Grafted polyaryl ether copolymers

Abstract

The present invention relates to a grafted polyarylether ('PAE') copolymer (P1), a method for preparing the grafted PAE copolymer (P1) from a side chain allyl / vinylidene functionalized PAE copolymer (P0) via a free-radical reaction with a vinyl pyrrolidone and the use of the grafted PAE copolymer (P1) in the preparation of an article, such as a film or a portion thereof. The grafted PAE copolymer (P1) comprises at least two types of repeating units, one of which has a side chain grafted poly (vinyl pyrrolidone). The invention also relates to amorphous side chain allyl / vinylidene functionalized polyaryletherketone copolymers (P0).

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Patent Application No. 63 / 409989, filed on September 26, 2022, and European Patent Application No. 22211450.6, filed on December 5, 2022, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] The present disclosure relates to grafted polyarylether copolymers (P1), to methods for preparing grafted copolymers (P1) from amorphous side-chain allyl / vinylidene functionalized polyarylether copolymers (P0), to articles, especially films, comprising such copolymers (P1), and to the use of copolymers (P1) for preparing such articles. The present disclosure also relates to amorphous side-chain allyl / vinylidene functionalized polyaryletherketone copolymers (P0) and their corresponding grafted polyaryletherketone copolymers (P1). Background Art

[0004] 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 resistance, heat resistance and mechanical resistance combined with their excellent hydrolytic stability and relatively cheap production cost make them suitable for being widely used in the manufacture of membranes, particularly porous hollow-fiber polymer membranes. Porous hollow-fiber polymer membranes are used in many applications, such as hemodialysis, ultrafiltration, nanofiltration, reverse osmosis, gas separation, microfiltration, desalination via membrane distillation, and pervaporation. For many of these applications, membranes with optimal selectivity and chemical, thermal and mechanical stability are desired.

[0005] While poly(arylether) polymers (PAE) have many advantages and favorable physical properties, it is sometimes desirable to adjust one or more properties to improve performance in a particular application (e.g., hemodialysis, bioseparation, or water filtration), such as becoming less susceptible to fouling, having increased hydrophilicity, and / or having improved biocompatibility.

[0006] The inherent hydrophobicity of PAE polymers does make membranes made therefrom prone to scaling, which negatively affects their performance. Scaling is caused by hydrophobic interactions between the membrane material and contaminants (e.g., microorganisms, proteins, or organic matter) from the fluid to be processed by the membrane. In particular, scaling is caused by the adsorption of contaminants onto the membrane surface and internal structure, resulting in pore blockage, cake layer formation, or biofilm formation. Membrane scaling not only reduces membrane permeability and overall life, but also increases maintenance costs due to extensive and frequent cleaning to remove contaminants.

[0007] Since most commercial pressure-driven membranes are made of hydrophobic polymers including polyethersulfone (PES), polysulfone (PSU), and poly(etheretherketone) (PEEK), enhancing the surface hydrophilicity can be achieved by increasing the density of hydrophilic groups at the membrane surface, as the hydrophilic modification of the membrane surface reduces the tendency of organic fouling.

[0008] For example, PAE can be blended with highly hydrophilic polymers such as polyvinylpyrrolidone to increase the hydrophilicity of PAE-based membranes, while PAE can be blended with zwitterionic polymers to impart anti-fouling properties. While this approach may be straightforward, there are serious limitations because the two or more polymers that are typically blended are incompatible, which results in severe macroscopic phase separation in the final product. Furthermore, since these polymers are simply physical mixtures, the resulting product may change its composition, and therefore its properties, due to the loss of one of the polymers due to diffusion during membrane operation.

[0009] Another approach to avoid this behavior is to covalently link the PAE homopolymer and another polymer so that the resulting material has a robust composition and does not substantially change during application.

[0010] Modification of hydrophilicity can also be achieved by combining two homopolymers to prepare block copolymers that have a combination of the inherent properties of each individual homopolymer. For example, in membrane applications, a PAES homopolymer can be covalently linked to a hydrophilic homopolymer to synthesize a new PAES-hydrophilic block copolymer that has superior membrane properties due to the enhanced wettability caused by the hydrophilic component while retaining the mechanical robustness and amorphous pore structure of the PAES component. In this technique, the mechanical properties of the final product may be compromised due to the inherent low molecular weight of the PAES component.

[0011] Another technology reported in the literature relates to covalent grafting as a means of changing the characteristics of polyarylether polymers. Graft copolymerization is a reaction in which a side chain graft (graft) derived from one or more vinyl monomers is 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 may involve a polymerization reaction between a base polymer with a functional group and a vinyl monomer, and involves forming a reactive group on the base polymer. With regard to fouling prevention, 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 causes them to be difficult to adsorb on the membrane surface through the interstices of the membrane.

[0012] Yang et al., “Cross-linked poly(aryl ether ketone) anion exchange membranewith high ion conductivity by two different functional imidazole side chains,” Reactive and Functional Polymers, vol. 151, 104551 (June 2020) and Xu et al., “A facile 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) reported the covalent attachment of vinyl monomers to polyaryletherketone and ketosulfone polymers with pendant allyl groups. In these examples, very short chains consisting of monomers or dimers are attached to the polymer via free radical grafting.

[0013] KR 20170115697 A relates to a permeable membrane comprising a support formed by reacting a functionalized polysulfone-based polymer "APSf" with a hydrophilic compound, thereby having hydrophilicity and, therefore, improved water permeability. The APSf polymer has double bonds in the side chains and is a homopolymer prepared by the polymerization reaction of 2,2'-diallylbisphenol A and difluorodiphenyl sulfone with potassium carbonate. However, the solvent for preparing APSf is not disclosed in this reference, and the molecular weight and glass transition temperature of the APSf homopolymer are not characterized. 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 free radical initiator. In the example, APSf homopolymer (1 g) was mixed with conventional polysulfone "PSf" (1 g) and treated with a vinyl monomer (0.8 g of N,N-dimethylaminoethyl methacrylate) in 7 g of N-methylpyrrolidone "NMP" in the presence of a free radical initiator (0.1 g of azobisisobutyronitrile) and reacted at 60°C for 3 hours. At the end of the free radical reaction, the mixture was used 'as is' to be applied to a non-woven fabric of polyethylene terephthalate attached to a glass plate. However, in this reference, the resulting PSf-based polymer was not separated from the ungrafted vinyl polymer, unreacted monomer and free radical initiator. In addition, the APSf homopolymer will be very hydrophobic because it contains two allyl groups in each repeating unit, and this type of homopolymer will be difficult to prepare in polar aprotic solvents (such as dimethyl sulfoxide, NMP). Summary of the invention

[0014] The present invention provides amorphous grafted polyarylether [hereinafter "PAE"] copolymers (P1) and methods for preparing such copolymers (P1). Amorphous side chain allyl / vinylidene functionalized polyarylether copolymers (P0) are grafted with functional vinyl monomers to produce graft copolymers (P1), wherein vinyl polymers are covalently attached to some of the side chains of the polyarylether copolymer backbone. The grafted polyarylether copolymers (P1) encompass the advantages of both polyarylether polymers and vinyl polymers for specific applications. The grafted polyarylether copolymers (P1) include complex polymer structures and can be used in many different applications, for example, to prepare films.

[0015] The present invention provides a way to introduce functionality into PAE polymers from reactive side chains via grafted vinyl polymers.

[0016] A first aspect of the present disclosure relates to a grafted PAE copolymer (P1) comprising a grafted vinyl polymer covalently attached to some of the side chains of the PAE copolymer backbone. The copolymer (P1) comprises a poly(arylether) (PAE) repeating unit (R P1) and a functionalized PAE repeating unit (R*) of a vinyl polymer having a side chain graft P1 ), more specifically may comprise poly(arylethersulfone) ('PAES') repeating units (R P1a ) and PAES repeat units functionalized with vinyl polymers grafted with side chains (R* P1a ), or poly(aryletherketone) ('PAEK') repeating units (R P1b ) and PAEK repeating units functionalized with vinyl polymers grafted with side chains (R* P1b ).

[0017] A second aspect of the present invention relates to an amorphous side-chain allyl / vinylidene functionalized polyaryletherketone copolymer (P0) comprising a total of at least 50 mol % of PAEK repeating units (R P1b ) and PAEK repeating units (R*) functionalized with reactive side chains containing allyl groups and / or functional groups containing carbon-carbon double bonds P1b ).

[0018] A third aspect of the present invention relates to a process for producing a grafted PAE copolymer (P1) from a pendant allyl / vinylidene functionalized PAE copolymer (P0) containing allyl and / or carbon-carbon double bond containing functional groups, which are reactive and can therefore be used to effectively modify the copolymer.

[0019] A fourth aspect of the present invention relates to the use of the obtained grafted PAE copolymer (P1) in various applications, for example for the preparation of membranes.

[0020] A fifth aspect of the present invention relates to an article comprising the grafted PAE copolymer (P1), said article preferably being a film or a part thereof.

[0021] Another aspect of the present invention relates to a solution comprising the grafted PAE copolymer (P1), in particular for use in forming a film, fiber or membrane.

[0022] A further aspect of the present invention may relate to a purification process comprising at least a filtration step through a membrane, fiber or film comprising or prepared from the grafted PAE copolymer (P1) described herein. DETAILED DESCRIPTION

[0023] In this application:

[0024] - even if any description relating to a specific embodiment is applicable to and interchangeable with other embodiments of the present disclosure, and each embodiment defined thereby can be combined with another embodiment, unless otherwise indicated or clearly incompatible;

[0025] - When an element or component is said to be included in and / or selected from a list of listed elements or components, it should be understood that in the relevant embodiments explicitly considered herein, the element or component may also be any of these listed independent elements or components, or may also be selected from a group consisting of any two or more of the explicitly listed elements or components; any element or component listed in the list of elements or components may be omitted from this list;

[0026] - Any recitation of numerical ranges by endpoints herein includes all numbers contained in the recited range as well as the endpoints of that range and equivalents thereof;

[0027] - the terms "comprising" or "comprise" include "consisting essentially of" or "consisting essentially of" as well as "consisting of" or "consist of"; and

[0028] - as used herein, the singular 'a' or 'one' includes the plural unless expressly stated otherwise; and

[0029] -It should be understood that the elements, properties and / or characteristics of the (co)polymers, products or articles, methods or uses described in this specification can be combined in all possible ways with other elements, properties and / or characteristics of the (co)polymers, products or articles, methods or uses, explicitly or implicitly, without departing from the scope of this specification.

[0030] In the present disclosure, the term "repeating unit" refers to the smallest unit of the PAE polymer, which is repeated in the chain and is composed of the condensation of an aromatic diol compound and an aromatic dihalogenated compound. The term "repeating unit" is synonymous with the terms "repeating unit" and "structural unit".

[0031] As used herein, the term "homopolymer" encompasses polymers having only one type of repeating unit.

[0032] As used herein, the term "copolymer" encompasses polymers that may have two or more different types of repeating units.

[0033] The term "solvent" is used herein in its ordinary sense and refers to a substance that is capable of dissolving another substance (solute) to form a mixture that is uniformly dispersed at the molecular level. In the case of polymer solutes, the convention is to refer to a solution of the polymer in the solvent when the resulting mixture is transparent and there is no visible phase separation in the system. The point at which phase separation occurs, often referred to as the "cloud point," is considered to be the point at which the solution becomes cloudy or turbid due to the formation of polymer aggregates.

[0034] The term "membrane" is used herein in its ordinary sense, i.e., it refers to a discrete, generally thin interface that attenuates the permeation of chemical species in contact with it. The interface may be molecularly uniform, i.e., completely uniform in structure (dense membrane), or it may be chemically or physically non-uniform, e.g., containing voids, holes or pores of finite size (porous membrane). A membrane generally has an outer surface and an inner surface within the pores that come into contact with the chemical species.

