation or devolatilization of the solvent S0. The solid form of the PAE copolymer (P0) can be dissolved in the solvent S1 (the same as or different from S0) used to produce the PAE copolymer (P1).

[0163] The PAE copolymer (P0) is an intermediate product used for the preparation of the grafted PAE copolymer (P1) according to the invention.

[0164] Use of grafted PAE copolymer (P1) Another aspect of the present invention provides the use of a grafted PAE copolymer (P1) for preparing an article (or part thereof) as described herein.

[0165] Method of preparing the article Another aspect of the present invention provides a method for preparing an article (or part thereof) comprising the grafted PAE copolymer (P1).

[0166] The article may be formed from a solution containing the grafted PAE copolymer (P1).

[0167] When the article is a membrane or portion thereof, the method preferably includes phase inversion occurring in a liquid phase (eg, a precipitation bath) to form the membrane or portion thereof.

[0168] One aspect of the present invention relates to a method for producing an article comprising a grafted PAE copolymer (P1), the method comprising the following steps: - Method (a): Use of the grafted PAE copolymer (P1) in forming an article or part thereof; or - Method (b): contacting a preformed article comprising a PAE copolymer (P0) or a portion thereof with a vinyl monomer and a free radical initiator to form a graft PAE copolymer (P1) from the copolymer (P0). The method may include performing one of the following:

[0169] Regarding method (b), the preformed article can be prepared by a phase inversion technique that occurs in the liquid phase. Method (b) can further include the steps of preparing a polymer solution comprising the copolymer (P0) described herein and a polar solvent, processing the polymer solution into a preformed article or a part thereof, and contacting the preformed article or a part thereof with a non-solvent bath. This is particularly applicable when the preformed article or part thereof is a membrane, fiber, or film.

[0170] Articles containing grafted PAE copolymer (P1) Another aspect of the present invention provides an article (preferably a shaped article) comprising the grafted PEA copolymer (P1) according to the present invention.

[0171] The article comprising the grafted PAE copolymer (P1) may 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 or non-porous film); and a solution-processed monofilament.

[0172] The grafted PAE copolymer (P1) can be incorporated into an article having a polymeric surface. The article can have a polymeric surface, at least a portion of which will be in direct contact with an aqueous medium, such as water, aqueous solutions, biological fluids, and / or food, in its intended use setting. The polymeric surface can be an external or internal surface of the article. For example, a medical device has an external surface intended to be in direct contact with biological fluids, such as blood, plasma, or serum. Those skilled in the art will understand which surface is intended to come into contact with biological fluids or food, based on the intended use setting of the article.

[0173] As another example, the surface of the article can include a coating or film comprising the grafted PAE copolymer (P1) disposed on an underlying substrate. In such embodiments, the underlying substrate can be a structural element having a different composition than the grafted PAE copolymer (P1).

[0174] In embodiments in which the grafted PAE copolymer (P1) is in a film, the film can have an average thickness of from about 25 μm to about 1 mm.

[0175] The grafted PAE copolymer (P1) can be included on at least a portion of the surface of an article whose surface is intended to come into contact with biological fluids such as blood, plasma, or serum, or the grafted PAE copolymer (P1) can form all or substantially all of the article.

[0176] The shaped article comprising the grafted PAE copolymer (P1) may be a membrane, or part thereof, preferably selected from proton exchange membranes, membranes for bioprocessing (e.g., enzyme or cell culture filtration), membranes for medical filtration, e.g., hemodialysis membranes, membranes for food and beverage processing, membranes for water purification, membranes for wastewater treatment and membranes for industrial process separations involving aqueous media.

[0177] Among membranes, the grafted PAE copolymers (P1) according to the invention are particularly suitable for producing membranes intended for contact with aqueous media, which may include biological fluids such as blood, or food products such as beverages (e.g. fruit juices, milk, beer).

[0178] From a structural point of view, membranes comprising the grafted PAE copolymer (P1) can be provided in the form of flat structures (e.g., films or sheets), corrugated structures (such as corrugated sheets), tubular structures, or hollow fibers; with regard to pore size, a whole range of membranes (non-porous and porous, such as for microfiltration, ultrafiltration, nanofiltration, and reverse osmosis) can be advantageously produced using the grafted PAE copolymer (P1); the pore distribution can be isotropic or anisotropic.

[0179] Among the applications of use, mention may be made of healthcare applications, in particular medical applications, where shaped articles comprising the grafted PAE copolymer (P1) can be advantageously used in single-use and reusable instruments and devices.

[0180] Among the applications of use, mention may be made of fuel cell applications, in which the grafted PAE copolymer (P1) can be advantageously used in the proton exchange membrane.

[0181] The article may comprise the grafted PAE copolymer (P1) and, optionally, another sulfone polymer different from the copolymer (P1), such as a PAE copolymer (P0), PSU, PES, PPSU, in an amount ranging from 1 to 99% by weight, for example, from 2 to 98% by weight, from 3 to 97% by weight, or from 4 to 96% by weight, based on the total weight of the polymers. In such cases where the article comprises the copolymer (P1) and another sulfone polymer, such as a PAE copolymer (P0), PSU, PES, and / or PPSU, the weight fraction of the copolymer (P1), based on the total weight of the copolymer (P1) and the other sulfone polymers 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.

