Polyarylether sulfones containing phosphorus and made from dihaloaryl sulfones and cycloaliphatic diols

Abstract

A poly(arylene ether sulfone) polymer ("PAES") made by condensation of at least one cycloaliphatic diol, optionally an aromatic and / or acyclic co-diol, and at least one dihaloaryl sulfone monomer in a reaction medium comprising a polar aprotic solvent and an inorganic metal phosphate. The PAES is characterized by a phosphorus content of at least 6 ppm. Preferably, the PAES has a Mw of at least 60 000 g / mol and its molecular weight distribution is characterized by a Mz / Mw of at least 1.5 and at most 1.8. A process for making such a PAES, the use of such a PAES for making an article, an article such as a film or a portion thereof comprising or made from such a PAES, and a dope for making a film comprising such a PAES.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Application No. 63 / 575342, filed April 5, 2024, and European Application No. 24179288.6, filed May 31, 2024, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] The present invention relates to a polyarylene ether sulfone polymer (“PAES”) containing phosphorus and made of at least one alicyclic diol monomer and at least one dihaloaryl sulfone monomer, a method for manufacturing such PAES, the use of such PAES in the manufacture of articles, and articles comprising such PAES or made therefrom. Background Technology

[0004] Poly(aryl ether sulfone) polymers (PAES) are a class of thermoplastic polymers characterized by high glass transition temperatures, good mechanical strength and stiffness, and excellent heat resistance and oxidation resistance. Due to their desirable mechanical, thermal, and other properties, these polymers are increasingly used to manufacture products for a wide variety of commercial applications, such as coatings and films for a broad range of applications, including the medical market, because of their superior mechanical and thermal properties, as well as excellent hydrolytic stability. PAES is a general term used to describe any polymer containing at least one sulfone group (-SO2-), at least one ether group (-O-), and at least one aryl group.

[0005] A commercially important group of PAES includes polysulfone polymers, referred to herein as polysulfones, or PSUs for short. PSU polymers contain repeating units derived from the condensation of the dihydroxy monomer bisphenol A (BPA) and a dihalogen monomer (such as 4,4'-dichlorodiphenyl sulfone (DCDPS)). These PSU polymers are commercially available from Solvay Specialty Polymers USA, LLC (a member of the SYENSQO Group) under the trademark UDEL® PSU.

[0006] Another important group of PAES includes polyethersulfone polymers, or PES for short. PES polymers are derived from the condensation of the dihydroxy monomer bisphenol S (BPS) and a dihalogen monomer (such as 4,4'-dichlorodiphenyl sulfone (DCDPS)). These PES polymers are commercially available from Solvay Specialty Polymers, LLC under the trademark VERADEL® PES.

[0007] PSU and PES polymers based on BPA and BPS, respectively, are frequently used to prepare membranes intended for contact with biological fluids such as blood.

[0008] BPA and BPS are industrial chemicals that have been present in many products since the 1960s, including plastic bottles and food and beverage cans. In recent years, concerns have arisen regarding the safety of BPA and BPS. BPS and BPA are suspected of inherently disrupting the endocrine system, although no conclusive studies are available, and their effects on the environment and human health are still under investigation. Given this controversy, the market is seeking economically viable alternatives to BPA and BPS.

[0009] Because polymeric materials that come into contact with food and drugs must meet certain requirements, such as those set by the FDA, the European Food Safety Authority, and the Environmental Protection Agency (EPA), it is important to continue developing polymeric materials that are safe for both humans and the environment for applications that require contact with water, food, drugs, and / or blood.

[0010] Therefore, manufacturers have turned their attention to partially or completely replacing these aromatic diols, such as bisphenol A, with aliphatic diols.

[0011] Previous efforts in developing novel polymeric materials made from monomers with weak binding affinity to estrogen receptors can be found, for example, in US 2014 / 0113093 (Solvay Specialty Polymers LLC) and in the work of Sundell and colleagues (Polymer [Polymers] (2014) Vol. 55(22), pp. 5623-5634).

[0012] The development of renewable polymers derived from bio-based feedstocks is also of particular interest. This is part of efforts to reduce the amount of petroleum consumed in the chemical industry and to open up new, high-value-added markets for agriculture; 1,4:3,6-didehydrohexitol is an example of such a chemical used as a bio-based feedstock.

[0013] Due to the confined bicyclic geometry and oxidized ring of 1,4:3,6-disodehydrated hexitol, it can provide advantageous characteristics when incorporated into polyarylether sulfone structures. Furthermore, the harmless properties of these molecules open up possibilities for application in packaging or medical devices, such as for hemodialysis membranes.

[0014] Depending on chirality, there are three isomers of 1,4:3,6-disodehydrated hexitol glycol diol: isosorbide (D1), isomannitol (D2), and iso-idylol (D3).

[0015] .

[0016] 1,4:3,6-Didehydrohexitol consists of two cis-fused tetrahydrofuran rings, nearly planar and V-shaped with an angle of 120° between the rings. The hydroxyl groups are located at carbons 2 and 5 and are positioned either inside or outside the V-shaped molecule. These are designated as endotype or exotype, respectively. An overview of the manufacture of these 1,4:3,6-didehydrohexitols can be found in US 2015 / 0011446 A1 (Solvay Special Polymers S.A., Italy).

[0017] Interest in the production of 1,4:3,6-didehydrohexitols (especially isosorbide) has arisen from potential industrial applications, including the synthesis of polymers such as, in particular, polyesters, polyethers, polyurethanes, and polyamides. The use of 1,4:3,6-didehydrohexitols in polymers, and more specifically in condensation polymers, is likely driven by several characteristics: they are rigid bicyclic chiral diols derived from sugars, are chiral, and are non-toxic. In particular, isosorbide is obtained from the didehydrogenation reaction of sorbitol (which itself is derived from the hydrogenation of glucose).

[0018] Kricheldorf et al. first reported the preparation and characterization of poly(ether sulfone) containing isosorbide derived from silylated isosorbide and difluorodiphenyl sulfone (DFDPS) in 1995 (H. Kricheldorf, M. Al Masri, J. Polymer Sci., Pt A: Polymer Chemistry, 1995, 33, 2667-2671). Due to the significant cost increase from the silylation step, Kricheldorf and Chatti (High Performance Polymers, 2009, 21, 105-118) modified their polymerization conditions and reported that poly(ether sulfone) containing isosorbide could be prepared from unfunctionalized isosorbide and DFDPS in the presence of potassium carbonate. The highest apparent molecular weight polymer obtained had an intrinsic viscosity (IV) of 0.65 dL / g, measured under the following conditions: CH₂Cl₂ / trifluoroacetic acid solution (9 / 1 v / v), 20°C, 0.20 g / dL. The glass transition temperature of this polymer was reported as 245°C. No examples of polymerization with isosorbide using the less reactive dichlorodiphenyl sulfone (DCDPS) are described.

[0019] WO 2014 / 072473 A2 (Solvay Specialty Polymers, LLC) describes a method for preparing isosorbide-based aromatic polyether sulfones. This method involves the reaction of difluorodiphenyl sulfone or dichlorodiphenyl sulfone (optionally in the presence of a fluorinating agent) with isosorbide at 210°C in the presence of potassium carbonate. However, no M above 58 kDa was observed. w Examples of poly(sulfone isosorbide).

[0020] US Patent 2015 / 0129487 A1 (Solvay Specialty Polymers, LLC) describes a method for preparing semi-aromatic polyethersulfones based on non-aromatic cyclic diols such as cyclohexanediol, 1,5-cyclooctanediol, or tetramethylcyclobutanediol. The method involves the reaction of 4,4′-difluorodiphenyl sulfone with a non-aromatic cyclic diol in the presence of potassium carbonate at a minimum temperature of 160°C, and the reaction of 4,4′-dichlorodiphenyl sulfone with a non-aromatic cyclic diol in the presence of potassium carbonate at a minimum temperature of 210°C–215°C.

[0021] EP 0739925 (Bayer AG) describes polysulfone-polyether block cocondensates having formula (I): -(OEO-Ar1-SO2-Ar2-)-W-, wherein E is a divalent bisphenol ester group and W is a polyether, polysulfide, or polyacetal having at least two hydroxyl groups and an average molecular weight of 400 to 30,000, and wherein the group W accounts for a total of 5 to 99 weight percent in the total polymer. Their synthesis is carried out by strong base chemistry, wherein an alkali metal alkoxylate is used to deprotonate the aliphatic polyether glycol. In examples, about 34-60 wt% polyethylene glycol is used.

[0022] US 6365678 B1 (Bayer) describes a method for producing polyether block cosulfone, comprising reacting (A) at least one aromatic sulfone polymer with (B) at least one aliphatic polyether having an average of at least one terminal OH functional group. The reaction is carried out between the resulting high molecular weight polysulfone and the polyether in the presence of a basic catalyst to incorporate polyether segments via transesterification. While various bases such as carbonates, phosphates (especially Na3PO4, K3PO4, or K2HPO4), amines, and hydroxides (such as NaOH) are suitable, only potassium carbonate is exemplified as a base. The synthesis of polyether block cosulfone using polyethylene glycol (PEG8000) or polytetrahydrofuran is carried out in DMSO without dihalogenated monomers using an azeotropic mixture forming agent (toluene) and at a mild reaction temperature (140°C–155°C). In the examples, the weight fraction of polyethylene glycol (PEG) is about 3.6–12.9 wt%. The PSU-b-PEG in Example 1 has a Mw of 37 kDa.

[0023] However, due to their lower reactivity than standard bisphenols (e.g., bisphenol A), these alicyclic and acyclic diols typically require the use of activating monomers 4,4'-difluorodiphenyl sulfones (DFDPS), which are much more expensive than DCDPS; or high temperatures (210°C–215°C) in the presence of a weak base (e.g., K₂CO₃), at which some side reactions such as polymer cleavage may be observed; or strong bases (e.g., NaH) are used, which allows for lower temperatures. However, strong bases are known to induce secondary hydrolysis of diphenyl sulfone dihalides (RN Johnson and AG Farnham, J. Polym. Sci. A-1 Polym. Chem., Vol. 5, No. 9, pp. 2415–2427, 1967).

[0024] Regarding the low reactivity of alicyclic and acyclic diols, compared to the OH groups in bisphenol monomers, the OH groups in alicyclic and acyclic diols involved in PAES polymerization are not phenolic groups and have high pKa (> 11), which makes them very difficult to react due to their low acidity. Summary of the Invention

[0025] This invention aims to address several challenges related to method economics and the use of alicyclic diol monomers to partially or completely replace bisphenols in order to mitigate the effects of endocrine disruption potential.

[0026] The specific advantages of the method of the present invention are as follows:

[0027] - By using more cost-effective sulfone chloride monomers (e.g., dichlorodiphenyl sulfone (DCDPS) and / or disulfonated DCDPS), the economic constraints of manufacturing PAES from less reactive alicyclic diols and optionally from less reactive acyclic compounds containing at least two hydroxyl groups, such as epoxides or poly(epoxides), can be reduced, while still achieving relatively high molecular weights (e.g., M... w >59 kDa), these less reactive alicyclic diols include 1,4:3,6-disodehydrated hexitol (e.g., isosorbide), 2,3-O-isopropylidene-1-threitol obtained from tartaric acid, 2,3-di-O-methylene-1-threitol, tetrahydrofurandiethanol, tetramethylcyclobutanediol, cis-1,5-cyclooctanediol, cyclohexanediethanol, etc.; and

[0028] - Reduce or eliminate the endocrine-disrupting potential of commercially available PAES materials (such as those made of bisphenol A (BPA) or bisphenol S (BPS)) for use in applications involving contact with food, drugs, blood, and / or water, such as in the membrane market.

[0029] Various aspects of the invention are set forth in the appended claims.

[0030] The first aspect of the invention relates to a polyarylether sulfone polymer (“PAES”) as defined in any one of claims 1-9 or 26.

[0031] A second aspect of the invention relates to a method for manufacturing PAES as defined in any one of claims 10-25.

[0032] Other aspects of the invention relate to the use of PAES as defined in any one of claims 27-29, and solutions or articles containing such PAES.

[0033] By referring to the specific implementation methods and examples, it will be easier to understand and appreciate more precise information and details regarding the various embodiments, advantages, and features of the present invention. Detailed Implementation

[0034] definition

[0035] In this descriptive specification, some terms are intended to have the following meanings.

[0036] As used herein, the term “heterocyclic” defines a structure (such as a diol or part thereof) containing one or more rings having more than one type of atom in the ring, one of which is a carbon atom and another is a heteroatom (i.e., a non-carbon atom, such as an oxygen atom, a sulfur atom, or a nitrogen atom).

[0037] As used herein, for the purposes of this invention, the term "aliphatic diol" refers to a non-aromatic organic compound containing two hydroxyl functional groups. Aliphatic diols can be linear, branched, or cyclic. In addition to the oxygen atoms of the two hydroxyl groups, aliphatic diols may also contain one or more heteroatoms (i.e., non-carbon atoms), such as oxygen, nitrogen, and / or sulfur atoms.