[0035] Weight average molecular weight (M w ) and number average molecular weight (M n ) can be estimated by gel permeation chromatography (GPC) calibrated with polystyrene standards and using a mobile phase. The mobile phase can be selected from any solvent used for the copolymers (P0), (P1) described herein, such as solvent S1 disclosed herein, such as dichloromethane, N-methyl-2-pyrrolidone (NMP), sulfolane or N,N′-dimethylacetamide (DMAc). The M of the PAE copolymer (P1) is w and M n It is preferably measured by GPC method 1 provided in the examples. M of the PAE copolymer (P0) w and M n It is preferably measured by GPC method 2 provided in the examples. The polydispersity index (PDI) is hereby expressed as the weight average molecular weight (M w ) and number average molecular weight (M n ) ratio.

[0036] The glass transition temperature 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.

[0037] Should the disclosure of any patents, patent applications, and publications incorporated herein by reference conflict with the description of the present application to the extent that it renders a term unclear, the present description shall take precedence.

[0038] Grafted PAE copolymer (P1)

[0039] The first aspect of the present invention relates to a grafted polyarylether copolymer (P1). The grafted PAE copolymer (P1) comprises at least two types of repeating units, one type of repeating unit being functionalized by a vinyl polymer having a side chain graft.

[0040] The functional groups of the grafted PAE copolymer (P1) are inherent to the PAE copolymer backbone, and these functional groups are generated by step-growth polymerization in the presence of at least one allyl-substituted diol monomer to form a pendant allyl / vinylidene functionalized PAE copolymer (P0) which is used as the basis for preparing copolymer (P1). This advantageously makes the PAE copolymer backbone versatile, because when forming the base PAE copolymer (P0), the content of functionality can be adjusted by varying the content of the allyl-substituted diol monomer relative to the other diol or diols in the reaction mixture. The allyl-substituted monomer contains two pendant allyl side chains, each containing 3 to 7 carbon atoms.

[0041] 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 are generally racemized during polymerization in such a way that the position of the double bond can vary along the side chain. This results in the formation of molecules that are different from each other because the C=C double bond may be at the end of the side chain or at one carbon before the end of the side chain. The amount of racemization depends on the reaction time and temperature.

[0042] The copolymer (P1) of the present invention comprises:

[0043] - a total of at least 50 mol.% of sulfone repeating units (R) of formula (M1) P1a ) and a functionalized sulfone repeating unit (R*) having formula (N1) P1a ), said mol.% is based on the total molar number of repeating units in the copolymer (P1):

[0044]

[0045] or

[0046] - a total of at least 50 mol.% of ketone repeating units (R) of formula (M2) P1b ) and a functionalized ketone repeating unit (R*) having formula (N2) P1b ), said mol.% is based on the total molar number of repeating units in the copolymer (P1):

[0047]

[0048]

[0049] in

[0050] -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;

[0051] - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;

[0052] - each i is independently 0 or an integer from 1 to 4, preferably i = 0 or 1;

[0053] -T is selected from the group consisting of: 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 R a and R b each independently of one another is hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; -(CH2) m -and-(CF2) m -, wherein m is an integer from 1 to 6; a straight or branched aliphatic divalent group having up to 6 carbon atoms; and combinations thereof; preferably T is selected from the group consisting of a bond, -C(CH3)2- and -SO2-;

[0054] -G N Select from the following formula (G N1 ) to (G N10 ) and any combination thereof:

[0055]

[0056]

[0057] in

[0058] -Group G N W in which is selected from the group consisting of a bond, -SO2-, -C(CH3)2- and any combination thereof, preferably selected from -C(CH3)2- and / or -SO2- or selected from -C(CH3)2- and / or a bond;

[0059] -Group GN Each k in is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2 or 3, more preferably k=0;

[0060] -Group G N The two grafted polymers P2 are the same as or different from each other and are grafted poly(vinyl pyrrolidone) polymers ('PVP'); and

[0061] -Group G N The two I's in are the same as or different from each other, and represent a fragment of a free radical initiator and / or a fragment of a PVP polymer.

[0062] The grafted PAE copolymers (P1) of the present invention exclude the functionalized sulfone repeating units (R*) having the formula (N1) only. P1a ) or consists only of functionalized ketone repeating units (R*) of formula (N2') P1b ) composed of homopolymers.

[0063] Repeating unit (R P1a ) / repeating unit (R* P1a ) or repeating unit (R P1b ) / repeating unit (R* P1b ) can 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. The repeating units (R P1a ) / repeating unit (R* P1a ) or repeating unit (R P1b ) / repeating unit (R* P1b ) can be in a molar ratio of 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, or 1 / 2 to 22 / 1.

[0064] The grafted PAE copolymer (P1) may be such that each R1 is independently selected from the group consisting of: C1-C12 moieties optionally containing one or more than one heteroatom; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amines and quaternary ammonium groups.

[0065] The grafted PAE copolymer (P1) may preferably be such that for each R1, i is zero (meaning that no benzene ring is substituted).

[0066] In other embodiments, the grafted PAE copolymer (P1) containing sulfone repeating units of formula (M1) and (N1) can be such that in some repeating units of formula (M1) and (N1), some R1 are selected from sulfonic acid groups; alkali metal or alkaline earth metal sulfonate groups; and / or alkyl sulfonate groups, wherein the corresponding i thereof is 1, while in other sulfone repeating units of formula (M1) and (N1), i=0 (i.e., the benzene ring is not substituted). The benzene ring optionally substituted with such R1 and i=1 is preferably connected to the -SO2- linking group of the sulfone repeating unit.

[0067] Alternatively, the grafted PAE copolymer (P1) containing ketone repeating units of formula (M2) and (N2) may be such that in some of the ketone repeating units of formula (M2) and (N2), some R1 are selected from sulfonic acid groups; alkali metal or alkaline earth metal sulfonate groups; and / or alkyl sulfonate groups, wherein the corresponding i thereof is 1, while in other ketone repeating units of formula (M2) and (N2), i=0 (i.e., the benzene ring is not substituted). The benzene ring optionally substituted with such R1 and i=1 is preferably attached to the -C(O)- linking group of the ketone repeating unit.

[0068] The grafted PAE copolymer (P1) may be such that in the case of a copolymer having the formula (G N1 ) to (G N10 ) any one of the groups G N , k is zero.

[0069] In some embodiments, the grafted PAE copolymer (P1) may be such that in the case of a copolymer having the formula (G N1 ) to (G N10 ) any one of the groups G N In the same grafted PAE copolymer (P1), W may be -C(CH3)2- and / or -SO2-. N In the case of -C(CH3)2-, W is in other groups G N However, preferably, in the same grafted PAE copolymer (P1), W is present in all groups G N are the same as in the examples and are -C(CH3)2- or -SO2-.

[0070] In other embodiments involving grafted PAEK copolymers (P1) containing ketone repeating units having formula (M2) and (N2), N1 ) to (G N10 ) any one of the groups G N W in the grafted PAEK copolymer (P1) may be a bond and / or -C(CH3)2-. NIn the case of -C(CH3)2-, W is in other groups G N However, preferably, in the same grafted PAEK copolymer (P1), W is present in all groups G N are the same in and are -C(CH3)2- or bonds.

[0071] In the repeating unit (R* P1a ) or (R* P1b ) in the formula (G N1 ) to (G N10 ) any one of the groups G N Each of the grafted polymers P2 in may contain at least 50 mol.%, based on the total number of moles of the recurring units in the grafted polymer P2, of recurring units Rp having the formula (P):

[0072]

[0073] 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 having 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.

[0074] In the case of (G N1 ) to (G N10 ) any one of the groups G N Each of the grafted polymers P2 in the above-mentioned embodiment may contain 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 recurring units Rp of formula (P), based on the total moles of recurring units in the grafted polymer P2. N1 ) to (G N10 ) any one of the groups G N Each of the grafted polymers P2 in may preferably consist essentially of repeating units Rp of formula (P).

[0075] The grafted PAE copolymer (P1) may be such that the group G NI in the formula (P) may 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 may be a fragment of a PVP polymer chain, the fragment 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 a repeating unit Rp having the formula (P) based on the total moles of the repeating units in the formula (P). When the group G N When at least one of I is a fragment of a PVP polymer chain, the chain length or molecular weight (M n ) is preferably smaller than the same group G N The chain length or molecular weight (M) of the two grafted polymers P2 n ).

[0076] Preferably, when the group G N When at least one of the two I's in is a fragment of a free radical initiator, such I may be a fragment of AIBN, such as

[0077]

[0078] When the group G N When at least one of the two I's is a fragment of a PVP polymer chain, such I preferably consists essentially of repeating units Rp having formula (P).

[0079] The grafted PAE copolymer (P1) is preferably prepared by free radical polymerization of a pendant allyl / vinylidene functionalized polyarylether copolymer (P0) containing pendant carbon-carbon double bonds and free of bound PVP with a vinyl pyrrolidone monomer and a free radical initiator.

[0080] The grafted PAE copolymer (P1) is preferably not crosslinked. During the preparation of copolymer (P1) from copolymer (P0), indeed no observable crosslinking occurs within the PAE copolymer or within the vinyl polymer or between them, as indicated by the resulting very good solubility of copolymer (P1) in the absence of any gel or undissolved material and a glass transition temperature of copolymer (P1) similar to that of copolymer (P0) from which copolymer (P1) was prepared (within + / -15°C, preferably within + / -11°C, more preferably within + / -10°C or within + / -8%, or within + / -6% or within + / -5%). Tg and Tg 0 Preferably it is measured by Differential Scanning Calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0081] In an alternative embodiment, the grafted PAE copolymer (P1) may have a Tg 0 -10℃ to Tg 0 +10℃ glass transition temperature, where Tg 0 is the glass transition temperature of the side-allyl / vinylidene functionalized PAE copolymer (P0) from which the copolymer (P1) is prepared. Tg and Tg 0 Preferably it is measured by Differential Scanning Calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0082] The grafted PAE copolymer (P1) preferably contains less than 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, still more preferably less than 0.3 wt% or less than 0.1 wt% of free vinyl pyrrolidone, based on the total weight of the grafted PAE polymer (P1). The detection of free vinyl pyrrolidone can be carried out via Fourier transform infrared spectroscopy (FTIR).

[0083] The grafted PAE copolymer (P1) preferably contains less than 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, still more preferably less than 0.3 wt% or less than 0.1 wt% of free poly(vinyl pyrrolidone), based on the total weight of the grafted PAE polymer (P1). The detection of free PVP can be carried out via Fourier transform infrared spectroscopy (FTIR).

[0084] The grafted PAE copolymer (P1) has the same polymer backbone as the base PAE copolymer (P0) from which the copolymer (P1) is prepared. The difference between the grafted PAE copolymer (P1) and the side-chain allyl / vinylidene functionalized PAE copolymer (P0) is the presence of grafted polymers P2 grafted on some of the side chains of the copolymer (P1), which are attached by reaction with the side-chain allyl / vinylidene groups in their corresponding PAE copolymer (P0).

[0085] 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 grafted 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 grafted PAE copolymer (P1) may have a weight average molecular weight Mw of 200 kDa to 1100 kDa, preferably 250 kDa to 1000 kDa, more preferably 300 kDa to 900 kDa, and even more preferably 300 kDa to 700 kDa. The Mw of the PAE copolymer (P1) w It is preferably measured by GPC Method 1 provided in the Examples.

[0086] PDI of grafted PAE copolymer (P1) = M w / M n Preferably greater than the PDI of the side allyl / vinylidene functionalized PAE copolymer (P0) used to prepare the grafted PAE copolymer (P1) 0 =M w 0 / M n 0 . M of PAE copolymer (P1) n and M w It is preferably measured by GPC method 1 provided in the examples, and the M of the PAE copolymer (P0) n 0 and M w 0 Preferably it is measured by GPC Method 2 provided in the Examples. Typically, 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.