[0182] As used herein, polyethersulfone (PES) refers to a polymer having 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 a compound of formula (J): [ka] (mol % is based on the total moles of repeat units in the PES polymer) PES PES refers to any polymer containing . PES can be prepared by known methods and is available, among others, as VERADEL® PESU from Solvay Specialty Polymers USA, LLC.

[0183] As used herein, polysulfone (PSU) refers to 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 a compound represented by formula (K): [ka] (mol % is based on the total moles of repeat units in the PSU polymer) PSU PSU may be produced by known methods and is available, among others, as Udel® PSU from Solvay Specialty Polymers USA, LLC.

[0184] As used herein, polyphenylsulfone (PPSU) refers to 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 a compound represented by formula (L): [ka] (mol % is based on the total moles of repeat units in the PPSU polymer) PPSU PPSU can be prepared by known methods and is available, among others, as RADEL® PPSU from Solvay Specialty Polymers USA, LLC.

[0185] Membranes, fibres or films (as articles) The article can be a film, fiber, membrane, or portion thereof.

[0186] A particular embodiment of the article (preferably a shaped article) relates to a membrane comprising the grafted PAE copolymer (P1), which can be used for proton exchange or for purifying biological fluids, such as water, food, or blood.

[0187] An embodiment of the membrane according to the present invention relates to a proton exchange membrane comprising a grafted PAE copolymer (P1).

[0188] Another embodiment of the membrane according to the invention relates to a purification membrane comprising the grafted PAE copolymer (P1), such as for purifying water, food or biological fluids such as blood.

[0189] The membrane may be a microporous membrane, which can be characterized by the average pore size and the porosity, ie, the percentage of the total membrane that is porous.

[0190] The membrane may have a weight porosity (%) of 20-90% and contain pores, where at least 90% by volume of the pores have an average pore size of less than 5 μm. The weight porosity of a membrane is defined as the volume of pores divided by the total volume of the membrane.

[0191] Membranes with a uniform structure throughout their thickness are generally known as symmetric membranes, while membranes with pores not uniformly distributed throughout their thickness are generally known as asymmetric membranes. Asymmetric membranes are characterized by a thin selective layer (0.1-1 μm thick) and a thick, highly porous layer (100-200 μm thick) that serves as a support and has little effect on the separation properties of the membrane.

[0192] The membrane can be in the form of a flat sheet or in the form of a tube.

[0193] The membrane may be formed using multiple films or multiple fibers.

[0194] Based on their dimensions, tubular membranes are classified into tubular membranes with a diameter greater than 3 mm, capillary membranes with a diameter between 0.5 mm and 3 mm, and hollow fibers with a diameter less than 0.5 mm, otherwise called hollow fibers.

[0195] Hollow fibers are particularly advantageous in applications where a compact module with high surface area is required.

[0196] Membranes, fibers or films according to the present invention can be made using any of the conventionally known membrane, fiber or film preparation methods, for example, by solution casting methods.

[0197] The membranes, fibers or films according to the present invention can be prepared by a phase inversion method occurring in a liquid phase, said method comprising the following steps: preparing a polymer solution comprising the copolymer (P1) described herein and a polar solvent, processing said polymer solution into a film; and contacting said film with a non-solvent bath.

[0198] The membrane, fiber, or film may further comprise at least one polymer different from the grafted PAE copolymer (P1) described herein. For example, the membrane, fiber, or film may further comprise at least one additional polymer selected from the group consisting of the PAE copolymer (P0), another sulfone polymer such as polysulfone (PSU), polyethersulfone (PES), poly(biphenylethersulfone) (PPSU), polyphenylene sulfide (PPS), poly(aryletherketone) (PAEK) such as poly(etheretherketone) (PEEK), poly(etherketoneketone) (PEKK), copolymers of poly(etherketone) (PEK) or PEEK with poly(diphenyletherketone) (PEEK-PEDEK copolymer), polylactide (PLA), polyetherimide (PEI), polycarbonate (PC), polyphenylene oxide (PPO), polyvinylpyrrolidone (PVP), and / or polyethylene glycol (PEG). If the membrane, fiber or film further comprises at least one polymer different from the grafted PAE copolymer (P1), at least the different polymer preferably excludes PVP.

[0199] More preferably, when the membrane, fiber or film further comprises at least another polymer different from the copolymer (P1), such different polymer may be selected from the group consisting of PAE copolymer (P0), PSU, PES, PPSU, PC, PPO, PEI, PLA, and any combination thereof.

[0200] The membrane, fiber or film may comprise the grafted PAE copolymer (P1) of the present invention in an amount of at least 1 wt.%, or at least 2 wt.%, at least 3 wt.%, at least 4 wt.%, at least 5 wt.%, at least 6 wt.%, or at least 7 wt.%, or at least 8 wt.%, based on the total weight of the polymer, and / or may comprise the copolymer (P1) described herein in an amount of more than 50 wt.%, for example more than 55 wt.%, more than 60 wt.%, more than 65 wt.%, more than 70 wt.%, more than 75 wt.%, more than 80 wt.%, more than 85 wt.%, more than 90 wt.%, more than 92 wt.%, or more than 95 wt.%, based on the total weight of the polymer.