[0038] As used herein, the term "alicyclic" defines a structure that is both alicyclic (meaning non-aromatic) and cyclic. Alicyclic structures (such as diols or portions) may contain one or more non-aromatic rings. Alicyclic structures may be unsaturated or saturated.

[0039] For the purposes of this invention, the terms "cycloaliphatic moiety" or "alicyclic moiety" are interchangeable and are intended to refer to any moiety that is both aliphatic (i.e., not aromatic) and cyclic (i.e., in which atoms are connected in a ring). The alicyclic moiety (M) can be unsubstituted or substituted. The alicyclic moiety can be heterocyclic. When the alicyclic moiety (or alicyclic portion) does not contain any heteroatoms in the ring, the ring skeleton of the alicyclic (or alicyclic) moiety is made solely of interconnected carbon atoms.

[0040] Similarly, for the purposes of this invention, the terms "cyclic aliphatic diol" and "alicyclic diol" are used interchangeably. Alicyclic diols can be heterocyclic in addition to the oxygen atoms of the two hydroxyl groups, because at least one ring contains one or more heteroatoms (i.e., non-carbon atoms), such as oxygen, nitrogen, and / or sulfur atoms.

[0041] As used herein, the term "acyclic" defines a structure that does not have any rings. Acyclic structures (such as diols or portions) can be unsaturated or saturated. For the purposes of this invention, "straight-chain aliphatic diols" and "branched-chain aliphatic diols" are acyclic diols. In addition to the oxygen atoms of the two hydroxyl groups, acyclic diols may contain one or more heteroatoms (i.e., non-carbon atoms, such as oxygen, nitrogen, and / or sulfur atoms) attached to at least one carbon atom, or may have a backbone consisting only of attached carbon atoms.

[0042] As used herein, the term "aromatic" defines a structure containing at least one aromatic ring (such as a diol or a portion thereof).

[0043] As used herein, the term "1,4:3,6-didehydrohexitol" refers to a heterocyclic diol obtained by double dehydration of hexitols such as mannitol, sorbitol, and idiotriol. 1,4:3,6-didehydrohexitol exists primarily in stereoisomers: isosorbide, isomannitol, and isoidiotriol. 1,4:3,6-didehydrohexitol can be used in this invention as at least one alicyclic diol (AA) to form PAES according to the invention. Preferably, the 1,4:3,6-didehydrohexitol used as an alicyclic diol (AA) in the method of this invention is isosorbide.

[0044] As used herein, the term “total weight % monomer” is defined as the weight of the monomer initially present in the reaction medium based on the total weight of the monomer and solvent.

[0045] The term "solvent" is used here in its usual sense, that is, it refers to a substance capable of dissolving another substance (solute) to form a mixture that is uniformly dispersed at the molecular level. In the case of a polymer solute, it conventionally refers 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 where phase separation occurs, often called the "cloud point," is considered to be the point at which the solution becomes cloudy or turbid due to the formation of polymer aggregates.

[0046] In this disclosure, the term "recurring unit" refers to the smallest unit of a PAES polymer that repeats in the chain and is composed of the condensation of diol compounds and dihaloaryl compounds. The term "recurring unit" is synonymous with the terms "repeating unit" and "structural unit".

[0047] As used herein, the term "homogeneous polymer" refers to a polymer having only one type of repeating unit. PAES homopolymers are obtained by the condensation of only one diol monomer and only one dihaloaryl monomer.

[0048] As used herein, the term "polymer" encompasses polymers that may have two or more different types of repeating units. PAES copolymers may be obtained by the condensation of at least two diol monomers and at least one dihaloaryl monomer, or by the condensation of at least one diol monomer and at least two dihaloaryl monomers.

[0049] As used in this article, the abbreviation "ISOSO" refers to isosorbide; the abbreviation "BPA" refers to bisphenol A or 4,4'-isopropylidene diphenol; the abbreviation "BPS" refers to bisphenol S or 4,4'-dihydroxydiphenyl sulfone; the abbreviation "BP" refers to 4,4'-biphenyl diphenol; the abbreviation "TMBPF" refers to tetramethylbisphenol F; and the abbreviations "daBPA", "daBPS" and "daBP" refer to diallyl bisphenol A, diallyl bisphenol S and diallyl 4,4'-biphenyl diphenol, respectively.

[0050] As used herein, polyethersulfone (PES) indicates a repeating unit (R) of formula (J) 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.%. PES Any polymer of:

[0051] (J),

[0052] (mol.% is based on the total number of moles of repeating units in the PES polymer). PES can be prepared by known methods, and especially from Solvay Specialty Polymers, LLC using VERADEL. ® PES is available.

[0053] As used herein, polysulfone (PSU) indicates a repeating unit (R) of formula (K) 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.%. PSU Any polymer of:

[0054] (K),

[0055] (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 particularly available from Solvay Specialty Polymers, LLC as Udel® PSU.

[0056] As used herein, polyphenylsulfone (PPSU) indicates a repeating unit (R) of formula (L) 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.%. PPSU Any polymer of:

[0057] (L),

[0058] (mol.% is based on the total number of moles of repeating units in the PPSU polymer). PPSU can be prepared by known methods, and especially from Solvay Specialty Polymers, LLC under the RADEL brand. ® PPSU is available.

[0059] The expression "weight-average molecular weight (M)" w This is used according to its general meaning, and mathematically it is expressed as:

[0060] M w = (Σ Ni• Mi 2 ) / Σ Ni•Mi

[0061] Where the sum Σ is over all chain lengths from 1 to ∞, Mi is a discrete value of the molecular weight of the polymer molecule, and Ni is the number of polymer molecules with weight Mi.

[0062] The expression "number-average molecular weight (M)" n This is used according to its general meaning, and mathematically it is expressed as:

[0063] M n = (Σ Ni•Mi) / Σ Ni

[0064] The sum Σ is over all chain lengths from 1 to ∞, and Mi and Ni are related to the expression "M w The same as defined in "".

[0065] The expression "size average molecular weight (M)" z This is used according to its general meaning, and mathematically it is expressed as:

[0066] M z = (Σ Ni• Mi 3 ) / Σ Ni•Mi 2

[0067] The sum Σ is over all chain lengths from 1 to ∞, and Mi and Ni are related to the expression "M w The same as defined in "".

[0068] As used herein, and unless otherwise expressly stated, the polydispersity index (PDI) is hereby expressed as the weight-average molecular weight (M). w ) and number-average molecular weight (M n The ratio of ) to ). This parameter indicates how wide the molecular weight range is in PAES.

[0069] As used herein, and unless otherwise expressly stated, “substantially free” of a component in a substance (such as a reaction mixture, monomer mixture, polymer, etc.) means that the concentration of that component is not more than 1 wt% or 0.5 wt% based on the total weight of the substance.

[0070] As used herein, and unless otherwise expressly stated, “free of” a component in a substance (such as a reaction mixture, monomer mixture, polymer, etc.) means that the concentration of that component is not more than 0.1 wt% or 0.05 wt% based on the total weight of the substance.

[0071] For the purposes of this invention, the expression “substantially all” in combination with the repeating units of the stated amount is intended to mean that small amounts, typically less than 1 mol.%, preferably less than 0.5 mol.%, of other repeating units may be permissible, for example as a result of lower purity of the monomer used.

[0072] For the purposes of this invention, the expression “substantially equimolar” used with respect to the total amount of hydroxyl groups from diol units and halogen groups from dihalomonomers in the reaction medium should be understood as the molar ratio between the total amount of hydroxyl groups from alicyclic diols (AA) and any optional co-diols (BB) and / or (BB') and the total amount of halogen groups from dihaloaryl sulfone monomers (CC) being 0.95 to 1.05, preferably 0.98 to 1.02, more preferably 0.99 to 1.01, and even more preferably 0.995 to 1.008.

[0073] In this specification, the selection of elements from a set of elements (such as the Markush set) is also explicitly described:

[0074] - Select two or more elements from this group.

[0075] - Select features from a subgroup of features that has had one or more features removed from it.

[0076] In the following paragraphs of this specification, even any description relating to specific embodiments is applicable to and interchangeable with other embodiments of this disclosure. Unless otherwise specified or clearly incompatible, each embodiment so defined may be combined with another embodiment. Furthermore, it should be understood that elements and / or features of the polymers, reaction media, compositions, solutions, products or articles, methods, or uses described in this specification may be expressly or implicitly combined with other elements and / or features of that polymer, reaction media, composition, solution, product or article, method, or use in all possible ways without departing from the scope of this specification.

[0077] In this application, when an element or component is referred to as being included in and / or selected from the list of enumerated elements or components, it should be understood that in the relevant embodiments explicitly considered herein, the element or component may also be any one of these individually enumerated elements or components, or may be a group consisting of any two or more of these explicitly enumerated elements or components. Any element or component listed in the list of elements or components may be omitted from this list. Furthermore, it should be understood that the elements, embodiments, and / or features of the polymers, processes, or methods described herein may be combined in various ways without departing from the scope and disclosure of this teaching, whether explicit or implicit herein.

[0078] In this specification, the description of a range of values ​​for a variable defined by a lower limit, or by an upper limit, or by both a lower limit and an upper limit, also includes embodiments in which the variable is selected from the following ranges of values: excluding the lower limit, excluding the upper limit, or excluding both the lower limit and the upper limit. Any enumeration of numerical ranges by endpoints herein includes all numbers contained within the enumerated range, as well as the endpoints and equivalents of that range.

[0079] The term "comprising" or "comprise" includes "consisting essentially of" or "consisting of" or "consist of".

[0080] The term "substantially composed of..." in relation to polymers, compositions, products, solutions, processes, methods, etc., is intended to mean any additional elements or features that may not be explicitly described herein and will not materially affect the essential and novel characteristics of such polymers, compositions, products, solutions, processes, methods, etc., may be included in such embodiments. For example, when a polymer, composition, compound, product, polymer, or solution is "substantially composed of the desired elements," it should generally be understood that any additional element may be present in amounts not exceeding 1 wt% based on the total weight of the polymer, composition, compound, product, polymer, solution, etc., or not exceeding 1 mol.% based on the total moles of the polymer, composition, compound, product, polymer, or solution. In the specific context of PAES polymers, the expression "substantially composed of..." is used to define the composition of PAES polymers to take into account end chains, defects, irregularities, and single-unit rearrangements that may be included in trace amounts in said PAES polymers without altering the essential properties of the PAES polymers.

[0081] Unless otherwise specified, the singular 'a' or 'one' used in this document includes the plural.

[0082] All disclosures of patent applications and publications cited herein are hereby incorporated by reference to the extent that they provide exemplary, procedural, or other detailed supplements to those presented herein. If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with this specification to the extent that it may obscure the terminology, this specification shall prevail.

[0083] Description of various aspects of the present invention

[0084] The inventors have unexpectedly discovered that certain cyclic aliphatic monomers with low or no endocrine-disrupting potential (some of which are derived from bio-based compounds) can be used to successfully prepare PAES homopolymers or copolymers with a suitable set of characteristics and properties (especially high molecular weight > 59 kDa) in polar aprotic solvents using inorganic metal phosphates (preferably tripotassium phosphate) as bases.

[0085] PAES homopolymers or copolymers incorporating this alicyclic monomer, as well as articles containing or made from this PAES (such as membranes for purifying water or biofluids), should exhibit lower or reduced estrogenic activity compared to PAES polymers made from bisphenol A or bisphenol S, and therefore should present a lower risk to human health.

[0086] The PAES homopolymers or copolymers according to the invention can also be efficiently prepared using cheaper dichlorodiphenyl sulfone monomers (DCDPS), thus providing a more cost-effective production, although it is true that these alicyclic diols tend to have poorer reactivity with DCDPS compared to the more reactive difluorodiphenyl sulfone monomers (DFDPS).

[0087] This is an improvement over previous PAES polymers, which were prepared from alicyclic diols using potassium carbonate as the sole base in a polar aprotic solvent, typically requiring expensive and more corrosive DFDPS. The DFDPS-based approach presents challenges for scaling up manufacturing plants for structural materials (e.g., Hasteloy®) and is also less economically viable due to higher operating costs.

[0088] Poly(aryl ether sulfone) polymer (PAES)

[0089] The applicant has now discovered that the poly(arylene ether sulfone) [PAES] prepared according to the present invention by condensation of at least one cyclic aliphatic diol monomer [hereinafter "aliphatic diol (AA)"] and at least one dihaloaryl sulfone monomer (CC) in the presence of a base containing an inorganic metal phosphate exhibits high molecular weight (preferably, M...w > 59 kDa).

[0090] In particular, compared with PAES produced by condensation of the same monomers but in the presence of potassium carbonate as the sole base during polycondensation, PAES according to the present invention have a higher Mo. w .

[0091] Furthermore, the PAES according to the invention have a narrower molecular weight distribution. In particular, the PAES according to the invention are characterized by a lower molecular weight distribution compared to PAES produced by the condensation of the same monomer but in the presence of potassium carbonate as the sole base during polycondensation. z / M w ratio.