[0087] The glass transition temperature Tg of the grafted PAE copolymer (P1) can be obtained by preparing the glass transition temperature Tg of the side chain allyl / vinylidene functionalized PAE copolymer (P0) of the grafted PAE copolymer (P1). 0 Tg and Tg 0 Preferably it is measured by Differential Scanning Calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0088] In an alternative embodiment, the grafted PAE copolymer (P1) may have a Tg 0 -10℃ to Tg 0 +10℃ glass transition temperature, where Tg 0is the glass transition temperature of the side-allyl / vinylidene functionalized PAE copolymer (P0) from which the copolymer (P1) is prepared. Tg and Tg 0 Preferably it is measured by Differential Scanning Calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0089] The solubility of the grafted PAE copolymer (P1) in a particular solvent is the same as or higher than the solubility of the PAE copolymer (P0) functionalized with side allyl / vinylidene groups used to prepare the copolymer (P1). 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.

[0090] Grafted PAES copolymer (P1)

[0091] When the grafted PAE copolymer (P1) comprises repeating units (R P1a ) and functionalized repeating units (R* P1a ), it can be referred to as a grafted "PAES" copolymer (P1).

[0092] 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.

[0093] The grafted PAES copolymer (P1) may contain 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 the repeating unit (R P1a ) and (R* P1a The grafted PAES copolymer (P1) may preferably consist essentially of repeating units (R P1a ) and (R* P1a )composition.

[0094] The repeating unit (R P1a ) / repeating unit (R* P1a ) can be:

[0095] - at least 1 / 4, at least 1 / 3, at least 1 / 2, at least 1 / 1, and / or

[0096] - Up to 50 / 1, Up to 40 / 1, Up to 30 / 1, Up to 25 / 1, or Up to 22 / 1.

[0097] The repeating unit (R P1a ) / repeating unit (R* P1a ) can be in a molar ratio of 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.

[0098] The grafted PAES copolymer (P1) may be such that in the repeating unit (R P1a ), T is selected from the group consisting of: a bond, -SO2-, -C(CH3)2- and any combination thereof. The grafted PAES copolymer (P1) may, for example, comprise some repeating units (R) in which T is -C(CH3)2- P1a ) and other repeating units in which T is -SO2- (R P1a ).

[0099] Preferred repeating units (R P1a ) may have formula (M1a), (M1b) or (M1c):

[0100]

[0101] in

[0102] - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and

[0103] - Each i is independently 0 or an integer from 1 to 4, preferably i=0.

[0104] More preferably, the repeating unit (R) in the grafted PAES copolymer (P1) P1a ) may have the formula (M1b') and / or (M1b"):

[0105]

[0106] in

[0107] Each R1 is independently selected from the group consisting of alkali metal or alkaline earth metal sulfonates and alkyl sulfonates; and

[0108] Each i is independently an integer from 1 to 4, preferably i=1.

[0109] Amorphous grafted PAEK copolymer (P1)

[0110] When the grafted PAE copolymer (P1) comprises repeating units (R P1b ) and functionalized repeating units (R* P1b ), it can be referred to as a grafted "PAEK" copolymer (P1).

[0111] 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.

[0112] The grafted "PAEK" copolymer (P1) is an amorphous polymer, which means that the grafted "PAEK" copolymer (P1) does not exhibit a melting point (Tm) determined by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0113] The grafted PAEK copolymer (P1) may contain 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 the repeating units (R P1b ) and (R* P1b The grafted PAEK copolymer (P1) may preferably consist essentially of repeating units (R P1b ) and (R* P1b )composition.

[0114] The repeating unit (R P1b ) / repeating unit (R* P1b ) can be:

[0115] - at least 1 / 4, at least 1 / 3, at least 1 / 2, or at least 1 / 1, and / or

[0116] - Up to 50 / 1, Up to 40 / 1, Up to 30 / 1, Up to 25 / 1, or Up to 22 / 1.

[0117] The repeating unit (R P1b ) / repeating unit (R* P1b ) can be in a molar ratio of 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, or 1 / 2 to 22 / 1.

[0118] Preferred repeating units (R P1b ) may have the formula (M2a):

[0119]

[0120] The grafted PAEK copolymer (P1) may further comprise one or more repeating units (R P1b ) and (R* P1b ) other repeating units (R' P1b ), such as those having the following formula (M2b) or (M2b'):

[0121]

[0122] in

[0123] - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and

[0124] - Each i is independently 0 or an integer from 1 to 4.

[0125] In such a case, the grafted PAEK copolymer (P1) may contain up to 20 mol%, up to 15 mol%, or up to 10 mol% of the repeating unit (R') based on the total moles in the grafted PAEK copolymer (P1). P1b ). The repeating unit (R') in the grafted PAEK copolymer (P1) P1b ) is such that the grafted PAEK copolymer (P1) maintains its amorphous state, thereby making it soluble in polar aprotic solvents like NMP, sulfolane, DMAc and other solvents described herein.

[0126] Process for preparing grafted PAE copolymer (P1)

[0127] The grafted PAE copolymer (P1) can be formed by a free radical reaction with a vinyl pyrrolidone monomer in the presence of a free radical initiator.

[0128] Therefore, a second aspect of the present invention relates to a process for preparing a grafted PAE copolymer (P1), the process comprising:

[0129] - reacting the side chain allyl / vinylidene functionalized polyarylether copolymer (P0) with vinylpyrrolidone monomer in the presence of at least one free radical initiator in solvent S1 to form a grafted polyarylether copolymer (P1); and

[0130] - removing any free poly(vinyl pyrrolidone) and optionally any unreacted vinyl pyrrolidone monomer and / or unreacted free radical initiator from the formed grafted PAE copolymer (P1) to produce a purified grafted PAE copolymer (P1).

[0131] The side chain allyl / vinylidene functionalized PAE copolymer (P0) comprises

[0132] - a sulfone-based repeating unit (R) defined later P0a ) and functionalized repeating units (R* P0a );or

[0133] - a ketone-based repeating unit (R) defined later P0b ) and functionalized repeating units (R* P0b ).

[0134] When the functionalized repeating units (R*) in the PAE copolymer (P0) used in the reaction mixture P0a ) or (R* P0b ) is n1; and the mole number of vinyl pyrrolidone monomer used in the reaction mixture is n2, 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.

[0135] The reaction step is preferably carried out in a reaction mixture comprising vinyl pyrrolidone monomer and solvent S 1. A free radical initiator may be added to the reaction mixture to initiate the reaction.

[0136] For the reaction step, the copolymer (P0) and the vinyl pyrrolidone monomer may be first added to a reactor vessel, and then dissolved in solvent S1 and heated at a suitable reaction temperature.

[0137] Alternatively, the copolymer (P0) can be first formed into an article and then contacted with a reaction mixture comprising vinyl pyrrolidone monomer, a free radical initiator and a solvent S1 and heated at a suitable reaction temperature.

[0138] Before adding the free radical initiator to start the free radical reaction, the reaction mixture is preferably purged with a non-oxidizing gas or atmosphere (such as nitrogen). The time period of the purge may vary from 10 to 120 minutes, with 20 to 60 minutes generally being sufficient.

[0139] 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, still more preferably at least 8 hours and at most 16 hours.

[0140] The reaction step for preparing the grafted PAE copolymer (P1) can be carried out under at least one of the following reaction conditions i) to iv):

[0141] i) in the presence of a solvent;

[0142] ii) in the presence of at least one free radical initiator;

[0143] iii) at a reaction temperature of 10°C to 200°C;

[0144] iv) In the absence of cross-linking conditions.

[0145] Reaction conditions (i): When the reaction for preparing the grafted PAE copolymer (P1) is carried out in solvent S1, solvent S1 is 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 known as tetramethylene sulfone or cyclopentane), N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N′-dimethylacetamide ( DMAc), N,N′-dimethylpropylene urea (DMPU), dimethylformamide (DMF), tetrahydrothiophene-1-monoxide and mixtures thereof; preferably selected from the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N′-dimethylacetamide (DMAc), N,N′-dimethylpropylene urea (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. The solvent S1 may also include 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.

[0146] 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).

[0147] 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.

[0148] Reaction condition (ii): The at least one free radical initiator is a thermal initiator, which can be a phenyl free radical initiator and / or an isobutyronitrile or isoheptonitrile free radical initiator capable of initiating polymerization of vinyl monomers. 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. As an example, when AIBN is used as a free radical initiator, AIBN decomposes partly due to the strong NN triple bond formed and partly due to the generation of relatively stable free radicals:

[0149]

[0150] Typically, about 0.1% to 1% by weight of free radical initiator (e.g., AIBN) based on the weight of the vinyl monomer is used. Generally, higher amounts of free radical initiator (e.g., AIBN) relative to the weight of the vinyl monomer will reduce the molecular weight of the resulting PVP polymer P2. Thus, up to 10% by weight of free radical initiator (e.g., AIBN) can be used to prepare short polymer chains of PVP polymer P2.

[0151] It is preferred to use all of the free radical initiator at once to initiate the reaction. However, if necessary, the free radical initiator can also be fed gradually into the reaction system.

[0152] 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, still more preferably from 50°C to 80°C.

[0153] Reaction conditions (iv): In the context of reaction conditions (iv), "crosslinking" means crosslinking between different molecules of the PAE copolymer (P1) and / or (P0), between different molecules of the vinyl polymer P2 and / or between molecules of the PAE copolymer and molecules of the vinyl polymer P2. The absence of crosslinking conditions preferably includes the absence of a crosslinking agent, the use of no radiation during the reaction and / or the absence of a radiation initiator.

[0154] In order to avoid crosslinking during the reaction, the reaction is preferably carried out in the absence of a crosslinking agent (such as a multifunctional vinyl compound containing at least 2 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.

[0155] At the end of the free radical reaction, the amount of grafted PAE copolymer (P1) can be at least 10 wt.%, eg, 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.

[0156] At the end of the free radical reaction, the reaction mixture may be cooled to stop the free radical reaction.

[0157] After the reaction mixture is cooled, most of the solvent S1 can be distilled off from the reaction mixture at subatmospheric pressure. For example, at least 50%, preferably at least 60 wt.%, more preferably 70 wt.% to about 80 wt.% of the solvent S1 present in the reaction mixture cooled at the end of the reaction is removed by distillation.

[0158] The grafted PAE copolymer (P1) is separated from other components of the reaction mixture (e.g., free poly(vinyl pyrrolidone), unreacted free radical initiator, fragments of free radical initiator, unreacted vinyl pyrrolidone) to obtain a purified copolymer (P1). The separation preferably comprises coagulation and one or more washings.

[0159] Coagulation can be used to precipitate the grafted PAE copolymer (P1) in a non-solvent or a poor solvent to form solid particles of the grafted PAE copolymer (P1) so as to separate it from other components remaining in the solution with the remainder of the solvent S1. The non-solvent or the poor solvent may contain at least 50%, preferably at least 60 wt% by weight of ethyl acetate, methyl acetate, acetone, butanone and / or C1-C5 alcohol. The non-solvent or the poor solvent may consist of ethyl acetate, methyl acetate, acetone, butanone and / or C1-C5 alcohol (such as methanol, ethanol, n-propanol, isopropanol, butanol).

[0160] The precipitate of the grafted PAE copolymer (P1) can be subjected to one or more washings with a washing liquid to further remove free (or unbound) PVP and / or unreacted vinyl pyrrolidone monomer and / or free radical initiator. The washing liquid is preferably water and / or a C1-C5 alcohol (e.g., methanol, ethanol, n-propanol, isopropanol). The washing 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 washing liquid should be at a temperature not exceeding its boiling point. The washing liquid is preferably at a temperature of at most 90°C, or at most 85°C, or at most 80°C, or at most 75°C. The washing liquid is more preferably water at a temperature of 60°C to 80°C, or 65°C to 75°C. The presence of free PVP can be monitored by FTIR in the spent washing liquid after each washing, and the washing steps are repeated until free PVP is no longer detected in the spent washing liquid.