[0201] According to an embodiment, the membrane, fiber or film may comprise the grafted PAE copolymer (P1) and, optionally, another sulfone polymer different from the copolymer (P1), such as copolymer (P0), PSU, PES, PPSU, in an amount ranging from 1 to 99 wt.%, for example, from 2 to 98 wt.%, from 3 to 97 wt.%, or from 4 to 96 wt.%, based on the total weight of the polymers. When the membrane, fiber or film comprises the grafted copolymer (P1) and another sulfone polymer, such as PSU, PES and / or PPSU, the weight fraction of the grafted copolymer (P1), based on the total weight of the copolymer (P1) and the other sulfone polymers in the membrane, fiber or film, is at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, and / or at most 99 wt.%, or at most 98 wt.%, or at most 96 wt.%, or at most 95 wt.%, or at most 90 wt.%.

[0202] The membrane, fiber or film may further comprise at least one non-polymeric component such as a solvent, a filler, a lubricant, a release agent, an antistatic agent, a flame retardant, an antifogging agent, a matting agent, a pigment, a dye and an optical brightener.

[0203] Suitable examples of methods for forming membranes from polyarylethersulfone polymers are described in U.S. Patent Application Publication No. 2019 / 054429 A1 (Solvay Specialty Polymers USA), which is incorporated herein by reference.

[0204] Polymer solutions (SP) for preparing membranes, fibers or films Another aspect of the present invention is a polar organic solvent [solvent (S SP The present invention relates to a polymer solution (SP) for preparing a membrane, fiber or film, comprising a grafted PAE copolymer (P1) in a copolymer (P1).

[0205] The polymer solution (SP) may further comprise at least one additional polymer different from the grafted PAE copolymer (P1) described herein, such as another sulfone polymer, for example copolymer (P0), PSU, PES, PPSU; PPS, PAEK, such as PEEK, PEKK, PEK, or PEEK-PEDEK copolymer; PPO; PLA; PEI; PC; PVP; and / or PEG. The polymer solution (SP) preferably excludes PVP.

[0206] The total concentration of the grafted PAE copolymer (P1) and optional additional polymers in the polymer solution (SP) can be at least 8% by weight, or preferably at least 10% by weight, based on the total SP weight, and / or at most 70% by weight, or at most 60% by weight, or at most 50% by weight, or at most 40% by weight, or at most 30% by weight, based on the total polymer solution weight. Concentrations of all polymers in the SP in the range of 10 to 25% by weight, more preferably 10 to 22% by weight, based on the total SP weight, are particularly advantageous.

[0207] Solvent in SP (S SP ) may be at least 20% by weight, preferably at least 30% by weight, based on the total SP weight, and / or at most 70% by weight; preferably at most 65% by weight; more preferably at most 60% by weight, based on the total SP weight.

[0208] Solvent in SP (S SP ) can be selected from the list of solvents provided for solvent S1 described above. Preferably, the solvent (S) in the polymer solution (SP) SP ) is N,N'-dimethylacetamide (DMAc), sulfolane, or NMP, and is particularly suitable for preparing membranes or films.

[0209] Exemplary solvents (S) that may be used alone or in combination in the polymer solution (SP) are: SP ) are described in U.S. Patent Application Publication No. 2019 / 054429A1 (Solvay Specialty Polymers Italy) (particularly the solvents described in paragraphs

[0057] to

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

[0210] The polymer solution (SP) may contain additional ingredients such as nucleating agents, fillers, etc.

[0211] Method for purifying biological fluids A further aspect of the present invention may be directed to a purification process, which comprises at least a filtration step through a membrane, fiber or film comprising the grafted PAE copolymer (P1) described herein.

[0212] Preferably, the purification method is for purifying a human biological fluid, preferably a blood product such as whole blood, plasma, fractionated blood components or mixtures thereof, and it is carried out in an extracorporeal circuit. The extracorporeal circuit for carrying out the method comprises at least one filtration device (or filter) comprising at least one membrane, fiber or film as described above.

[0213] As intended herein, methods of blood purification through extracorporeal circuits include hemodialysis (FD), hemofiltration (HF), plasma diafiltration (HDF), and hemoconcentration by diffusion. In HF, blood is filtered by ultrafiltration, while in HDF, blood is filtered by a combination of FD and HF.

[0214] Blood purification methods through extracorporeal circuits are typically performed by hemodialyzers, i.e., devices designed to perform either FD, HF, or HFD. In such methods, blood is filtered from waste solutes and waste fluids, such as urea, potassium, creatinine, and uric acid, thereby providing blood that is free of waste solutes and waste fluids.

[0215] Typically, a hemodialyzer for performing a blood purification method comprises a cylindrical bundle of hollow fibers of membranes, said bundle having two ends, each of which is fixed in a so-called potting compound, which is usually a polymeric material that acts as an adhesive to hold the bundle ends together. Potting compounds are known in the art and include polyurethanes, among others. By applying a pressure gradient, blood is pumped through the membrane bundle via blood ports, and the filtrate product ("dialysate") is pumped through the space surrounding the fibers.