[0092] According to the invention, PAES M z / M w Advantageously, it can be at least 1.5, preferably at least 1.51, more preferably at least 1.52, and / or PAES' M z / M w Advantageously, it can be at most 1.8, preferably at most 1.75, more preferably at most 1.7, and even more preferably at most 1.65, wherein M z It is the size average molecular weight of PAES and M w This is the weight-average molecular weight of PAES. The M of PAES w and M z Preferably, it is determined by gel permeation chromatography (GPC), which is calibrated with polystyrene standards and performed using DMAc as the mobile phase.

[0093] Phosphorus content

[0094] Therefore, one aspect of the invention relates to a PAES having a phosphorus content of at least 6 ppm P. The 'ppm P' content in the PAES is based on weight, meaning that 6 ppm corresponds to 6 micrograms of P / gram of PAES. The phosphorus content of the PAES according to the invention can be up to 150 ppm P, or up to 140 ppm P, or up to 130 ppm P, or up to 120 ppm P, or up to 110 ppm P, or up to 100 ppm P. At least a portion of the phosphorus in the PAES is not chemically bound to the PAES. Preferably, the phosphorus in the PAES is at least partially derived from inorganic metal phosphates. The phosphorus content is preferably measured by inductively coupled plasma optical emission spectrometry (ICP-OES) analysis after ashing and mineralization. A particularly suitable ICP-OES method is described in detail in the Examples section below.

[0095] The phosphorus content in PAES originates from free phosphorus-containing materials, such as residual inorganic metal phosphates (e.g., K3PO4, K2HPO4), and optionally from any phosphorus-containing materials bound to the PAES polymer chains (e.g., in side groups). At least a portion of the phosphorus in PAES is not chemically bound to the PAES. The term "free P" means that the phosphorus-containing material is not chemically bound to the PAES polymer chains and end groups. For example, free P-containing materials may be trapped in the polymer chains or adsorbed onto the polymer chains. The term "bound P" means that the phosphorus-containing material is chemically bound to the PAES polymer chains (e.g., through phosphate-containing side groups and / or phosphate-containing end groups). Preferably, more than 80 wt% and up to 100 wt% of the phosphorus content in PAES originates from free phosphorus-containing materials, preferably from inorganic metal phosphates, and more preferably from residual potassium phosphate (ternary, binary, or monophosphate).

[0096] Preferably, the PAES according to the invention has a free (unbound) phosphorus content of at least 6 ppm P, and preferably at most 150 ppm P, or at most 140 ppm P, or at most 130 ppm P, or at most 120 ppm P, or at most 110 ppm P, or at most 100 ppm P. The phosphorus content is preferably measured by ICP-OES analysis after ashing and mineralization.

[0097] PAES sulfone repeating unit (R) a )

[0098] PAES according to the present invention preferably contains at least one sulfone repeating unit (R a The at least one sulfone repeating unit is obtained by condensation of at least one dihaloaryl sulfone monomer (CC) containing at least one -S(=O)2- group and at least one alicyclic diol (AA) containing at least one alicyclic moiety (M).

[0099] The alicyclic moiety (M) may contain only one non-aromatic ring.

[0100] Alternatively, the alicyclic moiety (M) may contain two or more non-aromatic rings. The two or more non-aromatic rings may be fused together by sharing two or more adjacent ring carbon atoms, or they may be linked by single bonds or connected alkylene groups (such as -(CH2)). p - where p ≥ 1 or -C(CH3)2-) is connected.

[0101] The alicyclic moiety (M) may contain at least one heteroatom in the ring, such as at least one oxygen atom and / or at least one nitrogen atom.

[0102] Alternatively, at least one alicyclic moiety (M) does not contain any heteroatoms in the ring.

[0103] The sulfone repeating unit (R) of PAES according to the present invention a It has the following general formula (I):

[0104] -[Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ] m -OEO-(I),

[0105] Wherein E contains at least one alicyclic moiety (M) and is a group containing 4 to 30 carbon atoms, preferably 4 to 15 carbon atoms or 4 to 10 carbon atoms;

[0106] Where n and m are independently 0, 1, 2, 3 or 4;

[0107] Among them, Ar 3 Ar 4 They may be the same as or different from each other, and are aromatic components with the following formula:

[0108] ;

[0109] Among them, Ar 5 Choose from the following groups:

[0110]

[0111] Among them, Ar 3 Ar 4 Ar 5 Each R in any one of them is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO3H), alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and each i is independently 0, 1, 2, 3 or 4.

[0112] In the sulfone repeating unit (R) with general formula (I) a In this context, n and m are preferably 0, 1, or 2 independently; more preferably, n and m are 0 or 1.

[0113] Furthermore, when Ar 3 Ar 4 Ar 5When i in any one of them is 1, 2, 3 or 4, each R corresponding to such i is preferably independently selected from the group consisting of: halogens, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates and sulfonic acids (-SO3H).

[0114] More preferably, aspartic Ar 3 Ar 4 Ar 5 Each i in the formula is 0, and in the sulfone repeating unit (R) with the general formula (I) a ) in Ar 3 Ar 4 Ar 5 The aromatic rings in Ar were not replaced by R. In other words, Ar 3 Ar 4 Ar 5 It contains only unsubstituted aryl groups.

[0115] Sulfone repeating unit (R) a The part in formula (I) of ) - [Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ] m -Derived from at least one dihalogenated aryl sulfone monomer (CC).

[0116] Sulfone repeating unit (R) a The part of formula (I) of ) -OEO- is derived from at least one alicyclic diol (AA).

[0117] In particular, sulfone repeating units (R a Preferably, it has the following formula (Ia):

[0118] (Ia),

[0119] in:

[0120] - Each R1 is independently selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammoniums;

[0121] - For each R1, i is 0, 1, 2, 3, or 4; and

[0122] -E contains at least one cyclic aliphatic moiety (M) and is a group containing 4 to 30 carbon atoms, preferably 4 to 15 carbon atoms.

[0123] When i in formula (Ia) is not zero, each R1 corresponding to such i is preferably independently selected from the group consisting of: alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium.

[0124] In equation (Ia), for each R1, i is preferably 0.

[0125] Sulfone repeating unit (R) a More preferably, it has the following formula (Ib):

[0126] (Ib),

[0127] E, each R1, and each i are the same as those defined in equation (Ia).

[0128] When i in formula (Ib) is not zero, each R1 corresponding to such i is preferably independently selected from the group consisting of: alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium.

[0129] In equation (Ib), for each R1, i is preferably 0.

[0130] Sulfone repeating unit (R) a More preferably, it is represented by the following formula (Ic):

[0131] (Ic),

[0132] E is the same as that defined in equation (Ia).

[0133] In any of equations (I), (Ia), (Ib), and (Ic), E is preferably selected from the group consisting of those having equations (E1) to (E11):

[0134]

[0135]

[0136]

[0137]

[0138] (E11), and any combination thereof.

[0139] Each symbol in these equations (E1) to (E11) Indicates the position of the E bond to the oxygen atom in the -OEO- pattern; and

[0140] In equation (E11), each Q' that is the same or different is a non-cyclic part.

[0141] According to formulas (E4) to (E10), E can exist in different stereochemical arrangements. For simplicity, the stereochemistry of the bonds in formulas (E4) to (E10), especially C-, is not indicated in this specification. The stereochemical arrangement of the bonds. It must be understood that all stereoisomers, each individually and mixtures thereof, are covered by each of formulas (E4) through (E10).

[0142] Although not preferred, the -OEO- group in any of formulas (I), (Ia), (Ib), and (Ic) can be derived from an alicyclic diol (AA) containing a noncyclic alicyclic diol end group.

[0143] For example, when the alicyclic diol (AA) is isosorbide with a noncyclic aliphatic terminal group, E can be represented by formula (E11), where the noncyclic portion Q' can be represented by formula (VI): -[R k -O-] z -R k -,

[0144] Where R k Selected from alkylene groups, preferably R k Selected from alkylene groups having 1 to 10 carbon atoms, more preferably R k Choose from the following groups: methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH] 2- [CH2-CH2], 2,2-dimethylpropylidene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-1,3-propylidene [CH2-C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-1,3-pentylene [CH(C(CH3)2)-C(CH3)2-CH2], and any combination thereof; and z is 0 or an integer from 1 to 500, preferably z is an integer from 2 to 200, more preferably z is an integer from 2 to 100, and even more preferably z is an integer from 2 to 50.

[0145] Preferably, when E is represented by equation (E11), the non-circular portion Q' can be represented by any one of the following equations: (VI'), (VI”), (VI'”), and (VI””).

[0146] -[CH2-CH2-O] z -CH2-CH2-(VI'),

[0147] -[CH2-CH(CH3)-O] z -CH2-CH(CH3)-(VI”),

[0148] -[CH2-CH2-CH2-CH2-O] z -CH2-CH2-CH2-CH2-(VI'”),

[0149] -[CH2-C(CH3)2-CH2-O] z -CH2-C(CH3)2-CH2-(VI””),

[0150] Where z is 0 or an integer from 1 to 500, preferably z is an integer from 2 to 200, more preferably z is an integer from 2 to 100, and even more preferably z is an integer from 2 to 50.

[0151] The repeating unit in the PAES according to the invention may contain more than 10 wt%, preferably more than 30 wt%, more preferably more than 50 wt%, even more preferably more than 70 wt%, and most preferably more than 90 wt% of sulfone repeating units (R). a The wt% is relative to the total weight of the repeating units in PAES.

[0152] Preferred sulfone repeating units (R) for PAES polymers a It can be represented by any of the following equations (Ic-1) to (Ic-5):

[0153] (Ic-1)

[0154] (Ic-2)

[0155] (Ic-3)

[0156] (Ic-4)

[0157] (Ic-5).

[0158] Sulfone repeating unit (R) for PAES polymers aIt can be alternatively represented by any of the following equations (Ic-6) and / or (Ic-8):

[0159] (Ic-6)

[0160] (Ic-8).

[0161] The PAES according to the present invention can be a homopolymer, and its repeating units can be substantially composed of sulfone repeating units (R). a Composition. In this case, the sulfone repeating unit (R) a E is preferably represented by formula (Ic), where E is a portion represented by any one of formulas (E1), (E2), (E3), (E4), (E5), (E6), (E7), (E8), (E9), (E10) and / or (E11) as defined herein, preferably a portion represented by any one of formulas (E1), (E2), (E3), (E4), (E5), (E6), (E8) and / or (E11), more preferably a portion represented by any one of formulas (E1), (E4), (E5), (E6), (E8) and / or (E11), even more preferably a portion represented by any one of formulas (E1), (E4), (E5) and / or (E11), and even more preferably a portion represented by formulas (E1) and / or (E11).

[0162] Optional sulfone aromatic repeating unit (R) b ) and / or (R c )

[0163] The PAES according to the present invention may comprise sulfone repeating units (R) as detailed above. a ) and at least one additional sulfone repeating unit (R b ) and / or (R c copolymers of ).

[0164] Other repeating units (R) b A repeating unit is made of at least one dihaloaryl sulfone monomer (CC) and at least one aromatic diol (BB).

[0165] Other repeating units (R) c ) is a repeating unit made of at least one dihaloaryl sulfone monomer (CC) and at least one noncyclic diol (BB').

[0166] When the PAES according to the invention is a copolymer, its repeating unit may contain more than 10 wt%, preferably more than 30 wt%, more preferably more than 50 wt%, even more preferably more than 70 wt%, and most preferably more than 90 wt% of sulfone repeating units (R) as detailed above. a ) and at least one additional sulfone repeating unit (R b ) and / or (R c The wt% is relative to the total weight of the repeating units in PAES.

[0167] When PAES is a copolymer, its repeating units can be essentially composed of sulfone repeating units (R... a ) and at least one additional sulfone repeating unit (R b ) and / or (R c Composition.

[0168] Optional sulfone repeating unit (R) b )

[0169] Optional sulfone repeating unit (R) b It is made from at least one dihaloaryl sulfone monomer (CC) and at least one aromatic diol (BB). The at least one aromatic diol (BB) is different from the at least one alicyclic diol (AA).

[0170] It should be understood that at least one aromatic diol (BB) contains at least two hydroxyl groups. This means that, in the context of this invention, aromatic diols (BB) also encompass any aromatic compound (BB) having more than two hydroxyl groups. Aromatic compounds (BB) with 3 to 6 hydroxyl groups, especially 3 or 4 hydroxyl groups, can be envisioned. Used as an aromatic diol (BB) or as an aromatic diol (BB) to prepare a sulfone repeating unit (R) by reacting with at least one dihaloaryl sulfone monomer (CC). b For example, aromatic diols (BB) may include or may be aromatic triols, such as 1,1,1-tris-(4-hydroxyphenyl)-ethane.

[0171] As a method for preparing sulfone repeating units (R) by condensation with at least one dihaloaryl sulfone monomer (CC). b Non-limiting examples of suitable aromatic diols (BBs) may include bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4'-biphenyl, diallyl biphenyl, bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, hydroquinone, resorcinol, aromatic triols (such as 1,1,1-tri-(4-hydroxyphenyl)-ethane) and any combination thereof.