[0161] The purified copolymer (P1) can then be dried at a temperature of typically about 50 to 120°C, preferably about 80 to 120°C, more preferably at about 90-120°C, still more preferably at about 90-110°C, preferably under vacuum.

[0162] The dried purified grafted PAE copolymer (P1) can be used to prepare articles as described herein, such as fibers, films or membranes.

[0163] In an alternative embodiment, the grafting reaction can be performed as a finishing technique for a molded article (such as a film, membrane, sheet and / or fabric) containing a PAE copolymer (PO). In such a case, there may be an initial step to form an article containing a PAE copolymer (PO). The article may be substantially made of a PAE copolymer (PO), or may contain a PAE copolymer (PO) and one or more other polymers different from the PAE copolymer (PO) as described herein. Therefore, the method may include: contacting the molded article with a solution of a vinyl pyrrolidone monomer and a free radical initiator to allow controlled modification of the PAE copolymer (PO) in the molded article by covalently fixing the grafted PVP polymer P2 to a desired level. After the grafting reaction is completed, the article is subjected to washing to remove free PVP polymer and (if any) unreacted vinyl monomer and / or unreacted free radical initiator. This process embodiment can avoid film forming problems that may occur on the grafted copolymer (P1) and will allow the removal of unreacted monomers / free radicals or unbound PVP from the shaped article now containing the grafted PAE copolymer (P1) containing the grafted PVP polymer P2.

[0164] Side chain allyl / vinylidene functionalized polyarylether copolymer (P0)

[0165] The side chain allyl / vinylidene functionalized polyarylether copolymer (P0) comprises two types of repeating units (R P0 ) and (R* P0 ), one type is a functionalized repeat unit with two reactive pendant allyl / vinylidene side chains (R* P0 ).

[0166] PAE copolymer (P0) comprises:

[0167] - a total of at least 50 mol.% of sulfone repeating units (R) of formula (M1) P0a ) and a functionalized sulfone repeating unit (R*) having formula (N0) P0a ):

[0168]

[0169]

[0170] or

[0171] - a total of at least 50 mol.% of ketone repeating units (R) of formula (M2) P0b ) and a functionalized ketone repeating unit (R*) having formula (N0') P0b ):

[0172]

[0173] in

[0174] - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;

[0175] - each i is independently 0 or an integer from 1 to 4, preferably i=0;

[0176] -T in formula (M1) is selected from the group consisting of: 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 R a and R b each independently of one another is hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; -(CH2) m -and-(CF2) m-, wherein m is an integer from 1 to 6; a straight or branched aliphatic divalent group having up to 6 carbon atoms; and combinations thereof; T is preferably selected from the group consisting of a bond, -C(CH3)2- and -SO2-;

[0177] -G P Select from the following formula (G P1 )、(G P2 ) and (G P3 ) is a group consisting of at least one of:

[0178]

[0179] in

[0180] -Group G P W in which is selected from the group consisting of a bond, -SO2-, -C(CH3)2- and any combination thereof, preferably selected from -C(CH3)2- and / or -SO2- or selected from -C(CH3)2- and / or a bond;

[0181] -Group G P Each k in is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2 or 3, more preferably k=0; and

[0182] The sulfone repeating unit (R P0a ) / repeating unit (R* P0a ) or ketone repeating unit (R P0b ) / repeating unit (R* P0b ) is at least 1 / 5 and at most 100 / 1.

[0183] The PAE copolymer (P0) excludes the functionalized sulfone repeating units (R*) having the formula (N0) only. P0a ) or consists only of functionalized ketone repeating units (R*) of formula (N0') P0b ) composed of homopolymers.

[0184] A particular aspect of the present invention relates to an amorphous PAEK copolymer (P0) comprising a total of at least 50 mol.% of ketone repeating units (R P0b ) and a functionalized ketone repeating unit (R*) having formula (N0') P0b ).

[0185] Sulfone repeating unit (R P0a ) / repeating unit (R* P0a ) or ketone repeating unit (R P0b ) / repeating unit (R* P0b ) can be at least 1 / 5, at least 1 / 4, at least 1 / 3, at least 1 / 2, or at least 1 / 1. The sulfone repeating unit (RP0a ) / repeating unit (R* P0a ) or ketone repeating unit (R P0b ) / repeating unit (R* P0b ) can be at most 100 / 1, at most 50 / 1, at most 30 / 1, at most 25 / 1, or at most 22 / 1. The sulfone repeating units (R P0a ) / repeating unit (R* P0a ) or ketone repeating unit (R P0b ) / repeating unit (R* P0b ) may be in a preferred molar ratio of 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.

[0186] The PAE copolymer (P0) may be such that in the group G P where k is zero.

[0187] In some embodiments, the PAES copolymer (P0) containing sulfone repeating units having formula (M1) and (N0) can be such that the group G P W in the group G can be -C(CH3)2- and / or -SO2-. In the same PAES copolymer (P0), W in the group G P Some of them may be -C(CH3)2-, while W in other groups G P However, preferably, in the same PAES copolymer (P0), W is present in all groups G P are the same and are -SO2- or -C(CH3)2-.

[0188] In other embodiments involving PAEK copolymers (PO) containing ketone repeating units having formula (M2) and (N0′), formula (G P1 ) to (G P3 ) any one of the groups G P W in the group G is preferably a bond and / or -C(CH3)2-. P Some of them may be -C(CH3)2-, while W in other groups G P However, preferably, in the same PAEK copolymer (P0), W is present in all groups G P are the same in and are a bond or -C(CH3)2-.

[0189] The PAE copolymer (P0) may be such that each R1 is independently selected from the group consisting of: C1-C12 moieties optionally containing one or more than one heteroatom; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amines and quaternary ammonium groups.

[0190] In the PAE copolymer (P0), for each R1, i is preferably zero (meaning that the benzene ring is unsubstituted).

[0191] In other embodiments, the PAES copolymer (P0) containing sulfone repeating units of formula (M1) and (N0) can be such that in some of the sulfone repeating units of formula (M1) and (N0), some R1 are selected from sulfonic acid groups; alkali metal or alkaline earth metal sulfonate groups; and / or alkyl sulfonate groups, wherein the corresponding i thereof is 1, while in other sulfone repeating units of formula (M1) and (N0), i=0 (i.e., the benzene ring is unsubstituted). The benzene ring optionally substituted with such R1 and i=1 is preferably connected to the -SO2- linking group of the sulfone repeating unit.

[0192] Alternatively, the PAEK copolymer (P0) containing ketone repeating units of formula (M2) and (N0') may be such that in some of the ketone repeating units of formula (M2) and (N0'), some R1 are selected from sulfonic acid groups; alkali metal or alkaline earth metal sulfonate groups; and / or alkyl sulfonate groups, wherein the corresponding i thereof is 1, while in other ketone repeating units of formula (M2) and (N0'), i=0 (i.e., the benzene ring is not substituted). The benzene ring optionally substituted with such R1 and i=1 is preferably attached to the -C(O)- linking group of the ketone repeating unit.

[0193] 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, still 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, still more preferably at most 100 kDa. w The copolymer (P0) may have a weight average molecular weight M of 20 kDa to 200 kDa, preferably 30 kDa to 160 kDa, more preferably 60 kDa to 100 kDa. w . M of PAE copolymer (P0) w Preferably it is measured by GPC Method 2 provided in the Examples.

[0194] The PAE copolymer (P0) is soluble in a polar aprotic solvent, preferably solvent S1 described herein, more preferably in NMP, DMAc, DMI, DMSO, sulfolane or a mixture thereof.

[0195] Amorphous PAES copolymer (P0)

[0196] When the PAE copolymer (P0) comprises sulfone-based repeating units (R P0a ) and functionalized repeating units (R* P0a ), it can be referred to as a "PAES" copolymer (P0).

[0197] The PAES copolymer (P0) may have a Tg ranging from 130 to 260°C, preferably from 160 to 250°C, more preferably from 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.

[0198] The PAES copolymer (P0) may contain 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 the repeating units (R) based on the total moles in the PAES copolymer (P0). P0a ) and (R* P0a The PAES copolymer (P0) can be basically composed of repeating units (R P0a ) and (R* P0a )composition.

[0199] The repeating unit (R) in the PAES copolymer (P0) P0a ) / repeating unit (R* P0a ) can be:

[0200] - at least 1 / 4, at least 1 / 3, at least 1 / 2, at least 1 / 1, and / or

[0201] - Up to 50 / 1, Up to 40 / 1, Up to 30 / 1, Up to 25 / 1, or Up to 22 / 1.

[0202] The repeating unit (R) in the PAES copolymer (P0) P0a ) / repeating unit (R* P0a ) can be in a molar ratio of 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.

[0203] The PAES copolymer (P0) may be such that in the repeating unit (RP0a ), T is selected from the group consisting of a bond, -SO2-, -C(CH3)2- and any combination thereof. The PAES copolymer (P0) may, for example, comprise some repeating units (R) wherein T is -C(CH3)2- P0a ) and other repeating units in which T is -SO2- (R P0a ).

[0204] The preferred repeating unit (R) in the PAES copolymer (P0) P0a ) may have formula (M1a), (M1b) or (M1c), as previously described with respect to the repeating unit (R P1a ), where

[0205] - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and

[0206] - Each i is independently 0 or an integer from 1 to 4, preferably i=0.

[0207] The PAES copolymer (P0) may be such that the repeating unit (R P0a ) has previously been associated with the repeating unit (R P1a ) is represented by the formula (M1b').

[0208] Amorphous PAEK copolymer (P0)

[0209] When the PAE copolymer (P0) comprises at least 55 mol.% of ketone-based repeating units (R) having the formula (M2), based on the total moles of repeating units in the PAEK copolymer (P0), P0b ) and a functionalized ketone-based repeating unit (R*) having formula (N0') P0b ), another aspect of the invention is a "PAEK" copolymer (P0), as previously described.

[0210] The PAEK copolymer (P0) may contain 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 the repeating units (R) in total, based on the total moles of the repeating units in the copolymer (P0). P0b ) and (R* P0b The PAEK copolymer (P0) may preferably consist essentially of repeating units (R P0b ) and (R* P0b )composition.

[0211] The PAEK copolymer (P0) is an amorphous polymer, which means that the PAEK copolymer (P0) does not exhibit a melting point (Tm) determined by differential scanning calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the examples.

[0212] The PAEK copolymer (P0) may have a Tg ranging from 90 to 200°C, preferably from 95 to 160°C, more preferably from 100 to 150°C, as measured by Differential Scanning Calorimetry (DSC), preferably according to ASTM D3418 or according to the method provided in the Examples.

[0213] The repeating unit (R P0b ) / repeating unit (R* P0b ) can be:

[0214] - at least 1 / 4, at least 1 / 3, at least 1 / 2, at least 1 / 1, and / or

[0215] - Up to 50 / 1, Up to 40 / 1, Up to 30 / 1, Up to 25 / 1, or Up to 22 / 1.

[0216] The repeating unit (R P0b ) / repeating unit (R* P0b ) can be in a molar ratio of 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.

[0217] The preferred ketone repeating units (R P0b ) may have the same characteristics as previously described for the repeating unit (R P1b ) is represented by formula (M2a).

[0218] The preferred ketone repeating units (R*) in the PAEK copolymer (P0) P0b ) has the formula (N0') where for each R1, i is zero.

[0219] In some embodiments involving PAEK copolymers (P0) containing ketone repeating units having formula (M2) and (N0′), formula (G P1 ) to (G P3 ) any one of the groups G P W in the group G is preferably a bond and / or -C(CH3)2-. P Some of them may be -C(CH3)2-, while W in other groups G PHowever, preferably, in the same PAEK copolymer (P0), W is present in all groups G P are the same in and are a bond or -C(CH3)2-.