[0216] The present invention will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and not intended to limit the scope of the invention. [Example]

[0217] raw materials K2CO3 (potassium carbonate), available from Armand products daBPA (2,2'-diallylbisphenol A), available from Sigma-Aldrich, USA DCDPS (4,4'-dichlorodiphenyl sulfone), available from Solvay Specialty Polymers DHDPS (4,4'-dihydroxydiphenyl sulfone or bisphenol S) available from Konishi Chemical Industry, Japan DFBP (4,4'-difluorobenzophenone), available from Sigma-Aldrich, USA Resorcinol, available from Sigma-Aldrich, USA DMAc (dimethylacetamine), available from Sigma-Aldrich, USA NMP (2-methylpyrrolidone), available from Sigma-Aldrich, USA Sulfolane, available from Chevron Phillips AIBN (azobisisobutyronitrile), available from Sigma-Aldrich, USA Vinylpyrrolidone (VP), available from Sigma-Aldrich, USA Methanol, available from Sigma-Aldrich, USA Ethyl acetate, available from Sigma-Aldrich, USA

[0218] Test Method GPC Method 1 for Determining Molecular Weight (Mn, Mw) Equipment: Waters 515 pump, Waters 717plus autosampler, Waters 2487 absorbance detector, Waters 2414 refractive index detector

[0219] Columns: Two Agilent PLgel MiniMix-D, 5um, 250 x 4mm (part number PL1510-5504) + Agilent Mix Guard, 5um, 50 x 4.6mm (part number PL1510-1504)

[0220] Column temperature: 45C

[0221] Mobile phase: N,N-dimethylacetamide + 0.1M LiBr

[0222] Flow rate: 0.3ml / min

[0223] Injection amount: 20ul

[0224] UV detection: 270 nm

[0225] RI detection: + polarity

[0226] Calibration: Agilent EasiCal PS-2 GPC / SEC Standards (Part# PL2010-0601). Dissolve the standards in the mobile phase.

[0227] Sample preparation: Weigh 30 mg of sample into a 20 ml glass vial with a PTFE-lined cap. Add 5 ml of DMAC mobile phase. Heat to 105°C with stirring until complete dissolution. Filter through a 0.2 um PTFE syringe filter into a 4 ml autosampler vial.

[0228] GPC Method 2 for Determining Molecular Weight (Mn, Mw) Molecular weights were determined by gel permeation chromatography (GPC) using methylene chloride as the mobile phase. Two 5μ mixed D columns with guard columns from Agilent Technologies were used for the separation. A 254 nm UV detector was used to obtain the chromatograms. 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 12 narrow molecular weight polystyrene standards (peak molecular weight range: 371,000–580 g / mol). The number average molecular weight, Mn, weight average molecular weight, Mw, and higher average molecular weight, Mz, are reported.

[0229] Thermogravimetric analysis (TGA) TGA experiments were performed using a TA Instrument TGA Q500. TGA measurements were obtained by heating the samples under nitrogen from 20° C. to 800° C. at a heating rate of 10° C. / min.

[0230] 1 H NMR 1 H NMR spectra were measured on a 400 MHz Bruker spectrometer using TCE as the deuterated solvent, and all spectra are referenced to residual protons in the solvent.

[0231] DSC DSC was used to measure glass transition temperatures (Tg) and melting points (Tm), if present. DSC experiments were performed using a TA Instrument Q100. DSC curves were recorded by heating, cooling, reheating, and then recooling the sample from 25°C to 320°C at heating and cooling rates of 20°C / min. All DSC measurements were taken under a nitrogen purge. Reported Tg values ​​(and Tm values, if present) were provided using the second heating curve, unless otherwise noted.

[0232] elemental analysis The elemental composition of some polymer samples was measured using a Perkin Elmer 2400CHN elemental analyzer. The polymer samples were combusted according to the classical Pregl-Dumas method. The resulting combustion gases were completely converted to CO2, H2O, N2, and SO2. The gases were then separated by frontal chromatography. As the gases eluted, they were measured with a thermal conductivity detector, and the quantitative amounts of carbon, hydrogen, nitrogen, and sulfur were determined.

[0233] FTIR Because vinylpyrrolidone is a liquid and highly water-soluble, and because of the thorough washing, filtration, and drying of the graft copolymer (P1) sample, no free vinyl monomer should be detectable in the dried sample of graft copolymer (P1). Nevertheless, free residual vinyl monomer can be detected by FTIR using a Bruker Optics Vertex 70 FTIR Bench equipped with an MIR source. Spectra were obtained in absorption mode across a diamond ATR crystal.

[0234] The procedure for FTIR analysis of the reference sample was as follows: · Fresh 18 megaohm water was used to establish a background spectrum; · A drop of polymer sample was applied to the ATR crystal to ensure its complete coverage; · 32 repeated scans of the spectrum were collected to produce an average response; The following corrections were applied to each spectrum: - Extended ATR correction for diamonds - Atmospheric correction for moisture and CO2 - Baseline correction, which normalizes all spectra together based on their max-min peak values Overlaid normalized spectra; and 1641cm -1 The peak heights at the respective points were compared visually.

[0235] I. Preparation of Side-Chain Allyl / Vinylene-Functionalized PAES Copolymer (P0-A) PAES copolymer (P0-A) was prepared according to Scheme 1.