[0172] Sulfone repeating unit (R) b It can have the following general formula (II):

[0173] -[Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ] m -OWO-(II),

[0174] Where n, m, and Ar 3 Ar 4 and Ar 5 For repeating units (R) with general formula (I) a The same as those defined; and

[0175] Where W is defined by general formula (III): -Ar 6 -(T-Ar 7 ) y -(III),

[0176] in

[0177] -T is selected from the group consisting of: bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CCl3)2-, -C(=CCl2)-, -CH2-, -O-, -C(O)-, -S-, -SO-, -C(CH3)(CH2CH2COOH)- and any combination thereof; preferably, T is selected from the group consisting of: bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -CH2-, -C(O)- and any combination thereof; more preferably, T is selected from the group consisting of: bond, -SO2-, -C(CH3)2-, -CH2- and any combination thereof.

[0178] -y is 0 or 1, and

[0179] -Ar 6 Ar 7 The aromatic components are either identical or different from each other, and are represented by any one of the following formulas: (H), (H'), and (H”).

[0180] (H), (H'), (H”),

[0181] In any one of formulas (H), (H'), and (H”), R' is selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium; and in any one of formulas (H), (H'), and (H”), j' is 0, 1, 2, 3, or 4.

[0182] j' is 0 when the aromatic ring in any of the parts represented by equations (H), (H'), and (H”) is not substituted.

[0183] Sulfone repeating unit (R) b The part in equation (II) of ) - [Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ] m -Derived from at least one dihalogenated aryl sulfone monomer (CC).

[0184] Sulfone repeating unit (R) b The -OWO- in formula (II) is derived from at least one aromatic diol (BB) having the formula HO-W-OH.

[0185] Preferably, W in equation (II) is represented by equation (IIIa):

[0186] -Ar 6 -T-Ar 7 -(IIIa),

[0187] in:

[0188] -T can be selected from the following groups: bond, -SO2-, -C(CH3)2-, -CH2- and any combination thereof, and

[0189] -Ar 6 and Ar 7 Each of them is an unsubstituted aryl group having the formula (H), where j'=0.

[0190] Alternatively, W in equation (II) can be represented by equation (IIIa):

[0191] -Ar 6 -T-Ar 7 -(IIIa),

[0192] in:

[0193] -T is -CH2-, and

[0194] -Ar 6 and Ar 7 Each of them is an unsubstituted arylene with formula (H) where j'=0, or a substituted arylene with formula (H) where j'=2 and R' is methyl;

[0195] or

[0196] in:

[0197] -T can be selected from the following groups: bond, -SO2-, -C(CH3)2- and any combination thereof, and

[0198] -Ar 6 and Ar 7 Each of them is an unsubstituted aryl group having formula (H), where j'=0, or a substituted aryl group having formula (H), where j'=1, and each R' is an allyl group having any of the following formulas:

[0199] -(CH2) k -CH = CH-CH3 or -(CH2) k+1 -CH=CH2,

[0200] Where k is 0 or an integer from 1 to 4.

[0201] Alternatively, W in equation (II) can be represented by equation (IIIb):

[0202] -Ar 6 -(IIIb),

[0203] Among them, Ar 6 It is an unsubstituted aryl group having the formula (H) or (H'), where j'=0.

[0204] The other sulfone repeating unit (R) b Preferably, it is represented by the following formula (IIa):

[0205] (IIa),

[0206] in:

[0207] - Each R1 is independently selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammoniums;

[0208] - For each R1, i is 0, 1, 2, 3, or 4; and

[0209] -W is the same as that defined in equation (II).

[0210] When i in formula (IIa) is not zero, each R1 corresponding to such i is preferably independently selected from the group consisting of: alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium.

[0211] In equation (IIa), for each R1, i is preferably 0.

[0212] The other sulfone repeating unit (R) in PAES b More preferably, it is represented by any one of the following formulas (IIb), (IIc), (IId), (IIe), (IIIf), (IIg), or any combination thereof:

[0213] (IIb)

[0214] (IIc)

[0215] (IId)

[0216] (IIe)

[0217] (IIf)

[0218] (IIg),

[0219] Where each R1 and i in any of equations (IIb), (IIc), (IId), (IIe), (IIIf), and (IIg) is the same as that defined for equation (IIa), and

[0220] In formula (IIg), T is selected from the following groups: bond, -SO2-, -C(CH3)2- and any combination thereof.

[0221] When i is not zero in any of formulas (IIb) to (IIg), R1 corresponding to such i is preferably independently selected from the group consisting of: alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium.

[0222] In any of equations (IIb) to (IIg), for each R1, i is preferably 0.

[0223] The other sulfone repeating unit (R) in PAES b More preferably, it has formula (IIb).

[0224] The other sulfone repeating unit (R) in PAES b Even more preferably, it has equation (IIb), where for each R1, i is 0.

[0225] When PAES contains sulfone repeating units (R) a ) and (R b When both are present, the sulfone repeating unit (R) a ) and sulfone repeating unit (R b The molar ratio r b It could be:

[0226] - Up to 95:5, preferably up to 90:10, more preferably up to 85:15, and even more preferably up to 80:20, and / or

[0227] - At least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, even more preferably at least 50:50, even more preferably at least 60:40, or even more preferably at least 65:35.

[0228] When the PAES according to the present invention is wherein substantially all of its repeating units are sulfone repeating units (R) a ) and (R b When copolymerizing ), its preferred sulfone repeating unit (R) a This can be expressed by equation (Ib-1):

[0229] (Ib-1),

[0230] And its preferred sulfone repeating unit (R) b This can be expressed by equation (IIb-1):

[0231] (IIb-1).

[0232] This type of PAES copolymer [where its repeating units are essentially composed of repeating units (R) having the formula (Ib-1)] a ) and (R) having formula (IIb-1) b One of the advantages of the composition is that its repeating units are composed of units (R) having formula (IIb-1).b The Tg of the homopolymer (commonly known as PPSU) PPSU = 220°C) compared to a higher Tg.

[0233] Another advantage of this PAES copolymer is that it does not contain bisphenol S and bisphenol A.

[0234] Furthermore, at least two different sulfone repeating units exist: sulfone repeating units (R) having formula (Ib-1). a ) and sulfone repeating units (R) having formula (IIb-1) b In the case of ), the hydrophilicity of this PAES copolymer can be improved by changing these different sulfone repeating units (R). a ) and (R b The relative amount of ) can be adjusted. For example, if it is desired to increase the hydrophilicity of the PAES copolymer (e.g., for its use in membranes), it can be adjusted relative to other sulfone repeating units (R) having formula (IIb-1). b Add a sulfone repeating unit (R) with formula (Ib-1) a The amount of ). For example, 50:50 to 90:10 of sulfone repeating units (R) with formula (Ib-1). a ) and sulfone repeating units (R) having formula (IIb-1) b The molar ratio r b This is quite advantageous for the application of this membrane.

[0235] Optional sulfone repeating unit (R) c )

[0236] Another optional sulfone repeating unit (R) c ) can be present in the PAES copolymer of the present invention. Optional sulfone repeating units (R c It is made from at least one dihaloaryl sulfone monomer (CC) and at least one aliphatic (non-aromatic) noncyclic diol monomer (BB') having the formula (D”): HO-Q-OH [hereinafter “noncyclic diol (BB')”].

[0237] Acyclic diols (BB') differ from alicyclic diols (AA) and aromatic diols (BB). Acyclic diols (BB') can be straight-chain or branched.

[0238] Non-limiting examples of noncyclic diols (BB') may be selected from epoxides and / or poly(epoxides), preferably from the group consisting of: ethylene glycol, propylene glycol [HO-CH2-CH(CH3)-OH], 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, poly(ethylene glycol), poly(propylene glycol), poly(tetramethylene oxide), and any combination of two or more thereof.

[0239] Non-limiting examples of noncyclic diols (BB') that are straight-chain aliphatic diols are ethylene glycol, poly(ethylene glycol), tetramethylene oxide, poly(tetramethylene oxide), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and / or 1,10-decanediol.

[0240] Non-limiting examples of noncyclic diols (BB') that are branched aliphatic diols are 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, propylene glycol and / or poly(propylene glycol).

[0241] Suitable acyclic diols (BB') advantageously have a molecular weight of at least 60 g / mol and less than 2000 g / mol, preferably up to 1800 g / mol, more preferably up to 1500 g / mol, even more preferably up to 1300 g / mol, even more preferably up to 1100 g / mol, and most preferably up to 900 g / mol.

[0242] Preferably, the acyclic diol (BB') is polyethylene glycol [“PEG”] and / or 2,2-dimethylpropane-1,3-diol [“DMP”] (also known as neopentyl glycol). PEG may have a molecular weight of less than 2000 g / mol, preferably up to 1800 g / mol, more preferably up to 1500 g / mol, even more preferably up to 1300 g / mol, even more preferably up to 1100 g / mol, and most preferably up to 900 g / mol.

[0243] Sulfone repeating unit (R) c It can have the following general formula (IV):

[0244] -[Ar3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ] m -OQO-(IV),

[0245] Where Q is the acyclic portion derived from the acyclic diol (BB'); and

[0246] Where n, m, and Ar 3 Ar 4 and Ar 5 For repeating units (R) with general formula (I) a The same as those defined.

[0247] Optional sulfone repeating unit (R) c The part in formula (IV) of ) - [Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ] m -Derived from at least one dihalogenated aryl sulfone monomer (CC).

[0248] Optional sulfone repeating unit (R) c The part -OQO- in formula (IV) is derived from at least one noncyclic diol (BB') having formula (D”): HO-Q-OH.

[0249] At least one acyclic diol (BB') may be a straight-chain or branched aliphatic diol.

[0250] Non-limiting examples of acyclic diols (BB') from which the acyclic portion Q can be derived are selected from epoxides and / or poly(epoxides), preferably from the group consisting of: ethylene glycol, propylene glycol [HO-CH2-CH(CH3)-OH], 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, poly(ethylene glycol), poly(propylene glycol), poly(tetramethylene oxide), and any combination of two or more thereof.

[0251] The non-cyclic portion Q can be represented by equation (V): -[R k -O-]z -R k -,

[0252] Where R k Selected from alkylene groups, preferably alkylene groups having 1 to 10 carbon atoms, more preferably R k Choose from the following groups: methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH] 2- [CH2-CH2], 2,2-dimethylpropylidene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-1,3-propylidene [CH2-C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-1,3-pentylene [CH(C(CH3)2)-C(CH3)2-CH2] and any combination thereof; and z is 0 or an integer from 1 to 500.

[0253] Preferably, the non-circular portion Q is represented by any one of the following formulas: (V'), (V”), (V'”), and (V””).

[0254] -[(CH2)2-O] z -(CH2)2-(V'),

[0255] -[CH2-CH(CH3)-O] z -CH2-CH(CH3)-(V”),

[0256] -[(CH2)4-O] z -(CH2)4-(V'”),

[0257] -[CH2-C(CH3)2-CH2-O] z -CH2-C(CH3)2-CH2-(V””),

[0258] Where z is 0 or an integer from 1 to 500.

[0259] When the acyclic portion Q is derived from poly(epoxyalkylene), z is an integer from 1 to 500, preferably an integer from 2 to 200, and more preferably an integer from 2 to 100.

[0260] When the acyclic diol (BB') having the formula (D”): HO-Q-OH (where Q is represented by any one of formulas (V), (V'), (V”), (V”’) and (V””) is a poly(epoxide), z in any of these formulas is preferably selected such that the average molecular weight (Mn) of the acyclic diol (BB') having the formula (D”): HO-Q-OH does not exceed 30,000 g / mol.

[0261] Optional sulfone repeating unit (R) in PAES c Preferably, it has the following formula (IIIa):

[0262] (IIIa),

[0263] In equation (IIIa):

[0264] - Each R1 is independently selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammoniums;

[0265] - For each R1, i is 0, 1, 2, 3, or 4; and

[0266] -Q is represented by any one of the above-defined formulas (V), (V'), (V”), (V'”), and (V””).

[0267] When i in formula (IIIa) is not zero, each R1 corresponding to such i is preferably independently selected from the group consisting of: alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium.

[0268] In equation (IIIa), for each R1, i is preferably 0.

[0269] Sulfone repeating unit (R) in PAES c More preferably, it has the following formula (IIIb):

[0270] (IIIb),

[0271] In equation (IIIb), Q is represented by any one of the equations (V), (V'), (V”), (V'”), and (V””) as defined in this paper.

[0272] When PAES contains sulfone repeating units (R) a ) and (R c When both are present, the sulfone repeating unit (R) a ) and sulfone repeating unit (R c The molar ratio r c yes:

[0273] - Up to 95:5, preferably up to 90:10, more preferably up to 85:15, and even more preferably up to 80:20, and / or

[0274] - At least 10:90, preferably at least 20:80, more preferably at least 30:70, even more preferably at least 40:60, even more preferably at least 50:50, or even more preferably at least 60:40.