[0220] The PAEK copolymer (P0) may further comprise other repeating units (R' P0b ), such as with the previous description of the repeating unit (R' P1b ) shown in the following formula (M2b) or (M2b'). In this case, the PAEK copolymer (P0) may contain up to 20 mol.%, up to 15 mol.%, or up to 10 mol.% of the repeating unit (R') based on the total moles in the PAEK copolymer (P0). P0b ). The repeating unit (R') in the PAEK copolymer (P0) P0b ) should be such that the PAEK copolymer (P0) maintains its amorphous state.

[0221] Method for preparing side chain allyl / vinylidene functionalized PAE copolymer (P0)

[0222] Allyl / vinylidene functionalized PAE copolymer (P0) can be prepared by condensation of at least one aromatic dihydroxy monomer (a1) with 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 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).

[0223] The condensation for preparing 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 known as tetramethylene sulfone or sulfolane), N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (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. The 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.

[0224] The condensation for preparing the PAE copolymer (P0) can be carried out in the presence of at least one base, for example selected from the group consisting of potassium carbonate (K2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3) and sodium tert-butoxide. The base is used to deprotonate components (a1) and (a3) ​​during the condensation reaction.

[0225] The condensation for preparing the PAE copolymer (P0) can 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.

[0226] The monomer (a3) ​​contains at least 50 wt.% based on the total weight of the monomer (a3) ​​selected from the group consisting of monomers having the following formula (G M1 )、(G M2 ) and (G M3 ) of any one of the group consisting of 2,2'-diallyl glycol "G M ", or consisting of:

[0227]

[0228] in

[0229] G M W in which 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; and

[0230] G M Each k in is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2 or 3, more preferably k=0.

[0231] Monomer (a3) ​​preferably contains at least 50 wt.% of a monomer having the following formula (G M4 ), or consisting of:

[0232]

[0233] The formula (G M4 ) is a bond, -C(CH3)2- or -SO2-, which means that G M4 is 2,2'-diallyl bisphenol (daBP), 2,2'-diallyl bisphenol A (daBPA) or 2,2'-diallyl bisphenol S (daBPS). In a preferred embodiment, formula (G M4 ) can be -C(CH3)2- or -SO2-, which means that G M4 is daBPA or daBPS. In another alternative preferred embodiment, formula (G M4 ) can be -C(CH3)2- or a bond, which means that G M4 It is daBPA or daBP.

[0234] Monomer (a3) ​​may, for example, contain 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 a monomer having the formula (G M1 )、(G M2 )、(G M3 ) and (G M4 ) any of 2,2'-diallyl glycol G M In preferred embodiments, monomer (a3) ​​comprises 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 daBP, or daBPA or daBPS, based on the total weight of monomer (a3).

[0235] For the preparation of the PAES copolymer (P0), the monomer (a1) comprises at least 50 wt.% of at least one diol selected from the group consisting of 4,4'-dihydroxybiphenyl (bisphenol), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 4,4'-dihydroxydiphenyl sulfone (bisphenol S) and any combination thereof, based on the total weight of the monomer (a1). The monomer (a1) 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.% of at least one diol selected from 4,4'-bisphenol, bisphenol A or bisphenol S, based on the total weight of the monomer (a1). The monomer (a1) preferably consists essentially of at least one diol selected from 4,4'-bisphenol, bisphenol A or bisphenol S.

[0236] To prepare the PAES copolymer (P0), the monomer (a2) comprises 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 at least one 4,4-dihalodiphenyl sulfone having the formula:

[0237]

[0238] in

[0239] - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;

[0240] - each i is independently 0 or an integer from 1 to 4, preferably i = 0 or 1; and

[0241] - X and X' are independently halogen selected from the group consisting of Cl and F, preferably both X and X' are Cl.

[0242] In some embodiments, at least one R1 in the 4,4-dihalodiphenyl sulfone is selected from the group consisting of alkali metal or alkaline earth metal sulfonates and alkyl sulfonates, and its corresponding i is equal to 1.

[0243] For the preparation of the PAES copolymer (P0), the monomer (a2) preferably comprises 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'-dichlorodiphenyl sulfone (DCDPS), disulfonated 4,4'-dichlorodiphenyl sulfone (sDCDPS), 4,4'-difluorodiphenyl sulfone (DFDPS) or disulfonated 4,4'-difluorodiphenyl sulfone (sDFDPS), more preferably the following DCDPS and / or sulfonated DCDPS disodium:

[0244]

[0245] DCDPS

[0246]

[0247] Disodium DCDPS sulfonate [disodium bis(4-chloro-3-sulfophenyl)sulfone].

[0248] In some embodiments for preparing PAES copolymer (P0), monomer (a2) may include two or more 4,4-dihalogenated diphenyl sulfones. In particular, monomer (a2) may include 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 two 4,4-dihalogenated diphenyl sulfones having the following formula based on the total weight of monomer (a2):

[0249]

[0250] in

[0251] - in a dihalodiphenyl sulfone, X and X' are both Cl or F, preferably X=X'=Cl, and both i are equal to 0; and

[0252] - In another dihalodiphenyl sulfone, X and X' are both Cl or F, preferably X=X'=Cl; both i are 1 and each R1 can be independently selected from the group consisting of alkali metal or alkaline earth metal sulfonates and alkyl sulfonates.

[0253] In a more specific embodiment for preparing an amorphous PAES copolymer (P0), monomer (a2) may comprise a mixture of at least 90 wt.% or at least 95 wt.% of DCDPS and disulfonated DCDPS (sDCDPS) based on the total weight of monomer (a2), or may be substantially composed thereof. In such a case, monomer (a2) preferably contains greater than 50 mol.%, greater than 60 mol.%, greater than 70 mol.%, or greater than 80 mol.% of DCDPS based on the combined moles of DCDPS and sDCDPS in monomer (a2).

[0254] In order to prepare the amorphous PAES copolymer (P0), the monomers (a1), (a2) and (a3) ​​of the reaction mixture are usually reacted simultaneously. The reaction is preferably carried out in one stage. 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 stage without separation of intermediate products.

[0255] To prepare the amorphous PAEK copolymer (P0), the monomer (a1) comprises 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 a diol having the formula:

[0256]

[0257] wherein each R1 is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal 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.

[0258] The monomer (a1) used to prepare the PAEK copolymer (P0) may, for example, contain 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 resorcinol based on the total weight of the monomer (a1). The monomer (a1) used to prepare the PAEK copolymer (P0) may preferably consist essentially of resorcinol.

[0259] To prepare the amorphous PAEK copolymer (P0), the monomer (a2) comprises 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 difluorobenzophenone having the formula:

[0260]

[0261] in

[0262] - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;

[0263] - Each i is independently 0 or an integer from 1 to 4, preferably i=0 or 1.

[0264] In some embodiments for preparing PAEK copolymer (P0), monomer (a2) may include two or more difluoroketones. In particular, monomer (a2) may include 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 two 4,4'-difluorobenzophenones having the following formula based on the total weight of monomer (a2):

[0265]

[0266] in

[0267] - in one of the 4,4'-difluorobenzophenones, both i are equal to 0; and

[0268] In another 4,4'-difluorobenzophenone, both i=1 and each R1 is independently selected from the group consisting of alkali metal or alkaline earth metal sulfonates and alkyl sulfonates.

[0269] In an alternative embodiment for preparing PAEK copolymer (P0), each R1 in 4,4'-difluorobenzophenone is selected from the group consisting of alkali metal or alkaline earth metal sulfonates and alkyl sulfonates, and its corresponding i is equal to 1. In such a case, monomer (a2) is preferably sulfonated disodium 4,4'-difluorobenzophenone.

[0270] For the preparation of amorphous PAEK copolymer (P0), 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 monomer (a2). When monomer (a2) comprises both DFBP and sDFBP, then monomer (a2) preferably contains greater than 50 mol.% of DFBP based on the combined moles of DFBP and sDFBP in monomer (a2). Monomer (a2) preferably consists essentially of DFBP.

[0271] In order to prepare the PAE copolymer (P0), the monomers (a1), (a2) and (a3) ​​of the reaction mixture are usually reacted simultaneously. The reaction is preferably carried out in one stage. 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 stage without separation of intermediate products.

[0272] Condensation can be carried out in a mixture of a polar aprotic solvent SO and a cosolvent that forms an azeotropic mixture with water. The cosolvent that forms an azeotropic mixture with water includes aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, etc. The cosolvent is preferably toluene or chlorobenzene. The cosolvent that forms an azeotropic mixture and the polar aprotic solvent SO are typically used in a weight ratio of about 1:100 to about 1:1, preferably about 1:10 to about 1:1, more preferably about 1:5 to about 1:1. Water is continuously removed from the reaction mass of the azeotropic mixture as the cosolvent that forms an azeotropic mixture, so that the conditions of substantially anhydrous are maintained during polymerization. After the water formed in the removal reaction, the cosolvent that forms an azeotropic mixture (for example, chlorobenzene or toluene) is typically removed from the reaction mixture by distillation, so that the copolymer (PO) is dissolved in the polar aprotic solvent.

[0273] The temperature of the reaction mixture used to prepare 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 the solvent S0, the preferred temperature of the reaction mixture may be about 180° C. to about 220° C. When DMAc is used as the solvent S0, the preferred temperature of the reaction mixture may be about 150° C. to about 170° C.

[0274] Before or after isolating the copolymer (P0), the inorganic components (eg sodium chloride or potassium chloride or excess alkali) may be removed by a suitable method (eg dissolution and filtration, sieving or extraction).

[0275] At the end of the condensation, the amount of copolymer (P0) is at least 30 wt.%, such as at least 35 wt.%, or at least 37 wt.%, or at least 40 wt.%, based on the total weight of copolymer (P0) and polar aprotic solvent S0.

[0276] At the end of the condensation reaction, the copolymer (P0) is separated from the other components (salt, base, ...) to obtain a solution. Filtration can be used, for example, to separate the copolymer (P0) from the other components.

[0277] Then, the solution containing the PAE copolymer (P0) can be used as it is to react the PAE copolymer (P0) with the vinyl pyrrolidone monomer in the process of the present invention to produce the grafted PAE copolymer (P1) according to the present invention and described herein. Alternatively, the PAE copolymer (P0) in solid form can be recovered from the solvent S0 (used during the condensation), for example, by condensation or devolatilization of the solvent S0. The PAE copolymer (P0) in solid form can be dissolved in the solvent S1 (same or different from S0) used to produce the PAE copolymer (P1).

[0278] The PAE copolymer (P0) is an intermediate product for preparing the grafted PAE copolymer (P1) according to the present invention.

[0279] Application of Grafted PAE Copolymer (P1)

[0280] Another aspect of the present invention provides the use of a grafted PAE copolymer (P1 ) for the preparation of an article (or a part thereof) as described herein.

[0281] Method for preparing an article

[0282] Another aspect of the present invention provides a method for preparing an article (or a portion thereof) comprising a grafted PAE copolymer (P1).

[0283] An article may be formed from a solution comprising the grafted PAE copolymer (P1).

[0284] When the article is a membrane or a portion thereof, the method preferably comprises effecting a phase inversion in a liquid phase (eg, a precipitation bath) to form the membrane or portion thereof.

[0285] One aspect of the present invention relates to a method for preparing an article comprising a grafted PAE copolymer (P1). The method for preparing the article may comprise performing one of the following methods:

[0286] - Process (a): using the grafted PAE copolymer (P1) in forming an article or a part thereof; or

[0287] - Process (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 grafted PAE copolymer (P1) from the copolymer (P0).