[0236] Repeating unit (R P0a ), while diallyl bisphenol A (daBPA) and DCDPS were used to form the repeating unit (R* P0a The repeating unit (R*) in the side-chain allyl / vinylene functionalized polymer (PO-A) was P0a ) is the target mole percent of the repeat unit (R P0a ) / Repeating unit (R* P0a ) was 9.1 mol % to achieve a molar ratio of the main repeating unit (R P0a The value "n" in Scheme 1 for the three exemplified functionalized repeat units (R*) should be about 90.9 mole %. P0a The combined value for m1+m2+m3 should be 9.1 mole %, said mole % being based on the total number of moles of repeat units in the PAES copolymer (P0-A).

[0237] The polymerization was carried out in a 20 L glass reaction vessel equipped with an overhead stirrer, nitrogen inlet, and overhead distillation apparatus. The monomers DCDPS (2030.2 g; 7.07 mol), DHDPS (1594.2 g; 6.37 mol), and daBPA (197.25 g; 0.64 mol) were added to the vessel first, followed by potassium carbonate (977.14 g; 7.07 mol) and NMP (4018.9 g). The reaction mixture was heated from room temperature to 190 °C using a 10 °C / min temperature ramp. The reaction mixture temperature was maintained for approximately 6 hours, depending on the viscosity of the solution. Excess DCDPS (140.7 g) was added, allowing DCDPS to end-cap the polymer for an additional 30 minutes, and then the reaction was terminated by turning off the heat. The reaction mixture was filtered and coagulated into methanol. The polymer was then washed with methanol and water, washed again with methanol, and dried at 110 °C.

[0238] Characterization of PAES copolymer (P0-A) GPC method 2: M w = 58566 g / mol, M n = 21327 g / mol, PDI = 2.75 TGA: 488℃ DSC: Tg = 218°C 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1–6.4 ppm, indicating the incorporation of 2,2′-diallylbisphenol A monomer in the polymer (P0-A). 1 The estimated olefin content measured by H NMR was 8.97 mol %, which corresponds to a repeat unit (R P0a ) / Repeating unit (R* P0a The actual molar ratio of the main repeating unit (R P0a The actual value of "n" in Scheme 1 for ) was 91.03 mol %.

[0239] II. Preparation of grafted PAES copolymer (P1-A) by free radical reaction The grafted PAES copolymer (P1-A) was prepared according to Scheme 2. The main repeating unit (R P1a The actual value of "n" in Scheme 2 for (P0-A) was 91.03 mol%, the same as for the PAES copolymer (P0-A).

[0240] The reaction was carried out in a 2 L glass reaction vessel equipped with an overhead stirrer and nitrogen inlet. A sample of the side-chain allyl / vinylene-functionalized PAES copolymer (P0-A) (64 g, containing 0.024 moles of olefinic double bonds) and vinylpyrrolidone (184.32 g; 1.658 moles) were added to the reactor, and the mixture was dissolved in anhydrous NMP (1727 g) and heated to 65 °C. The molar ratio of the number of moles of vinylpyrrolidone monomer to the number of moles of functionalized repeat units in the PAES copolymer (P0-A) was 69.1. The reaction was purged with nitrogen for 30 minutes, and then AIBN (2.34 g) was added in one portion. The reaction was allowed to proceed at 65 °C for 12 hours. After 12 hours, the reaction mixture was cooled, and approximately 70-80% of the solvent was distilled off under reduced pressure. The copolymer (P1-A) was isolated by coagulation in ethyl acetate and repeatedly washed with hot water until no free polyvinylpyrrolidone was detected in the washings by FTIR. The purified copolymer (P1-A) was dried under high vacuum at 100°C.

[0241] Characterization of graft polyarylethersulfone copolymer (P1-A) GPC method (RI detector): Mn=80752 g / mol, Mw=672825 g / mol, PDI=8.3 DSC: Tg = 209°C TGA: 414℃

[0242] The mole % of PVP in the copolymer (P1-A) was estimated using the following formula:

number

[0243] 1 H NMR:56.2wt%PVP

[0244] III. Preparation of Side-Chain-Allyl / Vinylene-Functionalized PAEK Copolymer (P0-B) PAEK copolymer (P0-B) was prepared according to Scheme 3.

[0245] Repeating unit (R P0b ), while 4,4'-difluorobenzophenone (DFBP) and resorcinol were used to generate the repeating unit (R* P0b Diallyl bisphenol A (dABPA) and DFBP were used to prepare the repeating unit (R*) in the side-chain allyl / vinylene functionalized polymer (PO-B). P0b ) is the target mole percent of the 2:3 repeat unit (R P0b ) / Repeating unit (R* P0b ) was 60 mol % to achieve a molar ratio of the main repeating unit (RP0b The value "n" in Scheme 3 for the functionalized repeat unit (R*) should be about 40 mole %. P0b The value "1-n" for (P0-B) should be 60 mole %, said mole % being based on the total number of moles of repeat units in the PAEK copolymer (P0-B).