[0275] intrinsic viscosity of PAES

[0276] The PAES according to the invention preferably has an intrinsic viscosity (IV) of at least 0.40 dL / g. The PAES according to the invention may have an intrinsic viscosity (IV) of up to 1.5 dL / g. The intrinsic viscosity (IV) of the PAES is preferably measured at 20°C in dichloromethane / trifluoroacetic acid (9 / 1 v / v) at 0.2 g / 100 mL.

[0277] halogen content of PAES

[0278] The PAES according to the invention can have a halogen content greater than 0 ppm (> 0 ppm) and less than or equal to 4000 ppm (≤ 4000 ppm), where ppm is based on the weight of the PAES. Within this range, the halogen content can be greater than or equal to 200 ppm (≥ 200 ppm), or ≥ 300 ppm. Also within this range, the halogen content can be ≤ 3500 ppm, or ≤ 3000 ppm, or ≤ 2500 ppm, or even ≤ 2200 ppm.

[0279] Alternatively, the halogen content may be >0 ppm and ≤900 ppm, or >0 ppm and ≤800 ppm, or >0 ppm and ≤700 ppm, or >0 ppm and ≤500 ppm, or even >0 ppm and ≤300 ppm. The halogen is selected from the group consisting of chlorine, bromine, iodine, fluorine, and any combination thereof, preferably chlorine and / or fluorine.

[0280] The PAES according to the invention preferably has a chlorine content greater than 0 ppm and less than or equal to 4000 ppm (>0 ppm to 4000 ppm), where ppm is based on the weight of PAES. Within this range, the chlorine content can be ≥200 ppm or ≥300 ppm. Also within this range, the chlorine content can be ≤3500 ppm, or ≤3000 ppm, or ≤2500 ppm, or even ≤2200 ppm.

[0281] The 'ppm' of halogen content (preferably chlorine content) is based on weight, meaning that 100 ppm of halogen (Cl) is equivalent to 100 micrograms of halogen / g PAES. Halogen content, especially chlorine content, can be measured by combustion ion chromatography (IC combustion), a halogen analyzer, or X-ray fluorescence (XRF). A particularly suitable method for measuring chlorine content in PAES using a chlorine analyzer is detailed in the following examples.

[0282] The halogen content of PAES preferably includes the concentration of halogen end groups of PAES. Other sources of halogen content in PAES may be free halogens and / or any free halogenated compounds, where "free" means unbound to the polymer chain and end groups of PAES. Yet another source of halogens in PAES may be Cl and / or any chlorinated compounds bound to the PAES polymer chain (e.g., in side groups), (e.g., from repeating units (R... a In any one of the formulas (Ia) to (Ig), the optional repeating unit (R) b In equation (IIa) and the optional repeating unit (R) c The halogen of the R1 side group in formula (IIIa).

[0283] The halogen content of PAES can be basically composed of the content of halogen end groups in PAES.

[0284] Physical and thermal properties of PAES

[0285] The PAES according to the invention are advantageously transparent and amorphous. Amorphous PAES can have a heat of fusion of less than about 5 J / g, preferably less than about 3 J / g, which is measured using differential scanning calorimetry (“DSC”).

[0286] When the repeating unit of PAES is essentially composed of sulfone repeating units (R) having formula (Ic) a When PAES according to the invention is composed of (where E is selected from the group consisting of those formulas (E1) to (E5)), the PAES has the following glass transition temperature (Tg):

[0287] - At least 215°C, preferably at least 218°C, more preferably at least 220°C, even more preferably at least 222°C, and / or at least 225°C

[0288] - Up to 255°C, preferably up to 250°C, more preferably up to 245°C, even more preferably up to 240°C, and even more preferably up to 235°C.

[0289] The glass transition temperature (Tg) of the PAES according to the invention is preferably measured by differential scanning calorimetry (DSC). Unless otherwise indicated, a second heating curve is used to provide the Tg value. Particularly suitable DSC methods for measuring Tg are detailed in the following examples.

[0290] When the repeating unit of PAES is essentially composed of sulfone repeating units (R) having formula (Ic) a When PAES according to the present invention is composed of (where E has the formula (E8)), the following glass transition temperature (Tg) is obtained:

[0291] - At least 110°C, preferably at least 115°C, more preferably at least 120°C, and even more preferably at least 125°C; and / or

[0292] - Up to 200°C, preferably up to 190°C, more preferably up to 180°C, and even more preferably up to 170°C.

[0293] When the repeating unit of PAES is essentially composed of sulfone repeating units (R) having formula (Ic) a When PAES according to the present invention is composed of (where E has the formula (E6)), the following glass transition temperature (Tg) is obtained:

[0294] - At least 235°C, preferably at least 240°C, more preferably at least 245°C, and even more preferably at least 255°C; and

[0295] - Up to 270°C, preferably up to 265°C, more preferably up to 260°C, even more preferably up to 240°C, and even more preferably up to 235°C.

[0296] Molecular weight and molecular weight distribution of PAES

[0297] PAES according to the invention advantageously have a weight-average molecular weight (Mi) greater than 59,000 g / mol, preferably at least 60,000 g / mol, more preferably at least 65,000 g / mol. w Number-average molecular weight of PAES (M) w The upper limit of the molecular weight (M) is not particularly important and will be selected by those skilled in the art in view of the intended use. Typically, PAES according to the invention can have a weight-average molecular weight (M) equal to or less than 120,000 g / mol, preferably equal to or less than 110,000 g / mol, or more preferably equal to or less than 100,000 g / mol, and even more preferably equal to or less than 95,000 g / mol. w ).

[0298] PAES advantageously have a weight-average molecular weight (Mi) in the range of more than 59,000 g / mol and up to 120,000 g / mol, preferably in the range of 60,000 g / mol to 110,000 g / mol, and more preferably in the range of 65,000 g / mol to 100,000 g / mol. w ).

[0299] PAES according to the invention advantageously have a number-average molecular weight (Mg) greater than 21,000 g / mol, preferably at least 25,000 g / mol, more preferably at least 30,000 g / mol. n Number-average molecular weight of PAES (M) n The upper limit of the molecular weight (M) is not particularly important and will be selected by those skilled in the art in view of the intended use. Typically, PAES according to the invention can have a number-average molecular weight (Mn) of 100,000 g / mol or less, preferably 90,000 g / mol or less than 80,000 g / mol, more preferably 70,000 g / mol or less than 68,000 g / mol, even more preferably 60,000 g / mol or less than 55,000 g / mol, and even more preferably 50,000 g / mol or less than 50,000 g / mol. n ).

[0300] PAES advantageously have a number-average molecular weight (Mn) in the range of 21,000 g / mol to 80,000 g / mol, preferably in the range of 25,000 g / mol to 60,000 g / mol, and more preferably in the range of 30,000 g / mol to 50,000 g / mol. n ).

[0301] The molecular weight of PAES can be determined using any suitable method. For example, it can be determined using... 1 1H-NMR and gel permeation chromatography (GPC) (also known as size exclusion chromatography (SEC)). Unless otherwise explicitly stated, the weight-average molecular weight (M) of PAES is... w Number-average molecular weight (M) n ) and size average molecular weight (M z The GPC is estimated, preferably calibrated with polystyrene standards and performed using a mobile phase. The mobile phase can be selected from any solvent used in the PAES described herein, such as N-methyl-2-pyrrolidone (NMP), N,N′-dimethylacetamide (DMAc), tetrahydrofuran (THF), sulfolane, or dichloromethane, preferably NMP or DMAc, more preferably DMAc. The M of PAES w M n and Mz Preferably, the determination is made by GPC, which is calibrated with polystyrene standards and performed using DMAc as the mobile phase. Particularly suitable GPC methods are detailed in the following examples.

[0302] The molecular weight distribution (MWD) of PAES can be characterized by the weight-average molecular weight (Mb) of PAES. w The number-average molecular weight (M) of PAES n The polydispersity index (PDI) of PAES (=M). w / M n The PDI of PAES can advantageously be at least 1.8, preferably at least 1.85, and / or the PDI of PAES can advantageously be at most 2.5, preferably at most 2.3.

[0303] The molecular weight distribution (MWD) of PAES can be determined by the size-average molecular weight (Mb) of PAES. z The weight-average molecular weight (M) of PAES w The ratio of (M) z / M w To characterize PAES's M. z / M w Advantageously, it can be at least 1.5, preferably at least 1.51, more preferably at least 1.52, and / or PAES' M z / M w Advantageously, it can be up to 1.8, preferably up to 1.75, more preferably up to 1.7, and even more preferably up to 1.65.

[0304] To calculate the PAES ratio (M z / M w ) and PDI (M w / M n The M of PAES is preferably determined by gel permeation chromatography (GPC) (which is calibrated with polystyrene standards and uses DMAc as the mobile phase). w M n and M z .

[0305] Other features / characteristics of PAES

[0306] PAES advantageously contain less than 10 ppm, preferably less than 5 ppm, and more preferably less than 1 ppm of BPA, based on the total weight of PAES.

[0307] PAES advantageously contain less than 10 ppm, preferably less than 5 ppm, and more preferably less than 1 ppm of BPS, based on the total weight of PAES.

[0308] PAES are preferably substantially free of (e.g., less than 1 ppm) BPA and BPS.

[0309] The BPS content in PAES can be measured by liquid chromatography analysis of a PAES solution in N,N-dimethylformamide (DMF) after polymer precipitation with acetonitrile. Suitable analytical methods are described in examples.

[0310] The BPA content in PAES can be measured by gas chromatography analysis of a PAES solution in DMF or chloroform. Suitable analytical methods for measuring BPA content are described in the examples.

[0311] PAES advantageously contains no more than 10 wt%, preferably no more than 8 wt%, more preferably no more than 5 wt%, and most preferably no more than 2 wt% of an oligomer fraction having a molecular weight of less than 3000 g / mol, said wt% being based on the total weight of PAES.

[0312] The content of this oligomer fraction with a molecular weight of less than 3000 g / mol in PAES can be measured from the slice data of the GPC chromatogram using gel permeation chromatography software calibrated with polystyrene standards. In this case, it corresponds to:

[0313]

[0314] Where AU (detector response in mV) is the y-axis unit, and log M (logarithm of molecular weight) is the x-axis unit.

[0315] PAES advantageously have a residual polar aprotic solvent content of less than 3000 ppm, preferably less than 2500 ppm, more preferably less than 2000 ppm, most preferably less than 1000 ppm and most preferably less than 500 ppm, said ppm based on the total weight of PAES.

[0316] PAES are preferably substantially free of (e.g., less than 500 ppm) polar aprotic solvents.

[0317] The content of residual polar aprotic solvents in PAES can be measured by gas chromatography (GC) analysis of PAES solutions in solvents such as N,N-dimethylformamide (DMF) or different solvents (if DMF is the solvent to be quantified). A suitable method for measuring the content of residual polar aprotic solvents is described in the examples.

[0318] Advantageously, the PAES according to the invention has a phosphorus content of at least 6 ppm, and preferably at most 150 ppm, and preferably the PAES further has at least one of the following characteristics:

[0319] - A weight-average molecular weight (M) of at least 60,000 g / mol, and preferably at most 120,000 g / mol. w );

[0320] - A number-average molecular weight (Mn) of at least 21,000 g / mol, and preferably at most 80,000 g / mol. n );

[0321] - Characteristic M is at least 1.5 and at most 1.8 z / M w The molecular weight distribution of the ratio;

[0322] -The following chlorine content:

[0323] At least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm, and even more preferably at least 300 ppm, and / or

[0324] Up to 3000 ppm, preferably up to 2900 ppm, more preferably up to 2800 ppm;

[0325] - Bisphenol A in amounts less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm;

[0326] - Bisphenol S in amounts less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm;

[0327] - An amount of oligomer fraction having a molecular weight of less than 3000 g / mol, not exceeding 10 wt%, preferably not exceeding 8 wt%, more preferably not exceeding 5 wt%, and most preferably not exceeding 2 wt%; and / or

[0328] - Residual polar aprotic solvent content of less than 3000 ppm, preferably less than 2500 ppm, more preferably less than 2000 ppm, most preferably less than 1000 ppm and most preferably less than 500 ppm;

[0329] The ppm and wt% are based on the total weight of PAES.

[0330] Methods for manufacturing PAES

[0331] The present invention further relates to a method for manufacturing PAES, the PAES comprising a condensed sulfone repeating unit (R) derived from at least one dihaloaryl sulfone monomer (CC) containing at least one -S(=O)2- group and at least one alicyclic diol monomer (AA) containing at least one alicyclic moiety (M). a It may also optionally further comprise other sulfone repeating units derived from the condensation of a dihaloaryl sulfone monomer (CC) and at least one aromatic codiol monomer (BB) and / or an acyclic codiol monomer (BB'), said codiol monomer being different from an alicyclic diol (AA).

[0332] The method preferably involves reacting at least one alicyclic diol (AA), any optional co-diol (BB), and / or (BB') with at least one dihaloaryl sulfone monomer (CC) in a reaction medium containing a polar aprotic solvent and a base.