[0288] For method (b), the preformed article can be prepared by a phase inversion technique occurring in the liquid phase. The method (b) may further comprise 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 portion thereof; and contacting the preformed article or a portion thereof with a non-solvent bath. This is particularly applicable when the preformed article or a portion thereof is a membrane, fiber or film.

[0289] Articles containing grafted PAE copolymers (P1)

[0290] Another aspect of the present invention provides an article (preferably a shaped article) comprising the grafted PAE copolymer (P1) according to the present invention.

[0291] The article comprising the grafted PAE copolymer (P1) can be selected from the group consisting of: a film (eg, a solution cast film); a fiber; a sheet; a solution processed film (eg, a porous or non-porous film); and a solution processed monofilament.

[0292] The grafted PAE copolymer (P1) can be incorporated into an article having a polymer surface. The article can have a polymer surface, at least a portion of which is in direct contact with an aqueous medium such as water, an aqueous solution, a biological fluid, and / or a food product in its intended application setting. The polymer surface can be an outer surface or an inner surface of the article. For example, a medical device has an outer surface intended to be in direct contact with a biological fluid (such as blood, plasma, or serum). One of ordinary skill in the art will know which surface is intended to contact a biological fluid or food product based on the intended application setting of the article.

[0293] As another example, the surface of the article may include a coating or film comprising the grafted PAE copolymer (P1) disposed on an underlying substrate. In such an embodiment, the underlying substrate may be a structural component having a composition different from that of the grafted PAE copolymer (P1).

[0294] In embodiments where the grafted PAE copolymer (P1) is in a film, the film can have an average thickness of about 25 μm to about 1 mm.

[0295] The grafted PAE copolymer (P1) may be comprised in at least a portion of the surface of an article intended to be in contact with a biological fluid such as blood, plasma or serum. Alternatively, the grafted PAE copolymer (P1) may form all or substantially all of the article.

[0296] The shaped article comprising the grafted PAE copolymer (P1) can preferably be a membrane or a part thereof selected from the following: 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 separation in industrial processes involving aqueous media.

[0297] Among membranes, the grafted PAE copolymer (P1) according to the invention is particularly suitable for the manufacture of membranes intended to be in contact with aqueous media. The aqueous medium may include biological fluids such as blood, or food products such as beverages (eg juice, milk, beer).

[0298] From an architectural point of view, membranes comprising grafted PAE copolymers (P1) can be provided in the form of flat structures (e.g., films or sheets), corrugated structures (e.g., corrugated sheets), tubular structures, or hollow fibers; in terms of pore size, a variety of membranes (non-porous and porous, including for microfiltration, ultrafiltration, nanofiltration, and reverse osmosis) can be advantageously made with grafted PAE copolymers (P1); the pore distribution can be isotropic or anisotropic.

[0299] Among the applications of use, mention may be made of healthcare applications, in particular medical applications, wherein shaped articles comprising the grafted PAE copolymer (P1) can advantageously be used in disposable and reusable instruments and devices.

[0300] Among the applications of use, mention may be made of fuel cell applications, wherein the grafted PAE copolymer (P1) may advantageously be used in proton exchange membranes.

[0301] The article may comprise the grafted PAE copolymer (P1) in an amount ranging from 1 wt.% to 99 wt.%, for example, from 2 wt.% to 98 wt.%, from 3 wt.% to 97 wt.%, or from 4 wt.% to 96 wt.%, based on the total weight of the polymer, and optionally another sulfone polymer different from the copolymer (P1), for example, PAE copolymer (P0), PSU, PES, PPSU. In such a case, when the article comprises the copolymer (P1) and another sulfone polymer (such as PAE copolymer (P0), PSU, PES and / or PPSU), the weight fraction of the copolymer (P1) based on the combined weight of the copolymer (P1) and the other one or more sulfone polymers in the article is at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt% and / or up to 99 wt%, or up to 98 wt%, or up to 96 wt%, or up to 95 wt%, or up to 90 wt%.

[0302] As used herein, polyethersulfone (PES) refers to a polyethersulfone (PES) comprising at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units (R) of formula (J): PES ) of any polymer:

[0303]

[0304] (mol. % is based on the total moles of repeating units in the PES polymer). PES can be prepared by known methods and is available in particular from Solvay Specialty Polymers USA, LLC. Available from PESU.

[0305] As used herein, polysulfone (PSU) means a polysulfone 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 repeating units (R) of formula (K): PSU ) of any polymer:

[0306]

[0307] (mol.% is based on the total number of moles of repeating units in the PSU polymer). PSU can be prepared by known methods and is available in particular from Solvay Specialty Polymers, Inc., USA. PSU available.

[0308] As used herein, polyphenylsulfone (PPSU) means a polyphenylenesulfone (PPSU) comprising at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units (R) of formula (L): PPSU ) of any polymer:

[0309]

[0310] (mol. % is based on the total number of moles of repeating units in the PPSU polymer). PPSU can be prepared by known methods and is available in particular from Solvay Specialty Polymers, Inc., USA. PPSU available.

[0311] Membranes, fibers or films (as articles)

[0312] The article may be a film, a fiber, a membrane or a portion thereof.

[0313] A particular embodiment of the article, preferably a shaped article, relates to a membrane comprising the grafted PAE copolymer (P1).The membrane may be used for proton exchange or for purifying water, food products or biological fluids, such as blood.

[0314] An embodiment of the membrane according to the invention relates to a proton exchange membrane comprising a grafted PAE copolymer (P1).

[0315] 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 products or biological fluids, such as blood.

[0316] The membrane may be a microporous membrane, which may be characterized by its average pore size and porosity (ie, the fraction of the entire membrane that is porous).

[0317] The membrane may have a weight porosity (%) of 20% to 90% and comprise pores wherein at least 90% by volume of the pores have an average pore size of less than 5 μm. The weight porosity of the membrane is defined as the volume of the pores divided by the total volume of the membrane.

[0318] Membranes with a uniform structure throughout their thickness are generally referred to as symmetric membranes; membranes with pores that are non-uniformly distributed throughout their thickness are generally referred to as asymmetric membranes. Asymmetric membranes are characterized by a thin selective layer (0.1-1 μm thick) and a highly porous thick layer (100-200 μm thick) that acts as a support and has little effect on the separation characteristics of the membrane.

[0319] The membrane may be in the form of a flat sheet or in the form of a tube.

[0320] The membrane may be formed using multiple films or multiple fibers.

[0321] Tubular membranes are classified based on their size into tubular membranes with a diameter greater than 3 mm, capillary membranes with a diameter comprised between 0.5 mm and 3 mm, and hollow fibers with a diameter less than 0.5 mm. Capillary membranes are otherwise known as hollow fibers.

[0322] Hollow fibers are particularly advantageous in applications requiring compact modules with high surface area.

[0323] The membrane, fiber or film according to the present invention can be produced using any of the conventionally known membrane, fiber or film production methods, for example, by solution casting.

[0324] The membrane, fiber or film according to the present invention can be prepared by a phase inversion method occurring in the liquid phase, the method comprising the steps of: preparing a polymer solution comprising the copolymer (P1) described herein and a polar solvent, processing the polymer solution into a film; and contacting the film with a non-solvent bath.

[0325] 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: PAE copolymer (P0), another sulfone polymer such as polysulfone (PSU), polyethersulfone (PES), poly(biphenyl ether sulfone) (PPSU), polyphenylene sulfide (PPS), poly(aryletherketone) (PAEK) such as poly(etheretherketone) (PEEK), poly(etherketoneketone) (PEKK), poly(etherketone) (PEK) or copolymers of PEEK and poly(diphenyletherketone) (PEEK-PEDEK copolymers), polylactide (PLA), polyetherimide (PEI), polycarbonate (PC), polyphenylene oxide (PPO), polyvinylpyrrolidone (PVP) and / or polyethylene glycol (PEG). When the membrane, fiber or film further comprises at least one polymer different from the grafted PAE copolymer (P1), the at least different polymer preferably excludes PVP.

[0326] 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.

[0327] The membrane, fiber or film may contain 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.% of the grafted PAE copolymer (P1) of the present invention, based on the total weight of the polymer, and / or may contain the copolymer (P1) described herein in an amount greater than 50 wt.%, for example greater than 55 wt.%, greater than 60 wt.%, greater than 65 wt.%, greater than 70 wt.%, greater than 75 wt.%, greater than 80 wt.%, greater than 85 wt.%, greater than 90 wt.%, greater than 92 wt.%, or greater than 95 wt.%, based on the total weight of the polymer.

[0328] According to an embodiment, the membrane, fiber or film may contain a grafted PAE copolymer (P1) in an amount ranging from 1 wt.% to 99 wt.%, for example, from 2 wt.% to 98 wt.%, from 3 wt.% to 97 wt.% or from 4 wt.% to 96 wt.% based on the total weight of the polymer and optionally another sulfone polymer different from the copolymer (P1), for example, copolymer (P0), PSU, PES, PPSU. In such a case, when the membrane, fiber or film contains the grafted copolymer (P1) and another sulfone polymer (such as PSU, PES and / or PPSU), the weight fraction of the grafted copolymer (P1) is at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt% and / or up to 99 wt%, or up to 98 wt%, or up to 96 wt%, or up to 95 wt%, or up to 90 wt% based on the combined weight of the copolymer (P1) and the other one or more sulfone polymers in the membrane, fiber or film.

[0329] The film, fiber or membrane may further comprise at least one non-polymer component, such as solvents, fillers, lubricants, release agents, antistatic agents, flame retardants, antifogging agents, matting agents, pigments, dyes and optical brighteners.

[0330] Suitable examples of methods for forming membranes from polyaryl ether sulfone polymers are described in US2019 / 054429 A1 (Solvay Specialty Polymers, Inc.), which is incorporated herein by reference.

[0331] Polymer solutions (SP) for the preparation of membranes, fibers or films

[0332] Another aspect of the present invention relates to a polymer solution (SP) for preparing a membrane, fiber or film, comprising a polymer solution (SP) in a polar organic solvent [solvent (S SP )] in the grafted PAE copolymer (P1).

[0333] 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, for example, PEEK, PEKK, PEK or PEEK-PEDEK copolymer; PPO; PLA; PEI; PC; PVP; and / or PEG. The polymer solution (SP) preferably excludes PVP.

[0334] The total concentration of the grafted PAE copolymer (P1) and optionally one or more additional polymers in the polymer solution (SP) may be at least 8 wt.%, or preferably at least 10 wt.%, based on the total SP weight, and / or at most 70 wt.%; or at most 60 wt.%; or at most 50 wt.%; or at most 40 wt.%; or at most 30 wt.% based on the total polymer solution weight. A concentration of all polymers in the SP ranging between 10% wt and 25% wt, and more preferably between 10% wt and 22% wt, based on the total SP weight, is particularly advantageous.

[0335] The solvent in SP (S SP ) may be present in a concentration of at least 20 wt.%, preferably at least 30 wt.%, based on the total SP weight, and / or at most 70 wt.%, based on the total SP weight; preferably, at most 65 wt.%; more preferably, at most 60 wt.%.

[0336] The solvent in SP (S SP ) can be selected from the list of solvents provided for solvent S1 described previously. Preferably, the solvent (S SP ) is N,N′-dimethylacetamide (DMAc), sulfolane or NMP, and is particularly suitable for preparing membranes or films.

[0337] Exemplary solvents (S) that can be used alone or in combination in the polymer solution (SP) SP ) are described in patent application US2019 / 054429 A1 (Solvay Specialty Polymers, Italy) (in particular the solvents described in paragraphs

[0057] -

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

[0338] The polymer solution (SP) may contain additional components, such as nucleating agents, fillers and the like.

[0339] Purification methods for biological fluids

[0340] A further aspect of the invention may relate to a purification process comprising at least a filtration step through a membrane, fiber or film comprising the grafted PAE copolymer (P1 ) described herein.