[0246] The polymerization was carried out in a 1 L glass reaction vessel equipped with an overhead stirrer, nitrogen inlet, and overhead distillation apparatus. The monomers: DFBP (283.66 g; 1.3 mol), resorcinol (57.25 g; 0.52 mol), and daBPA (240.55 g; 0.78 mol) were added to the vessel first, followed by potassium carbonate (188.64 g; 1.365 mol) and sulfolane (1235 g). The reaction mixture was heated from room temperature to 210 °C using a 15 °C / min temperature ramp. The reaction mixture temperature was maintained for approximately 5 hours, depending on the viscosity of the solution. The reaction was terminated by turning off the heat to the reaction vessel and diluting with cold sulfolane. The reaction mixture was filtered; the PAEK copolymer (P0-B) was coagulated into methanol and then dried at 110 °C.

[0247] Characterization of PAEK copolymer (P0-B) GPC method (RI detector): Mw=54998 g / mol, Mn=17477 g / mol, PDI=3.14 TGA: 428℃ DSC: Tg = 121°C 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm, indicating the incorporation of 2,2′-diallylbisphenol A monomer in the polymer (P0-B). 1 The estimated olefin content measured by H NMR was 65.6 mol %, which corresponds to a repeat unit (R P0b ) / Repeating unit (R* P0b The actual molar ratio of the main repeating unit (R P0bThe actual value of "n" in Scheme 3 for ) was 34.6 mol %.

[0248] The PAEK copolymer (P0-B) was amorphous since no Tm was observed by DSC.

[0249] IV. Preparation of grafted PAEK copolymer (P1-B) via free radical reaction The grafted PAEK copolymer (P1-B) was prepared according to Scheme 4. The main repeating unit (R P1b The actual value of "n" in Scheme 4 for PAEK copolymer (P0-B) was 34.6 mol%, the same as for the PAEK copolymer (P0-B).

[0250] The reaction was carried out in a 2 L glass reaction vessel equipped with an overhead stirrer and nitrogen inlet. A sample of allyl / vinylene-functionalized PAEK copolymer (P0-B) (12.2 g, containing 0.035 moles of unsaturated groups) and vinylpyrrolidone (268 g; 2.41 moles) were added to the reaction vessel, and the mixture was dissolved in anhydrous NMP (1588 g) and heated to 65 °C. The molar ratio of the moles of vinylpyrrolidone monomer to the moles of functionalized repeat units in the amorphous PAEK copolymer (P0-B) was 69:1. The reaction vessel was purged with nitrogen for 30 minutes, and then AIBN (3.35 g) was added in one portion. The reaction was allowed to proceed at 65 °C for 12 hours. After this 12-hour period, the reaction mixture was cooled, and approximately 70-80% of the NMP solvent was distilled off under reduced pressure below atmospheric pressure. The PAEK copolymer (P1-B) was isolated by coagulation in ethyl acetate. The grafted PAEK copolymer (P1-B) precipitate was washed repeatedly with hot water until no free polyvinylpyrrolidone was detected in the washings by FTIR. The purified grafted PAEK copolymer (P1-B) was dried under high vacuum at 100°C.

[0251] Characterization of grafted PAEK copolymer (P1-B) GPC method (RI detector): Mw=309148 g / mol, Mn=47468 g / mol, PDI=6.5 TGA: 411℃ DSC: Tg = 126°C Nitrogen content: 9.89% by weight The nitrogen content comes from the PVP bound to the parent polyarylether polymer (P0-B) and was determined by elemental analysis, the method for which is described above.

[0252] The grafted PAEK copolymer (P1-B) was amorphous since no Tm was observed by DSC.

[0253] Accordingly, the scope of protection is not limited by the above description, but only by the following claims, each and every claim being incorporated herein by reference as an embodiment of the present invention, and therefore the claims are further description and additions to preferred embodiments of the present invention. [ka] [ka] [ka] [ka]

Claims

1. A graft polyarylether (“PAE”) copolymer (P1), - at least 50 mol % in total of sulfone repeat units (R Ｐ１ａ ) and functionalized sulfone repeating units (R*) of formula (N1) Ｐ１ａ ) (the mole % is based on the total moles of repeat units in the grafted PAE copolymer (P1)): 【Chemical 1】 or - at least 50 mol % in total of ketone repeat units (R Ｐ１ｂ ) and functionalized ketone repeating units (R*) of formula (N2) Ｐ１ｂ ) (the mole % is based on the total moles of repeat units in the grafted PAE copolymer (P1)): 【Chemistry 2】 Including, Here, the repeating unit (R Ｐ１ａ ) / repeating unit (R* Ｐ１ａ ) or repeating unit (R Ｐ１ｂ ) / repeating unit (R* Ｐ１ｂ ) is at least 1 / 5 and at most 100 / 1; During the ceremony, - Each R １ are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each i is independently 0 or an integer from 1 to 4, preferably i=0 or 1; - T is a bond, -C(CH ３ ) ２ -;-SO ２ -;-CH ２ -;-O-;-S-;-C(O)-;-C(CF ３ ) ２ -; -C(=CCl ２ ) -; -C(CH ３ ) (CH ２ CH ２ COOH)-; -N=N-; and -R ａ C=CR ｂ - (where each R ａ and R ｂ are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy, or C6-C18 aryl group; m is an integer from 1 to 6; ２ ) ｍ - and - (CF ２ ) ｍ - -; a linear or branched, aliphatic divalent radical of up to 6 carbon atoms; and combinations thereof; preferably, T is a bond, -C(CH ３ ) ２ - and - SO ２ - selected from the group consisting of - G Ｎは , the following formula (G Ｎ１ ) ~ (G Ｎ１０ ) and any combination thereof: 【Chemistry 3】 (In the formula, - Group G Ｎ W in the formula is a bond, -SO ２ -, -C(CH ３ ) ２ - and any combination thereof, preferably -C(CH ３ ) ２ - and / or -SO ２ - or -C(CH ３ ) ２ - and / or a bond; - Group G Ｎ wherein each k is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2, or 3, more preferably k=0; groups G, which may be the same or different from one another Ｎ Two grafted polymers P ２ is a grafted poly(vinylpyrrolidone) polymer ("PVP"); groups G, which may be the same or different from one another Ｎ The two I's in the formula represent fragments of a free radical initiator and / or fragments of a PVP polymer. selected from the group consisting of Copolymer (P1).