[0333] The reaction is preferably carried out in one stage. This means that the deprotonation of alicyclic diols (AA) and optional co-diols (BB) and / or (BB') with a base, and the condensation reaction between alicyclic diols (AA) and optional co-diols (BB) and / or (BB') with dihaloaryl sulfone monomers (CC) are carried out in a single reactor vessel without separating the intermediate products.

[0334] Alternatively, the reaction can also take place in two or more stages.

[0335] For example, the reaction can take place in two stages:

[0336] - By premixing monomers [(AA), (CC), optional (BB), optional (BB')] with a polar aprotic solvent in a reactor vessel, and then adding a base to the premix, or

[0337] - By premixing the base with a polar aprotic solvent in a reactor vessel, and then later adding one or more monomers to the premix.

[0338] Alternatively, the reaction can be carried out in two or more consecutive polymerization stages, wherein the reaction medium is gradually diluted with a solvent to gradually reduce the concentration (wt%) of monomers (i.e., alicyclic diols (AA), optional co-diols (BB) and / or (BB'), dihaloaryl sulfone monomers (CC)) in the reaction medium during the polymerization process. This gradual solvent dilution allows for optimization between reactivity and the viscosity of the reaction medium. Preferably, the initial monomer concentration (total wt% monomers) in the reaction medium can be 55 wt% to 45 wt% (in the first stage), while the final monomer concentration (total wt% monomers) in the reaction medium can be 30 wt% to 44 wt%, preferably 33 wt% to 40 wt% (in the final stage). More preferably, the difference between the initial total wt% monomer in the first stage and the final total wt% monomer in the final stage may be at least 10 wt%, or at least 12 wt%, or at least 14 wt%, or at least 15 wt%, and at most 25 wt%, or at most 23 wt%, or at most 21 wt%, or at most 20 wt%. The continuous polymerization stages are typically carried out in the same reaction vessel, but are not mandatory.

[0339] For illustrative purposes, a base, monomer, and an initial amount of solvent (for dissolving the monomer) are loaded into and mixed in a container to obtain an initial monomer concentration in the reaction medium, and the first polymerization stage begins once the reaction medium is heated to a suitable reaction temperature. As polymerization proceeds, the polymer molecular weight increases, resulting in an increase in the viscosity of the reaction medium. When the target viscosity of the reaction medium (preferably in the range of 5000 to 8000 cP) is reached, another amount of solvent is added to the reaction medium in the same container to begin a subsequent (second) polymerization stage, but at a monomer concentration lower than the initial monomer concentration in the first stage. When the target viscosity of the reaction medium (preferably in the range of 5000 to 8000 cP) is reached, the reaction medium can be diluted with solvent again in one or more additional successive polymerization stages. That is, an additional amount of solvent is added to the reaction medium to begin a subsequent polymerization stage, but at a monomer concentration lower than the previous stage.

[0340] alkali

[0341] The reaction medium contains alkali.

[0342] The base comprises an inorganic metal phosphate, wherein the metal is selected from Group 1, 2 or 3 of the IUPAC periodic table.

[0343] The inorganic metal phosphate is preferably an alkali metal phosphate, characterized in that the pKa of its conjugate acid is greater than 10.5 and less than 15 (10.5 < pKa < 15).

[0344] The inorganic metal phosphate is preferably a ternary alkali metal phosphate, wherein the alkali metal is K, Na, Cs and / or Li; preferably tripotassium phosphate (K3PO4) and / or trisodium phosphate (Na3PO4); more preferably K3PO4.

[0345] Particularly preferred are ternary alkali metal phosphates (preferably K3PO4 and / or Na3PO4, more preferably K3PO4) having a median particle size (D50) of at least 10 micrometers and at most 400 micrometers. More preferably, a median particle size of up to 200 micrometers is used. Even more preferably, a median particle size of up to 160 micrometers is used. Even more preferably, the median particle size of the ternary alkali metal phosphate can be at least 20 micrometers and at most 100 micrometers, or at least 20 micrometers and at most 80 micrometers. Although the median particle size can be measured by any suitable method, the median particle size D50 is preferably measured by light scattering in a dry mode.

[0346] The use of ternary alkali metal phosphates with this median particle size allows the synthesis of PAES to be carried out at relatively low reaction temperatures (e.g., > 110°C up to 200°C).

[0347] The molar amount of the tribasic alkali metal phosphate in the reaction medium is relative to the molar amounts of the alicyclic diol (AA) and any optional co-diol (such as diol (BB) and / or (BB')).

[0348] - At least 1.00, or at least 1.04, or at least 1.10, or at least 1.15, or at least 1.2, or at least 1.25, or at least 1.30; and / or

[0349] - Up to 3.0, or up to 2.8, or up to 2.75, or up to 2.5, or up to 2.4.

[0350] Bases can further comprise anhydrous alkali metal carbonates. Anhydrous alkali metal carbonates are sometimes referred to as "co-bases".

[0351] Anhydrous alkali metal carbonates or co-alkalis may be selected from the group consisting of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, preferably sodium carbonate and / or potassium carbonate, more preferably potassium carbonate.

[0352] When the alkali contains a mixture of tripotassium phosphate (K3PO4) and sodium carbonate (K2CO3), the molar ratio r of K2CO3 to K3PO4 is... k It could be:

[0353] - at most 75:25, or at most 70:30, or at most 67:33, and / or

[0354] - At least 10:90, or at least 12:88, or at least 13:87.

[0355] Median particle size (D) of alkali metal carbonates 50 The median particle size (D) of the alkali metal carbonate can be at least 10 micrometers and at most 400 micrometers, preferably at least 15 micrometers and at most 200 micrometers, more preferably at least 20 micrometers and at most 100 micrometers. Even more preferably, a median particle size (D) of at least 20 micrometers and at most 50 micrometers is used. 50 ).

[0356] When the method of the present invention is carried out in the presence of anhydrous K2CO3, the anhydrous K2CO3 may have a volume average particle size (D[4,3]) of less than about 100 µm, for example less than 45 µm, less than 30 µm, or less than 20 µm. Specifically, the method of the present invention is carried out in the presence of a carbonate component comprising not less than 50 wt% of K2CO3 based on the total weight of the carbonate component in the reaction medium, the K2CO3 having a volume average particle size of less than about 100 µm, for example less than 45 µm, less than 30 µm, or less than 20 µm. The volume average particle size of the carbonate used can be determined, for example, using a Mastersizer 2000 from Malvern for a suspension of particles in chlorobenzene / sulfolane (60 / 40).

[0357] Ternary alkali metal phosphates can be used to provide PAES polymers with desired molecular weight characteristics and distributions. Surprisingly, it has been found that higher molecular weight PAES homopolymers and copolymers can be obtained when tripotassium phosphate (K3PO4) is used in the reaction or when a combination of tripotassium phosphate (K3PO4) and potassium carbonate (K2CO3) (as co-alkalis) is used during the condensation reaction.

[0358] The base used in the reaction medium is preferably anhydrous.

[0359] Preferably, the inorganic metal phosphates used in the reaction medium, especially ternary alkali metal phosphates, are anhydrous.

[0360] Preferably, when a co-alkali such as an alkali metal carbonate (preferably K2CO3) is used in combination with an inorganic metal phosphate (preferably K3PO4) in the reaction medium, the co-alkali (preferably K2CO3) is anhydrous.

[0361] As used herein, the term "anhydrous" means a substance containing less than 2 wt% water, preferably less than 1 wt% water, more preferably less than 0.5 wt% water, and most preferably less than 0.25 wt% water, as measured by Karl Fischer titration or by loss on drying.

[0362] The base does not contain strongly hindered potassium bases, such as potassium trimethylsilanolate. For example, the strongly hindered bases disclosed in WO 2020 / 201522 (Roquette Freres) are not present in the base.

[0363] The alkali preferably does not contain organic bases.

[0364] Apart from the inorganic metal phosphates and optional alkali metal carbonates present in the base that participate in the polycondensation reaction, the base does not contain any organic catalysts. For example, the crown ether catalyst disclosed in EP 3653661 (Korea Research Institute of Chemical Technology) is not present in the base.

[0365] Apart from inorganic metal phosphates used in the alkali, it is preferable not to use other phosphorus-containing materials in the reaction medium. For example, phosphorus-containing solvents (such as hexamethyltriamide phosphate) are not used during PAES polymerization.

[0366] Dihaloaryl sulfone monomers (CC)

[0367] The reaction medium contains at least one dihaloaryl sulfone monomer (CC) having the general formula (C):

[0368] X-[Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ] m -X'(C),

[0369] Where n, m, and Ar 3 Ar 4 and Ar 5 For repeating units (R) with general formula (I) a The same as those defined; and

[0370] In formula (C), X and X', which are the same or different from each other, are independently halogen atoms, preferably Cl or F, more preferably Cl.

[0371] The dihalosulfone monomer (CC) preferably has the formula (C1):

[0372] (C1),

[0373] in:

[0374] In formula (C1), X and X', which are the same or different from each other, are independently halogen atoms, preferably Cl or F, more preferably Cl;

[0375] - Each R1—whether identical or different from each other—is selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium compounds; and

[0376] - Each i - whether the same or different from each other - is independently zero or an integer from 1 to 4, preferably independently zero or 1, more preferably zero.

[0377] When i in formula (C1) is not zero, R1 is preferably independently selected from the group consisting of: alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium.

[0378] In equation (C1), for each R1, i is preferably 0.

[0379] More preferably, the dihaloaryl sulfone monomer (CC) consists essentially of at least one 4,4-dihalodiphenyl sulfone selected from the group consisting of: 4,4'-dichlorodiphenyl sulfone (DCDPS), monosulfonated 4,4'-dichlorodiphenyl sulfone (msDCDPS), disulfonated 4,4'-dichlorodiphenyl sulfone (dsDCDPS), 4,4'-difluorodiphenyl sulfone (DFDPS), monosulfonated 4,4'-difluorodiphenyl sulfone (msDFDPS), disulfonated 4,4'-difluorodiphenyl sulfone (dsDFDPS), and any combination thereof.

[0380] The dihaloaryl sulfone monomer (CC) is more preferably composed of essentially DCDPS and / or disodium bis(4-chloro-3-sulfophenyl)sulfone (dsDCDPS), and most preferably composed of essentially DCDPS.

[0381] Alicyclic diols (AA)

[0382] The reaction medium contains at least one cyclic aliphatic diol monomer comprising at least one alicyclic moiety (M) [hereinafter "aliphatic diol (AA)"].

[0383] The term "alicyclic moiety" is intended to refer to any moiety that is both aliphatic (i.e., non-aromatic) and cyclic (i.e., in which carbon atoms and optional heteroatoms are attached to a ring). The alicyclic moiety (M) may contain 4 to 30 carbon atoms, preferably 4 to 15 carbon atoms, or 4 to 10 carbon atoms, or 4 to 8 carbon atoms, or 4 to 6 carbon atoms. The alicyclic moiety (M) may be unsubstituted or substituted.

[0384] The alicyclic moiety (M) may contain at least one heteroatom in the ring, such as at least one oxygen atom.

[0385] Alternatively, the alicyclic moiety (M) does not contain any heteroatoms in the ring, meaning that the ring skeleton of the alicyclic moiety (M) is made up of only interconnected carbon atoms.

[0386] Alicyclic diols (AA) may contain more than one alicyclic moiety (M). If an alicyclic diol (AA) contains more than one alicyclic moiety (M), these moieties may be the same or different.

[0387] Alicyclic diols (AA) may comprise polycyclic alicyclic moieties, which contain more than one condensed alicyclic moiety (M). Typically, the polycyclic alicyclic moieties contain two, three, or even four condensed alicyclic moieties (M). Each condensed alicyclic moiety (M) typically contains 4 to 8 carbon atoms, preferably 4 to 6 carbon atoms.

[0388] It should be further understood that alicyclic diols (AA) can exist in different stereochemical and regiochemical arrangements. Thus, for example, the two hydroxyl groups in an alicyclic diol (AA) can have cis or trans configurations relative to each other.

[0389] Alicyclic diols (AA) preferably have the general formula (D):

[0390] HO-E-OH(D),

[0391] Wherein E contains at least one alicyclic moiety (M) and is a group containing 4 to 30 carbon atoms, preferably 4 to 15 carbon atoms.

[0392] Alicyclic diols (AA) are more preferably diols having formula (D), wherein E is at least one group selected from those having formulas (E1) to (E11) previously described with respect to formula (I). That is, at least one alicyclic diol (AA) is selected from the group consisting of those conforming to formulas (D1) to (D11):

[0393]

[0394]

[0395] , and any combination thereof,

[0396] In equation (D11), each Q' that is the same or different is a non-cyclic part.

[0397] The acyclic portion Q' in formula (D11) may be derived from an acyclic diol selected from epoxides and / or poly(epoxides), preferably from the group consisting of: ethylene glycol, propylene glycol [HO-CH2-CH(CH3)-OH], 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, poly(ethylene glycol), poly(propylene glycol), poly(tetramethylene oxide), and any combination of two or more thereof.