[0341] 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, the method being performed in an extracorporeal circuit. The extracorporeal circuit for performing the method comprises at least one filtration device (or filter) comprising at least one membrane, one or more fibers or one or more membranes as described above.

[0342] As contemplated herein, blood purification methods through an extracorporeal circuit include hemodialysis (FD) by diffusion, hemofiltration (HF), hemodiafiltration (HDF), and hemoconcentration. In HF, the blood is filtered by ultrafiltration, whereas in HDF, the blood is filtered by a combination of FD and HF.

[0343] Blood purification methods through an extracorporeal circuit are typically performed with the aid of a hemodialyzer, i.e., a device designed to perform any of FD, HF, or HFD. In such methods, blood is filtered out of waste solutes and fluids (such as urea, potassium, creatinine, and uric acid) to provide blood free of waste solutes and fluids.

[0344] Typically, the hemodialyzer for performing a blood purification method comprises a cylindrical bundle of hollow fibers of a membrane, the bundle having two ends, each of which is fixed in a so-called perfusion compound, which is typically a polymer material that acts as a glue that holds the bundle ends together. Perfusion compounds are known in the art and notably include polyurethanes. By applying a pressure gradient, blood is pumped through the bundle of membranes via a blood port, and the filtered product ("dialysate") is pumped through the space around the fiber.

[0345] 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 limiting the scope of the present invention.

[0346] Examples

[0347] raw materials

[0348] K2CO3 (potassium carbonate), available from Armand Products

[0349] daBPA (2,2'-diallylbisphenol A), available from Sigma-Aldrich, USA

[0350] DCDPS (4,4'-dichlorodiphenyl sulfone), available from Solvay Speciality Polymers

[0351] DHDPS (4,4'-dihydroxydiphenyl sulfone or bisphenol S), available from Konishi Chemicals, Japan

[0352] DFBP (4,4'-difluorobenzophenone), available from Sigma-Aldrich, USA Resorcinol, available from Sigma-Aldrich, USA

[0353] DMAc (dimethylacetamide), available from Sigma-Aldrich, USA

[0354] NMP (2-methylpyrrolidone), available from Sigma-Aldrich, USA Sulfolane, available from Chevron Phillips

[0355] AIBN (azobisisobutyronitrile), available from Sigma-Aldrich, USA Vinylpyrrolidone (VP), available from Sigma-Aldrich, USA

[0356] Methanol, available from Sigma-Aldrich, USA

[0357] Ethyl acetate, available from Sigma-Aldrich, USA

[0358] Test Method

[0359] GPC Method for Molecular Weight (Mn, Mw)1

[0360] Instruments: Waters 515 pump, Waters 717plus autosampler, Waters 2487 absorbance detector, Waters 2414 refractive index detector

[0361] Column: Two Agilent PLgel MiniMix-D, 5um, 250×4mm (Part No. PL1510-5504) + Agilent Mix Guard, 5um, 50×4.6mm (Part No. PL1510-1504)

[0362] Column temperature: 45°C

[0363] Mobile phase: N,N-dimethylacetamide + 0.1M LiBr

[0364] Flow rate: 0.3ml / min

[0365] Injection volume: 20ul

[0366] UV detection: 270nm

[0367] RI detection: + polarity

[0368] Calibration: Agilent EasiCal PS-2 GPC / SEC Standard (Part No. PL2010-0601). Dissolve the standard in the mobile phase.

[0369] 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 to complete dissolution. Filter through a 0.2 um PTFE syringe filter into a 4 ml autosampler vial.

[0370] GPC Method 2 for Molecular Weight Measurement (Mn, Mw)

[0371] Molecular weight was measured by gel permeation chromatography (GPC) using methylene chloride as mobile phase. Two 5 μ mixed D columns with guard columns from Agilent Technologies were used for separation. Chromatograms were obtained using a 254 nm UV detector. A flow rate of 1.5 ml / min and an injection volume of 20 μL of a 0.2 w / v% solution in mobile phase were selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (peak molecular weight range: 371,000 to 580 g / mol). Number average molecular weight Mn, weight average molecular weight Mw, and higher average molecular weight Mz were reported.

[0372] Thermogravimetric analysis (TGA)

[0373] TGA experiments were performed using a TA Instrument TGA Q500. TGA measurements were obtained by heating the sample from 20°C to 800°C at a heating rate of 10°C / min under nitrogen.

[0374] 1 H NMR

[0375] Measured using a 400 MHz Bruker spectrometer with TCE as the deuterated solvent 1 H NMR spectroscopy. All spectra are referenced to residual protons in the solvent.

[0376] DSC

[0377] DSC was used to determine the glass transition temperature (Tg) and melting point (Tm) (if present). DSC experiments were performed using the Q100 of TA Instruments. The DSC curve was recorded by heating, cooling, reheating and then recooling the sample at a heating and cooling rate of 20°C / min between 25°C and 320°C. All DSC measurements were taken under nitrogen purge. Unless otherwise noted, the Tg value (and Tm value, if any) reported was provided using the second heating curve.

[0378] Elemental analysis

[0379] The elemental composition of some polymer samples was determined using the 2400CHN elemental analyzer of Perkin Elmer. The polymer samples were burned based on the classical Pregl-Dumas method. The resulting combustion gases were completely reduced to CO2, H2O, N2 and SO2. The gases were then separated via frontier chromatography. As the gases eluted, they were measured by a thermal conductivity detector to determine the quantitative amounts of carbon, hydrogen, nitrogen and sulfur.

[0380] FTIR

[0381] Since vinyl pyrrolidone is liquid and highly water soluble, and due to the extensive washing, filtering and drying of the graft copolymer (P1) sample, there should be no detectable free vinyl monomer in the dried sample of the graft copolymer (P1). Nevertheless, free residual vinyl monomer can be detected by FTIR using a Bruker Optics Vertex 70 FTIR station with a MIR source. The spectra were obtained in absorption mode through a diamond ATR crystal.

[0382] The FTIR analysis procedure used for the reference samples was as follows:

[0383] Use 18 megohm fresh water to establish a background spectrum;

[0384] Apply a drop of polymer sample to the ATR crystal to ensure complete coverage.

[0385] 32 replicate spectral scans were collected to produce an average response.

[0386] The following corrections were applied to each spectrum:

[0387] -Extended ATR correction for Diamond

[0388] - Atmospheric correction for water and CO2

[0389] - Baseline correction, normalizing all spectra together based on their max-min peak values.

[0390] Overlaying the normalized spectra; and

[0391] · Visual comparison 1641cm -1 The peak height.

[0392] I. Preparation of PAES copolymers with side-chain allyl / vinylidene functionalization (PO-A) PAES copolymer (P0-A) was prepared according to Scheme 1.

[0393] In order to generate the repeating unit (R P0a), using 4,4'-dichlorodiphenyl sulfone (DCDPS) and 4,4'-dihydroxydiphenyl sulfone or bisphenol S (DHDPS), and diallyl bisphenol A (daBPA) and DCDPS to generate repeating units (R* P0a ). The repeating unit (R*) in the side chain allyl / vinylidene functionalized polymer (PO-A) P0a The target mol.% of ) is 9.1 mol.% to achieve a 10:1 repeat unit (R P0a ) / repeating unit (R* P0a That is, the main repeating unit (R P0a ) should be about 90.9 mol.%, and the combined values: three functionalized repeating units (R* P0a ) should be 9.1 mol%. The mol%. is based on the total moles of repeating units in the PAES copolymer (P0-A).

[0394] The polymerization took place in a 20-L glass reactor vessel equipped with an overhead stirrer, a nitrogen inlet, and an overhead distillation mechanism. The monomers DCDPS (2030.2 g; 7.07 moles), DHDPS (1594.2 g, 6.37 moles), and daBPA (197.25 g; 0.64 moles) were first added to the vessel, followed by potassium carbonate (977.14 g; 7.07 moles) and NMP (4018.9 g). The reaction mixture was heated from room temperature to 190°C using a heating ramp of 10°C / min. The temperature of the reaction mixture was maintained for about six hours, depending on the viscosity of the solution. The reaction was terminated by adding an excess of DCDPS (140.7 g), thereby allowing DCDPS to cap the polymer for another 30 minutes, and then stopping the heating. The reaction mixture was filtered and coagulated in methanol. The polymer was then washed with methanol and water, and again with methanol, and dried at 110°C.

[0395] Characterization of PAES copolymer (P0-A)

[0396] GPC Method 2:

[0397] M w =58566 g / mol, M n =21327 g / mol, PDI = 2.75

[0398] TGA: 488℃

[0399] DSC: Tg = 218°C

[0400] 1H NMR: The presence of unsaturated groups was confirmed by the appearance of multiple peaks at 6.1-6.4 ppm, indicating that 2,2'-diallylbisphenol A monomer was incorporated into the polymer (P0-A).

[0401] pass 1 The estimated olefin content measured by H NMR was 8.97 mol%. This value provided a repeat unit (R P0a ) / repeating unit (R* P0a ) in the actual molar ratio. In Scheme 1, the main repeating unit (R P0a ) is 91.03 mol.%.

[0402] II. Preparation of Grafted PAES Copolymer (P1-A) by Free Radical Reaction

[0403] The grafted PAES copolymer (P1-A) was prepared according to Scheme 2. In Scheme 2, the main repeating unit (R P1a ) is 91.03 mol.%, which is the same as that of the PAES copolymer (P0-A).

[0404] The reaction took place in a 2-L glass reactor vessel equipped with an overhead stirrer and a nitrogen inlet. A sample of the side-chain allyl / vinylidene functionalized PAES copolymer (PO-A) (64 g, containing 0.024 moles of olefin double bonds) and vinyl pyrrolidone (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 vinyl pyrrolidone monomer to the number of moles of functionalized repeating units in the PAES copolymer (PO-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 continue at 65°C for 12 hours. After 12 hours, the reaction mixture was cooled and about 70%-80% of the solvent was distilled off under reduced pressure. The copolymer (P1-A) was isolated by coagulation in ethyl acetate and the copolymer (P1-A) was repeatedly washed with hot water until no free polyvinyl pyrrolidone was detected in the water washes via FTIR. The purified copolymer (P1-A) was dried at 100° C. under high vacuum.

[0405] Characterization of Grafted Polyaryl Ether Sulfone Copolymer (P1-A)

[0406] GPC method (RI detector):

[0407] Mn=80752g / mol, Mw=672825g / mol, PDI=8.3

[0408] DSC: Tg = 209°C

[0409] TGA: 414℃

[0410] The mol% of PVP in copolymer (P1-A) was estimated by 1 H NMR was analyzed by integrating the peaks attributed to polyvinylpyrrolidone attached to the polyarylethersulfone using the following equation:

[0411]

[0412] Where ∫PVP and ∫PSU will represent the sum of all hydrogen protons of PVP and PSU signals, respectively; and #HPVP and #HPSU represent the number of protons corresponding to PVP and PSU molecules, respectively. Then, the PVP weight content (wt.%) in the grafted polyarylethersulfone copolymer (P1-A) sample was calculated based on the following equation:

[0413] wt% PVP = ((mol PVP)(molecular weight PVP)) / ((g PVP + g PSU)) (100),

[0414] Wherein mol PVP is as described above by 1 H NMR measurement; the molecular weight of PVP is 111.1 g / mol, and the denominator: (g PVP + g PSU) is used for 1 The weight of the grafted polyarylethersulfone copolymer (P1-A) sample analyzed by H NMR.

[0415] 1 H NMR: 56.2 wt.% PVP

[0416] III. Preparation of Side-Chain-Allyl / Vinylene Functionalized PAEK Copolymers (P0-B)

[0417] PAEK copolymer (P0-B) was prepared according to Scheme 3.