2. The sulfone repeating unit (R Ｐ１ａ ) is represented by the formula (M1a), (M1b), or (M1c): 【Chemistry 4】 2. The graft polyarylether copolymer (P1) according to claim 1, which is of the formula:

3. i is each R １ The graft polyarylether copolymer (P1) according to claim 1 or 2, wherein the graft polyarylether copolymer (P1) is zero.

4. The ketone repeating unit (R Ｐ１ｂ ) is represented by the formula (M2a): 【Chemistry 5】 3. The graft polyarylether copolymer (P1) according to claim 1 or 2, which is of the formula:

5. A total of at least 80 mol % of sulfone repeat units (R Ｐ１ｂ ) and (R* Ｐ１ｂ ) or ketone repeating units (R Ｐ１ａ ) and (R* Ｐ１ａ 5. The graft polyarylether copolymer (P1) according to claim 1, wherein the mol % is based on the total number of moles of repeating units in the graft PAE copolymer (P1).

6. k is the repeating unit (R* Ｐ１ａ ) or (R* Ｐ１ｂ 6. The graft polyarylether copolymer (P1) according to any one of claims 1 to 5, wherein the graft polyarylether copolymer (P1) is 0.

7. Sulfone repeating units (R Ｐ１ａ ) / repeating unit (R* Ｐ１ａ ) or ketone repeating units (R Ｐ１ｂ ) / repeating unit (R* Ｐ１ｂ 7. The graft polyarylether copolymer (P1) according to claim 1, wherein the molar ratio of aryl ether to aryl ether is from 1 / 4 to 50 / 1, preferably from 1 / 3 to 40 / 1, more preferably from 1 / 2 to 30 / 1, or from 1 / 2 to 25 / 1.

8. Repeating unit (R* Ｐ１ａ ) or (R* Ｐ１ｂ ) in the formula (G Ｎ１ ) ~ (G Ｎ１０ ) any group G Ｎ The grafted polymer P ２ Each of the formula (P): 【Chemistry 6】 The repeating unit Rp is The mole percentage is the mole percentage of the grafted polymer P ２ Based on the total number of repeating units of wherein n in formula (P) is an integer of at least 3, or at least 5, or at least 8, or at least 10 and at most 200, or at most 175, or at most 150, or at most 100, and n is preferably from 3 to 200, more preferably from 10 to 150; A graft polyarylether copolymer (P1) according to any one of claims 1 to 7.

9. A graft polyarylether copolymer (P1) according to any one of claims 1 to 8, which is not crosslinked.

10. The graft polyarylether copolymer (P1) according to any one of claims 1 to 9, containing less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. % of free vinylpyrrolidone or free poly(vinylpyrrolidone), based on the total weight of the graft PAE polymer (P1).

11. An amorphous side-chain olefin-functionalized polyaryletherketone copolymer (P0), a total of at least 50 mol % of ketone repeat units (R Ｐ０ｂ ) and functionalized ketone repeating units (R*) of formula (NO') Ｐ０ｂ ) (the mole percentages are based on the total moles of repeating units in the copolymer (P0)): 【Chemistry 7】 Including, During the ceremony, - Each R １ are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each i is independently 0 or an integer from 1 to 4; preferably i=0; - G Ｐ is expressed by the following formula (G Ｐ１ ), (G Ｐ２ ) and (G Ｐ３ ): 【Chemistry 8】 (In the formula, - Group G Ｐ W in the formula is a bond, -SO ２ -, -C(CH ３ ) ２ - and any combination thereof, preferably -C(CH ３ ) ２ - and / or -SO ２ - or -C(CH ３ ) ２ - and / or a bond; - Group G Ｐ wherein each k is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2, or 3, and more preferably k=0. selected from the group consisting of at least one of: Here, the ketone repeat (R Ｐ０ｂ ) / repeating unit (R* Ｐ０ｂ ) is at least 1 / 5 and at most 100 / 1; Copolymer (P0).