[0398] Q' in equation (D11) can be represented by equation (VI): -[R k -O-] z -R k -,

[0399] Where R k Selected from alkylene groups, preferably alkylene groups having 1 to 10 carbon atoms, and more preferably selected from the group consisting of: methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH2] 2- [CH2-CH2], 2,2-dimethylpropylidene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-1,3-propylidene [CH2-C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-1,3-pentylene [CH(C(CH3)2)-C(CH3)2-CH2], and any combination thereof; and z is 0 or an integer from 1 to 500, preferably an integer from 2 to 200, more preferably an integer from 2 to 100, and even more preferably an integer from 2 to 50.

[0400] Preferably, Q' in equation (D11) is represented by any one of the following equations: (VI'), (VI”), (VI'”), and (VI””).

[0401] -[CH2-CH2-O] z -CH2-CH2-(VI'),

[0402] -[CH2-CH(CH3)-O] z -CH2-CH(CH3)-(VI”),

[0403] -[CH2-CH2-CH2-CH2-O]z -CH2-CH2-CH2-CH2-(VI'”),

[0404] -[CH2-C(CH3)2-CH2-O] z -CH2-C(CH3)2-CH2-(VI””),

[0405] Where z is 0 or an integer from 1 to 500, preferably an integer from 2 to 200, more preferably an integer from 2 to 100, and even more preferably an integer from 2 to 50.

[0406] Alicyclic diols (AA) may be selected from 1,4:3,6-didehydrohexitol and / or 1,4:3,6-didehydrohexitol having acyclic aliphatic end groups.

[0407] Alicyclic diols (AA) are more preferably selected from the group consisting of: 1,4:3,6-didehydrohexitols, such as isosorbide (“ISOSO”) (D1); 2,3-di-O-alkylene-1-threitols, such as 2,3-O-isopropylene-1-threitol (D4) and / or 2,3-di-O-methylene-1-threitol; tetrahydrofurandiethanol (D5); tetramethylcyclobutanediol (“CBDO”) (D6); cis-1,5-cyclooctanediol (“CODO”) (D7); cyclohexanediol (“CHDM”) (D8); and hydrogenated bisphenols, such as hydrogenated bisphenol A (“H-BPA”). (D9); decahydronaphthalenediol, such as 2,6-decahydronaphthalenediol (D10); and 1,4:3,6-disodehydrated hexitols with acyclic aliphatic end groups, such as isosorbide (D11) with acyclic aliphatic end groups.

[0408] Alicyclic diols (AA) are more preferably selected from the group consisting of isosorbide (D1), 2,3-O-isopropylidene-1-threitol (D4), tetrahydrofurandiethanol (D5), and isosorbide (D11) having a non-cyclic aliphatic end group.

[0409] Even more preferably, the alicyclic diol (AA) is 1,4:3,6-disodehydrated hexitol.

[0410] Most preferably, the alicyclic diol (AA) is isosorbide.

[0411] Alicyclic diols (AAs) selected from isosorbide (D1), isomannitol (D2), iso-idyl alcohol (D3), 2,3-O-isopropylidene-l-threitol (D4), tetrahydrofurandimethyl (D5), and / or isosorbide with a non-cyclic aliphatic end group (D11) can be used to provide PAES polymers with improved hydrophilicity and / or higher Tg. The improvement in hydrophilicity and / or increase in Tg is compared with the following commercial polyarylether sulfones: PSU, PES, and PPSU.

[0412] Therefore, the improved properties allow for similar or improved performance relative to current commercial PAES grades made from DCDPS and bisphenols selected from BPA, BPS or BP for applications such as films, coatings, additive manufacturing and 3D printing.

[0413] Good hydrophilicity is particularly advantageous in filtration applications, such as for reducing the overpressure required to filter aqueous media.

[0414] Since isosorbide, isomannitol, iso-idyl alcohol, isosorbide with a noncyclic aliphatic end group, 2,3-O-isopropylidene-l-threitol and / or tetrahydrofurandimethyl are sugar-based diols derived from biomass, the resulting PAES are at least partially bio-based.

[0415] Optional codiols

[0416] In addition to alicyclic diols (AA), the reaction medium may further contain at least one codiol different from at least one alicyclic diol (AA).

[0417] The molar ratio r of at least one alicyclic diol (AA) to at least one codiol can be:

[0418] - Up to 95:5, preferably up to 90:10, more preferably up to 85:15, and even more preferably up to 80:20, and / or

[0419] - At least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, even more preferably at least 50:50, and even more preferably at least 60:40.

[0420] Aromatic diols (BBs) are an optional co-diol.

[0421] In particular, the reaction medium may further comprise at least one dihydroxyaryl monomer [hereinafter “aromatic diol (BB)”] as a codiol.

[0422] It should be understood that at least one aromatic diol (BB) contains at least two hydroxyl groups. This means that, in the context of this invention, aromatic diols (BB) also encompass any aromatic compound (BB) having more than two hydroxyl groups. Aromatic compounds (BB) with 3 to 6 hydroxyl groups, especially 3 or 4 hydroxyl groups, can be envisioned. Used as an aromatic diol (BB) or as an aromatic diol (BB) to prepare a sulfone repeating unit (R) by reacting with at least one haloaryl sulfone monomer (CC). b Non-restricted aromatic compounds (BB) containing three or more hydroxyl groups. The alcohol can be selected from: phloroglucinol, 4,6-dimethyl-2,4,6-tris-(4-hydroxy-5-phenyl)-heptene-2-(polyisopropenephenol), 4,6-dimethyl-2,4,6-(4-hydroxyphenyl)-heptane (hydrogenated polyisopropenephenol), 1,3,5-tris-(4-hydroxyphenyl)-benzene, 1,1,1-tris-(4-hydroxyphenyl)-ethane, 1,1,1-tris-(4-hydroxyphenyl)-propane, tetra-(4-hydroxyphenyl)-methane, 1,4-bis-(4′,4″-dihydroxytriphenyl)-methyl]-benzene, and 2,2-bis-[4,4′-bis-(4-hydroxyphenyl)-cyclohexyl]-propane. For example, aromatic diols (BBs) can include or can be aromatic triols, such as 1,1,1-tris-(4-hydroxyphenyl)-ethane.

[0423] At least one aromatic diol (BB) may have the general formula (D'):

[0424] HO-W-OH(D').

[0425] W in equation (D') is defined by general equation (III): -Ar 6 -(T-Ar 7 ) y -,

[0426] in

[0427] -T is selected from the group consisting of: bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CCl3)2-, -C(=CCl2)-, -CH2-, -O-, -C(O)-, -S-, -SO-, -C(CH3)(CH2CH2COOH)- and any combination thereof, preferably selected from the group consisting of: bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -CH2-, -C(O)- and any combination thereof, more preferably selected from the group consisting of: bond, -SO2-, -C(CH3)2-, -CH2- and any combination thereof,

[0428] -y is 0 or 1, and

[0429] -Ar 6 Ar 7 They may be the same as or different from each other, and are aromatic parts of any one of the following formulas (H), (H'), and (H”):

[0430] (H), (H'), (H”),

[0431] R' in any of formulas (H), (H'), and (H”) is selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, sulfonic acids (-SO3H), alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammonium, and j' in any of formulas (H), (H'), and (H”) is 0, 1, 2, 3, or 4.

[0432] j' is 0 when the aromatic ring in any part of equations (H), (H'), and (H”) is not substituted.

[0433] In equation (D'), W is preferably defined by equation (IIIa): -Ar 6 -T-Ar 7 -,

[0434] in:

[0435] -T can be selected from the following groups: bond, -SO2-, -C(CH3)2-, -CH2-, and any combination thereof, and

[0436] -Ar 6 and Ar 7 It is an unsubstituted aryl group with the formula (H), where j'=0.

[0437] In equation (D'), W can be alternatively defined by equation (IIIb): -Ar 6 -,

[0438] Among them, Ar 6 It is an unsubstituted aryl group having the formula (H) or (H'), where j'=0.

[0439] In equation (D'), W can be, and alternatively, defined by equation (IIIa):

[0440] -Ar 6 -T-Ar7 -,

[0441] in:

[0442] -T is -CH2-; and

[0443] -Ar 6 and Ar 7 It is an unsubstituted arylene with formula (H) where j'=0, or a substituted arylene with formula (H) where j'=2 and R' is methyl.

[0444] At least one aromatic diol (BB) may be selected from the group consisting of: bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4'-biphenyl, diallyl biphenyl, tetramethyl bisphenol F, bisphenol F, hydroquinone, resorcinol, aromatic triols such as 1,1,1-tri-(4-hydroxyphenyl)-ethane and any combination thereof; more preferably selected from the group consisting of: bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4'-biphenyl, diallyl biphenyl, tetramethyl bisphenol F and any combination thereof; even more preferably selected from the group consisting of: 4,4'-biphenyl, diallyl biphenyl, tetramethyl bisphenol F and combinations thereof; most preferably 4,4'-biphenyl.

[0445] When at least one aromatic diol (BB) is used in the reaction medium, the molar ratio r of at least one alicyclic diol (AA) to at least one aromatic diol (BB) in the reaction medium is... b yes:

[0446] - Up to 95:5, preferably up to 90:10, more preferably up to 85:15, and even more preferably up to 80:20, and / or

[0447] - At least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, even more preferably at least 50:50, and even more preferably at least 60:40.

[0448] When aromatic triols (BB) are used in the reaction medium When 1,1,1-tris-(4-hydroxyphenyl)-ethane is used as a co-diol (BB), it is generally advantageous to use 0.5 mol% to 5 mol% of aromatic triols (BBs). The mol% is based on the total molar amount of diol in the reaction medium.

[0449] Acyclic diols (BB') are optional co-diols.

[0450] In addition to at least one alicyclic diol (AA), the reaction medium may further comprise at least one aliphatic (non-aromatic) and acyclic dihydroxy monomer [hereinafter “acyclic diol (BB’)”] as a codiol.

[0451] Acyclic diols (BB') are different from at least one alicyclic diol (AA) and at least one aromatic diol (BB).

[0452] Acyclic diols (BB') are selected from straight-chain aliphatic diols or branched-chain aliphatic diols.

[0453] As a non-limiting example of a straight-chain aliphatic diol as a noncyclic diol (BB'), ethylene glycol, poly(ethylene glycol), tetramethylene oxide, poly(tetramethylene oxide), 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and / or 1,10-decanediol may be mentioned.

[0454] As non-limiting examples of branched aliphatic diols as noncyclic diols (BB'), 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, propylene glycol and / or poly(propylene glycol) may be mentioned.

[0455] Acyclic diols (BB') can be represented by formula (D”):

[0456] HO-Q-OH(D”),

[0457] Q represents the non-cyclic part.

[0458] Advantageously, the noncyclic diol (BB') having formula (D”) can have a molecular weight of less than 2000 g / mol, preferably up to 1800 g / mol, more preferably up to 1500 g / mol, even more preferably up to 1300 g / mol, even more preferably up to 1100 g / mol, and most preferably up to 900 g / mol.

[0459] Acyclic diols (BB') can be alkylene oxides or poly(alkylene oxides).

[0460] Equation (D”a) represents: HO-[R k -O] z -R k -OH(D”a),

[0461] Where R kSelected from alkylene groups, preferably alkylene groups having 1 to 10 carbon atoms, and more preferably selected from the group consisting of: methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH2] 2- [CH2-CH2], 2,2-dimethylpropylidene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-1,3-propylidene [CH2-C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-1,3-pentylene [CH(C(CH3)2)-C(CH3)2-CH2] and any combination thereof; and z is 0 or an integer from 1 to 500.

[0462] Preferably, the acyclic diol (BB') is represented by any one of the following formulas (D”a1), (D”a2), (D”a3), and (D”a4):

[0463] HO-[(CH2)2-O] z -(CH2)2-OH(D”a1),

[0464] HO-[CH2-CH(CH3)-O] z -CH2-CH(CH3)-OH(D”a2),

[0465] HO-[(CH2)4-O] z -(CH2)4-OH(D”a3),

[0466] HO-[CH2-C(CH3)2-CH2-O] z -CH2-C(CH3)2-CH2-OH(D”a4),

[0467] Where z is 0 or an integer from 1 to 500.

[0468] When the acyclic diol (BB') is an epoxide or poly(epoxide), it has at least two free hydroxyl groups (-OH).

[0469] When the acyclic diol (BB') is a poly(epoxyalkane), z in any one of formulas (D”a), (D”a1), (D”a2), (D”a3) and (D”a4) is an integer from 1 to 500, preferably an integer from 2 to 200, and more preferably an integer from 2 to 100.