[0418] In order to generate the repeating unit (R P0b ), using 4,4'-difluorobenzophenone (DFBP) and resorcinol, and in order to generate repeating units (R* P0b ), using diallyl bisphenol A (daBPA) and DFBP. The repeating unit (R*) in the side chain allyl / vinylidene functionalized polymer (PO-B) P0b The target mol.% of ) is 60 mol.% to achieve a 2:3 repeating unit (R P0b ) / repeating unit (R* P0b That is, the main repeating unit (R P0b) should be about 40 mol.%, and the functionalized repeating unit (R* P0b ) should be 60 mol.%, said mol.% being based on the total moles of repeating units in the PAEK copolymer (P0-B).

[0419] The polymerization took place in a 1-L glass reactor vessel equipped with an overhead stirrer, a nitrogen inlet, and an overhead distillation mechanism. Monomers: DFBP (283.66 g; 1.3 moles), resorcinol (57.25 g; 0.52 moles), and daBPA (240.55 g; 0.78 moles) were first added to the vessel, followed by potassium carbonate (188.64 g; 1.365 moles) and sulfolane (1235 g). The reaction mixture was heated from room temperature to 210° C. using a heating ramp of 15° C. / min. The temperature of the reaction mixture was maintained for about five hours, depending on the viscosity of the solution. The reaction was terminated by stopping the heating of the reactor vessel and by diluting with cold sulfolane. The reaction mixture was filtered; the PAEK copolymer (P0-B) was coagulated in methanol and then dried at 110° C.

[0420] Characterization of PAEK copolymer (P0-B)

[0421] GPC method (RI detector):

[0422] Mw=54998g / mol; Mn=17477g / mol; PDI=3.14

[0423] TGA: 428℃

[0424] DSC: Tg = 121°C

[0425] 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of multiple peaks at 6.1-6.4 ppm, indicating that 2,2'-diallylbisphenol A monomer was incorporated into the polymer (P0-B).

[0426] pass 1 The estimated olefin content measured by H NMR was 65.6 mol%. This value provided a repeat unit (R P0b ) / repeating unit (R* P0b ) in the actual molar ratio. In Scheme 3, the main repeating unit (R P0b ) is 34.6 mol.%.

[0427] The PAEK copolymer (P0-B) was amorphous as no Tm was observed via DSC.

[0428] IV. Preparation of Grafted PAEK Copolymer (P1-B) by Free Radical Reaction

[0429] The grafted PAEK copolymer (P1-B) was prepared according to Scheme 4. In Scheme 4, the main repeating unit (R P1b ) is 34.6 mol.%, which is the same as that of the PAEK copolymer (P0-B).

[0430] The reaction took place in a 2-L glass reactor vessel equipped with an overhead stirrer and a nitrogen inlet. A sample of allyl / vinylidene functionalized PAEK copolymer (PO-B) (12.2 g, containing 0.035 moles of unsaturated groups) and vinyl pyrrolidone (268 g; 2.41 moles) were added to the reactor vessel, and the mixture was dissolved in anhydrous NMP (1588 g) and heated to 65°C. The molar ratio of the number of moles of vinyl pyrrolidone monomer to the number of moles of functionalized repeating units in the amorphous PAEK copolymer (PO-B) was 69:1. The reaction vessel was purged with nitrogen for 30 minutes, and then AIBN (3.35 g) was added in one go. The reaction was allowed to continue at 65°C for 12 hours. After the 12-hour period, the reaction mixture was cooled and about 70%-80% of the NMP solvent was distilled off at reduced subatmospheric pressure. The PAEK copolymer (P1-B) was isolated by condensation in ethyl acetate. The grafted PAEK copolymer (P1-B) precipitate was washed repeatedly with hot water until no free polyvinyl pyrrolidone was detected in the water washes via FTIR.The purified grafted PAEK copolymer (P1-B) was dried at 100°C under high vacuum.

[0431] Characterization of Grafted PAEK Copolymer (P1-B)

[0432] GPC method (RI detector):

[0433] Mw=309148g / mol, Mn=47468g / mol, PDI=6.5

[0434] TGA: 411℃

[0435] DSC: Tg = 126°C

[0436] Nitrogen content: 9.89wt.%

[0437] The nitrogen content originates from the PVP attached to the parent polyarylether polymer (PO-B) and is measured by elemental analysis as described above.

[0438] The grafted PAEK copolymer (P1-B) was amorphous as no Tm was observed via DSC.

[0439] Therefore, the scope of protection is not limited by the description listed above, but only by the following claims. Each claim is incorporated into this specification as an embodiment of the present invention. Therefore, the claims are a further description and an addition to the preferred embodiments of the present invention.

[0440]

[0441]

[0442]

[0443]

Claims

1. A grafted polyarylether ("PAE") copolymer (P1) comprising: - a total of at least 50 mol.% of sulfone repeating units (R) of formula (M1) P1a ) and a functionalized sulfone repeating unit (R*) having formula (N1) P1a ), said mol.% is based on the total moles of repeating units in the grafted PAE copolymer (P1): or - a total of at least 50 mol.% of ketone repeating units (R) of formula (M2) P1b ) and a functionalized ketone repeating unit (R*) having formula (N2) P1b ), said mol.% is based on the total moles of repeating units in the grafted PAE copolymer (P1): 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; and in - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal 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 selected from the group consisting of: 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 R a and R b each independently of one another is hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; -(CH2) m -and-(CF2) m -, wherein m is an integer from 1 to 6; a straight or branched aliphatic divalent group having 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 Select from the following formula (G N1 ) to (G N10 ) and any combination thereof: in - The group G N W in which is selected from the group consisting of a bond, -SO2-, -C(CH3)2- and any combination thereof, preferably selected from -C(CH3)2- and / or -SO2- or selected from -C(CH3)2- and / or a bond; - The group G N Each k in is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2 or 3, more preferably k=0; - The group G N The two grafted polymers P2 are the same as or different from each other and are grafted poly(vinyl pyrrolidone) polymers ('PVP'); and - The group G N The two I's in are the same as or different from each other, and represent a fragment of a free radical initiator and / or a fragment of a PVP polymer.

2. The grafted polyarylether copolymer (P1) according to claim 1, wherein These sulfone repeating units (R P1a ) has the formula (M1a), (M1b) or (M1c):

3. The grafted polyarylether copolymer (P1) according to claim 1 or 2, wherein For each R1, i is zero.

4. The grafted polyarylether copolymer (P1) according to claim 1 or 2, wherein These ketone repeating units (R P1b ) has the formula (M2a):

5. The grafted polyarylether copolymer (P1) according to any one of claims 1 to 4, comprising a total of at least 80 mol.% of sulfone repeating units (R P1b ) and (R* P1b ) or ketone repeating unit (R P1a ) and (R* P1a ), said mol.% is based on the total molar number of repeating units in the grafted PAE copolymer (P1).

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

7. The grafted polyarylether copolymer (P1) according to any one of claims 1 to 6, wherein Sulfone repeating unit (R P1a ) / repeating unit (R* P1a ) or ketone repeating unit (R P1b ) / repeating unit (R* P1b ) is 1 / 4 to 50 / 1, preferably 1 / 3 to 40 / 1, more preferably 1 / 2 to 30 / 1 or 1 / 2 to 25 / 1.

8. The grafted polyarylether copolymer (P1) according to any one of claims 1 to 7, wherein Repeating unit (R* P1a ) or (R* P1b ) has these formulas (G N1 ) to (G N10 ) any one of the groups G N Each of the grafted polymers P2 in contains at least 50 mol.% of repeating units Rp of formula (P): The mol.% is based on the total number of repeating units of the grafted polymer P2, 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, preferably n is 3 to 200, more preferably 10 to 150.

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

10. The grafted 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 grafted PAE polymer (P1).

11. An amorphous side chain olefin functionalized polyaryletherketone copolymer (P0), comprising: A total of at least 50 mol.% of ketone repeating units (R) having the formula (M2) P0b ) and a functionalized ketone repeating unit (R*) having formula (N0') P0b ), said mol.% is based on the total moles of repeating units in the copolymer (P0): in - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal 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 Select from the following formula (G P1 )、(G P2 ) and (G P3 ) is a group consisting of at least one of: in - The group G P W in which is selected from the group consisting of a bond, -SO2-, -C(CH3)2- and any combination thereof, preferably selected from -C(CH3)2- and / or -SO2- or selected from -C(CH3)2- and / or a bond; - The group G P Each k in is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2 or 3, more preferably k=0; and The ketone repeating unit (R P0b ) / repeating unit (R* P0b ) is at least 1 / 5 and at most 100 / 1.

12. The amorphous side chain olefin functionalized polyaryletherketone copolymer (P0) according to claim 11, wherein The group G P W in is a bond or -C(CH3)2-.

13. A method for preparing a grafted polyarylether copolymer (P1) according to any one of claims 1 to 10, the method comprising: - reacting a side chain allyl / vinylidene functionalized polyarylether copolymer (P0) with a vinylpyrrolidone monomer in the presence of at least one free radical initiator in a solvent S1 to form the grafted polyarylether copolymer (P1); and - removing any free poly(vinyl pyrrolidone) and optionally any unreacted vinyl pyrrolidone monomer and / or unreacted free radical initiator from the formed grafted PAE copolymer (P1) to produce a purified grafted PAE copolymer (P1), Wherein the allyl / vinylidene functionalized polyarylether copolymer (P0) comprises: - a total of at least 50 mol.% of sulfone repeating units (R) of formula (M1) P0a ) and a functionalized sulfone repeating unit (R*) having formula (N0) P0a ), said mol.% is based on the total moles of repeating units in the copolymer (P0): or - a total of at least 50 mol.% of ketone repeating units (R) of formula (M2) P0b ) and a functionalized ketone repeating unit (R*) having formula (N0') P0b ), said mol.% is based on the total moles of repeating units in the copolymer (P0): in - each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal 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 selected from the group consisting of: 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 R a and R b each independently of one another is hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; -(CH2) m -and-(CF2) m -, wherein m is an integer from 1 to 6; a straight or branched aliphatic divalent group having 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 P Select from the following formula (G P1 )、(G P2 ) and (G P3 ) is a group consisting of at least one of: in - The group G P W in which 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; - The group G P Each k in is independently 0 or an integer from 1 to 4, preferably k=0, 1, 2 or 3, more preferably k=0; and The sulfone repeating unit (R P0a ) / repeating unit (R* P0a ) or ketone repeating unit (R P0b ) / repeating unit (R* P0b ) is at least 1 / 5 and at most 100 / 1; and The functionalized repeating units (R*) in the PAE copolymer (P0) used in the reaction mixture P0a ) or (R* P0b ) is n1; the number of moles of vinyl pyrrolidone monomer used in the reaction mixture is n2, and the molar ratio n2 / n1 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, n is preferably 3 to 200, more preferably 10 to 150.

14. The method of claim 13, wherein: The reaction step is carried out under at least one of 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 S1 is 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 known as tetramethylene sulfone or cyclopentane), N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N′-dimethylacetamide (DMAc), N,N′-dimethylpropyleneurea ( DMPU), dimethylformamide (DMF), tetrahydrothiophene-1-monoxide and mixtures thereof; preferably selected from the group consisting of: 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), N-butylpyrrolidone (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; still more preferably 50°C to 80°C; and / or - in the absence of crosslinking conditions, preferably in the absence of a crosslinking agent, in the absence of radiation and / or in the absence of a radiation initiator.

15. Use of the grafted polyarylether copolymer (P1) according to any one of claims 1 to 10 or the grafted polyarylether copolymer prepared by the method according to any one of claims 13 to 14 in the preparation of at least a part of an article, preferably a film, wherein The membrane is selected from the group consisting of proton exchange membranes, membranes for bioprocessing (eg 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. An article comprising the grafted polyarylether copolymer (P1) according to any one of claims 1 to 10 or the grafted polyarylether copolymer made by the method according to any one of claims 13 to 14, preferably wherein the article is 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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