12. The group G Ｐ W in the formula is a bond or -C(CH ３ ) ２ 12. The amorphous side-chain olefin-functionalized polyaryletherketone copolymer (P0) according to claim 11, wherein

13. A process for the preparation of a graft polyarylether copolymer (P1) according to any one of claims 1 to 10, comprising: - Solvent S １ wherein a side-chain allyl / vinylidene functionalized polyarylether copolymer (P0) is reacted with vinylpyrrolidone monomer in the presence of at least one free radical initiator to form a graft polyarylether copolymer (P1); removing any free poly(vinylpyrrolidone) and optionally any unreacted vinylpyrrolidone monomer and / or unreacted free radical initiator from the formed grafted PAE copolymer (P1) to produce a purified grafted PAE copolymer (P1); Including, wherein the allyl / vinylidene functionalized polyarylether copolymer (P0) is - at least 50 mol % in total of sulfone repeat units (R Ｐ０ａ ) and functionalized sulfone repeating units (R*) of formula (N0) Ｐ０ａ ) (the mole percentages are based on the total moles of repeating units in the copolymer (P0)): 【Chemistry 9】 Or, - at least 50 mol % in total of ketone repeat units (R Ｐ０ｂ ) and functionalized ketone repeating units (R*) of formula (NO') Ｐ０ｂ ) (the mole percentages are based on the total moles of repeating units in the copolymer (P0)): 【Chemistry 10】 Including, During the ceremony, - Each R １ are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each i is independently 0 or an integer from 1 to 4, preferably i=0 or 1; - T is a bond, -C(CH ３ ) ２ -;-SO ２ -;-CH ２ -;-O-;-S-;-C(O)-;-C(CF ３ ) ２ -; -C(=CCl ２ ) -; -C(CH ３ ) (CH ２ CH ２ COOH)-; -N=N-; and -R ａ C=CR ｂ - (where each R ａ and R ｂ are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy, or C6-C18 aryl group; m is an integer of 1 to 6 -(CH ２ ) ｍ - and - (CF ２ ) ｍ -; a linear or branched, aliphatic divalent radical of up to 6 carbon atoms; and combinations thereof; preferably, T is a bond, -C(CH ３ ) ２ - and - SO ２ - selected from the group consisting of; - G Ｐ is expressed by the following formula (G Ｐ１ ), (G Ｐ２ ) and (G Ｐ３ ): 【Chemistry 11】 (In the formula, - Group G Ｐ W in the formula is a bond, -C(CH ３ ) ２ -, -SO ２ - and any combination thereof, preferably -C(CH ３ ) ２ - and / or -SO ２ - or -C(CH ３ ) ２ - and / or a bond; - Group G Ｐ wherein each k is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2, or 3, more preferably k=0. selected from the group consisting of at least one of: Here, the sulfone repeating unit (R Ｐ０ａ ) / repeating unit (R* Ｐ０ａ ) or ketone repeating units (R Ｐ０ｂ ) / repeating unit (R* Ｐ０ｂ ) is at least 1 / 5 and at most 100 / 1; The functionalized repeating unit (R*) in the PAE copolymer (P0) used in the reaction mixture Ｐ０ａ ) or (R* Ｐ０ｂ The number of moles of １ and the number of moles of vinylpyrrolidone monomer used in the reaction mixture is n ２ and the molar ratio n ２ / n １ is at least 3, or at least 5, at least 8, or at least 10 and at most 200, or at most 175, or at most 150, or at most 100, and n is preferably 3 to 200, more preferably 10 to 150; process.

14. The reaction step is carried out under the following conditions: in the presence of 2,2'-azobis(2-methylpropionitrile) (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN) as at least one free radical initiator; and / or - the solvent S １ are 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-methyl-2-pyrrolidone (NMP), N-butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropylene urea (DMPU), and dimethylformamide (DMF). , tetrahydrothiophene-1-monoxide, and mixtures thereof; preferably a polar aprotic solvent selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), N-butylpyrrolidinone (NBP), N-ethylpyrrolidone (NEP), N,N'-dimethylacetamide (DMAc), N,N'-dimethylpropyleneurea (DMPU), dimethylformamide (DMF), and / or sulfolane; and / or at a reaction temperature of 10°C to 200°C, preferably room temperature to 150°C, or more preferably 35°C to 100°C; even more preferably 50°C to 80°C; and / or in the absence of crosslinking conditions, preferably in the absence of crosslinking agents, in the absence of radiation and / or in the absence of radiation initiators 14. The process of claim 13, wherein the process is carried out in at least one of the following steps:

15. 15. Use of a graft polyarylether copolymer (P1) according to any one of claims 1 to 10 or a graft polyarylether copolymer produced by the process according to any one of claims 13 to 14 in the preparation of at least part of an article, preferably a membrane, said membrane being selected from the group consisting of proton exchange membranes, membranes for bioprocessing (e.g. enzyme or cell culture filtration), membranes for medical filtration, such as hemodialysis membranes, membranes for food and beverage filtration and / or membranes for water purification.

16. 15. An article comprising a graft polyarylether copolymer (P1) according to any one of claims 1 to 10 or a graft polyarylether copolymer produced from the process according to any one of claims 13 to 14, preferably said article being a membrane selected from the group consisting of proton exchange membranes, membranes for bioprocessing such as enzyme or cell culture filtration, membranes for medical filtration such as hemodialysis membranes, membranes for food and beverage filtration, and membranes for water purification.

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