[0470] When the acyclic diol (BB') is a poly(epoxide), it preferably has an average molecular weight (Mn) of 160 to 30,000 g / mol. In this case, the z in the acyclic diol (BB') represented by any one of formulas (D”a), (D”a1), (D”a2), (D”a3), and (D”a4) is preferably selected such that its average molecular weight (Mn) does not exceed 30,000 g / mol. The z in any one of formulas (D”a), (D”a1), (D”a2), (D”a3), or (D”a4) is preferably selected such that the molecular weight of the acyclic diol (AA) is less than 2000 g / mol, preferably at most 1800 g / mol, more preferably at most 1500 g / mol, even more preferably at most 1300 g / mol, even more preferably at most 1100 g / mol, and most preferably at most 900 g / mol.

[0471] When at least one acyclic diol (BB') is used in the reaction medium, the molar ratio r of at least one alicyclic diol (AA) to at least one acyclic diol (BB') in the reaction medium is... c yes:

[0472] - Up to 95:5, preferably up to 90:10, more preferably up to 85:15, and even more preferably up to 80:20, and / or

[0473] - At least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, even more preferably at least 50:50, and even more preferably at least 60:40.

[0474] polar aprotic solvents

[0475] At least one dihaloaryl sulfone monomer (CC), at least one alicyclic diol (AA), any optional co-diol (BB) and / or (BB'), and a base are dissolved and / or dispersed in a polar aprotic solvent.

[0476] The polar aprotic solvents used are those commonly known in the art and widely used in the manufacture of aromatic sulfone polymers. For example, the use of dialkyl sulfoxides and dialkyl sulfones (sulfur-containing solvents, including their cyclic alkylene analogs, in which the alkyl group may contain 1 to 8 carbon atoms) for the manufacture of PAES is disclosed in the art. Specifically, among the sulfur-containing solvents that may be suitable for the purposes of this invention are dimethyl sulfoxide, dimethyl sulfone, diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (often referred to as tetramethylene sulfone or sulfolane), and tetrahydrothiophene-1-monoxide and mixtures thereof. Nitrogen-containing polar aprotic solvents, including N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP), have been disclosed in the art for use in these methods, and it may also be found that these nitrogen-containing polar aprotic solvents are useful in the practice of this invention.

[0477] The polar aprotic solvent is preferably selected from the group consisting of: 1,3-dimethyl-2-imidazolinone (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′-dimethylacrylurea (DMPU), N,N'-dimethylformamide (DMF), N-methylcaprolactam, N-ethylcaprolactam, tetrahydrothiophene-1-monoxide, and any mixture of two or more thereof.

[0478] The polar aprotic solvent is more 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-imidazolinone (DMI), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), sulfolane, and any combination thereof.

[0479] The polymerization reaction for preparing PAES is more advantageously carried out in a polar aprotic solvent, such as sulfolane, DMAc, or NMP.

[0480] Optional cosolvents

[0481] For the purposes of this invention, the terms "another solvent" or "co-solvent" should be understood to refer to a solvent that is different from the reactants and products of the condensation reaction.

[0482] If desired, an additional solvent can be used with a polar aprotic solvent to form an azeotropic mixture with water, thereby continuously removing water, which may originate from at least one raw material (e.g., an inorganic metal phosphate) and / or may form as a byproduct during polymerization (e.g., when an alkali metal carbonate is used as a alkali promoter), throughout the polymerization process by azeotropic distillation. Typically, the reaction medium can be maintained under substantially anhydrous conditions by continuously removing water from the reactants during polymerization. Water can be removed by distillation or as part of the azeotropic mixture along with the solvent forming the mixture, as described above.

[0483] The other solvent that forms an azeotropic mixture with water will typically be chosen to be inert with respect to the monomer components and the polar aprotic solvent. Suitable solvents for forming azeotropic mixtures in such polymerization methods include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, etc.

[0484] The solvents and polar aprotic solvents that form the azeotropic mixture are typically used in a weight ratio of about 1:20 to about 1:1, preferably about 1:10 to about 1:1, and more preferably about 1:5 to about 1:3.

[0485] However, the condensation reaction is preferably carried out in the absence of a co-solvent that forms an azeotropic mixture.

[0486] reaction medium

[0487] A reaction medium containing monomers, a base, and a polar aprotic solvent can be formed in the following ways:

[0488] 1 / Mix all these ingredients together, or

[0489] 2 / Premix some ingredients together to obtain a premix, and then add the missing ingredients to the premix.

[0490] The mixing or premixing is preferably carried out at a 'mixing' temperature that is not suitable for polycondensation reactions, such as a mixing temperature of up to 150°C, or up to 130°C, or up to 110°C.

[0491] The addition step in 2 / can be carried out at a reaction temperature of >110°C, or >130°C, or >150°C, or at a 'mixing' temperature that is not suitable for polycondensation reactions, such as a mixing temperature of up to 150°C, or up to 130°C, or up to 110°C.

[0492] The molar ratio of halogen groups (preferably chlorine) to hydroxyl groups in the reaction medium can vary, depending on factors such as control over the type and content of end groups, or control over the reaction rate and the molecular weight of PAES. Generally, it is preferred to control or adjust the molar ratio of the hydroxyl groups of alicyclic diols (AA) and optionally diols (BB) and / or (BB') that are reactive with each other to the halogen groups of the dihaloaryl sulfone monomer (CC).

[0493] The molar ratio between the total amount of hydroxyl groups from alicyclic diols (AA) and optionally other diols (BB) and / or (BB') in the reaction medium and the total amount of halogen groups from dihaloaryl sulfone monomers (CC) is typically 0.95 to 1.05, preferably 0.98 to 1.02, more preferably 0.985 to 1.015, and even more preferably 0.99 to 1.01. Molar ratios of hydroxyl groups to halogen groups of 0.995 and 1.008, or 0.997 and 1.007, are suitable for achieving high M values ​​greater than 59 kDa. w It is particularly advantageous.

[0494] Although the molar ratio of hydroxyl to halogen groups is preferably substantially equimolar (M) for obtaining higher molecular weights. w > 59 kDa), but alternatively, the molar ratio of halogen groups (preferably chlorine) can be higher than the molar ratio of hydroxyl groups, or vice versa. For example, to increase the number of phenolic OH-terminal groups, the molar ratio of halogen (chlorine)-terminal groups to phenolic OH-terminal groups is adjusted by using a starting diol (AA) and optionally a diol (BB) or (BB') in molar excess compared to the starting dihaloaryl sulfone monomer (CC). For example, the molar ratio of OH groups to halogen (chlorine) groups can be 1.005 to 1.2, especially 1.007 to 1.15, and most preferably 1.01 to 1.1.

[0495] When lower reactivity of the terminal groups in PAES is desired, it is preferable to increase the number of halogen (chlorine) terminal groups, particularly phenyl chloride groups, and to adjust the molar ratio of halogen (chlorine) terminal groups to phenolic OH terminal groups by using a molar excess of a starting dihaloaryl sulfone monomer (CC) compared to the starting diol (AA) and optionally diols (BB) and (BB'). Thus, an excess of chlorine terminal groups is preferred. In this case, the molar ratio of halogen (chlorine) groups to OH groups can be 1.005 to 1.2, particularly 1.007 to 1.15, and most preferably 1.01 to 1.1.

[0496] The reaction medium in which the polycondensation reaction takes place has the following total weight % monomer concentration based on the total weight of the alicyclic diol (AA), dihaloaryl sulfone monomer (CC), optional co-diol: aromatic diol (BB) and / or acyclic diol (BB') and polar aprotic solvent [hereinafter "total wt% monomer"]:

[0497] - At least 30 wt%, preferably at least 35 wt%, more preferably at least 38 wt%, and / or

[0498] - Up to 60 wt%, preferably up to 55 wt%, more preferably up to 50 wt%.

[0499] Although the reaction medium contains a base comprising an inorganic metal phosphate and optionally an alkaline metal carbonate, it preferably does not contain any organophosphate bases. For example, the strongly hindered bases disclosed in WO 2020 / 201522 (Roquette Brothers) are not present in the reaction medium.

[0500] Apart from the base (which comprises inorganic metal phosphates and optionally alkali metal carbonates) contained in the reaction medium participating in the polycondensation reaction, the reaction medium preferably does not contain a catalyst. For example, the crown ether catalyst disclosed in EP 3653661 (Korea Institute of Chemical Technology) is not present in the reaction medium.

[0501] Reaction conditions

[0502] The reaction medium used to prepare PAES is kept at a temperature suitable for polycondensation to occur. Such a suitable temperature for the reaction medium can be:

[0503] - Above 110°C, preferably at least 115°C, more preferably at least 120°C, and even more preferably at least 125°C, and

[0504] - Less than 210°C, preferably up to 205°C, more preferably up to 200°C, and even more preferably up to 195°C.

[0505] When NMP and / or sulfolane are used as solvents, the preferred temperature of the reaction medium may be from about 115°C to about 205°C, preferably from about 120°C to about 200°C.

[0506] When DMAc is used as a solvent, the preferred temperature of the reaction medium is from about 115°C to about 175°C, preferably from about 120°C to about 175°C.

[0507] When the alicyclic diol (AA) contains or is composed of isosorbide, and when NMP and / or sulfolane are used as a polar aprotic solvent, the temperature of the reaction medium can be from about 150°C to about 205°C, preferably from about 160°C to about 200°C.

[0508] When the alicyclic diol (AA) contains or is composed of isosorbide, and when DMAc is used as a polar aprotic solvent, the temperature of the reaction medium can be from about 155°C to about 175°C, preferably from about 160°C to about 175°C.

[0509] The method for producing PAES is to achieve a reaction conversion rate of at least 90%, preferably at least 95%.

[0510] The reaction time for preparing PAES can be approximately 3 to 24 hours, or approximately 4 to 20 hours, or 5 to 18 hours.

[0511] Typically, if the reaction is carried out at atmospheric pressure, the boiling temperature of the chosen solvent usually limits the reaction temperature. The reaction can suitably be carried out at atmospheric pressure in an inert atmosphere (such as nitrogen), but higher or lower pressures can also be used.

[0512] Recycling of PAES in solid form

[0513] The PAES of the present invention are recovered using methods well-known and widely used in the art, such as coagulation and solvent evaporation. After polymerization, the resulting PAES is in solution form.

[0514] The resulting PAES can be separated from the PAES solution by the following method: after the salt separation of the reaction medium, with or without the prior addition of an additional solvent to completely dissolve any polymer and cause precipitation of a metal halide (preferably KCl), is carried out. The additional solvent may be different from the polar aprotic solvent used in the reaction, but preferably it is the same.

[0515] Alternatively, PAES polymers can be separated from PAES solutions by precipitation and / or coagulation through contacting the reaction medium (optionally after salt removal by filtration) with a non-solvent for the PAES polymer, such as C1-C5 alcohols, water, or any mixture thereof. The precipitate / coagulate can be rinsed and / or washed with softened water or C1-C5 alcohol prior to drying at a temperature ranging from at least 70°C to about 170°C. Although a vacuum can be applied during drying, drying is typically carried out at ambient pressure.

[0516] Apart from the inorganic metal phosphates used in the alkali during polymerization, other phosphorus-containing materials are preferably not used during PAES recycling.

[0517] For example, preferably, phosphoric acid is not used to acidify or neutralize the PAES solution after salt separation and during rinsing and / or washing of PAES solids.

[0518] Preferably, phosphorus-containing solvents (such as hexamethyltriamide phosphate) are not used to quench or dilute the PAES solution after polymerization, after salt separation, and during rinsing and / or washing of PAES solids.

[0519] The obtained PAES solids can be further processed by extrusion and granulation. The granulated product can then undergo further melt processing, such as injection molding and / or sheet extrusion. The conditions for using PAES obtained by molding, extrusion, and thermoforming are well known in the art.

[0520] The PAES according to the invention are characterized by all the benefits of currently marketed polyarylether sulfones, and also unexpectedly by a reduced content of potential endocrine disruptors and a potentially higher renewable content, especially when biologically derived alicyclic diols (such as those selected from alicyclic diols (D1) to (D5)) are used to prepare such PAES.

[0521] Uses of PAES

[0522] The present invention also relates to polymer compositions comprising at least one PAES of the present invention and at least one other component.

[0523] The polymer composition advantageously contains more than 1 wt%, preferably more than 10 wt%, even more than 50 wt%, and most preferably more than 90 wt% of the PAES of the present invention, said wt% being relative to the total weight of the composition.

[0524] This other component may be one or more PAES polymers, such as commercially available PPSU, PSU and / or PES polymers.

[0525] These other components can also be polymers other than PAES polymers, such as polyvinylpyrrolidone or polyethylene glycol.

[0526] These other components can also be non-polymer components, such as solvents, fillers, lubricants, mold release agents, antistatic agents, flame retardants, antifogging agents, matting agents, pigments, dyes, and optical brighteners.

[0527] Dope solution

[0528] An example of such polymer composition is a polymer stock solution suitable for preparing membranes. The term "polymer stock solution" refers to a polymer solution used for preparing membranes (i.e., by casting, spinning, etc.).

[0529] The stock solution used for membrane preparation preferably contains the PAES of the present invention in a polar organic solvent.

[0530] Suitable polar organic solvents for the stock solution can be any of the polar aprotic solvents described herein as reaction solvents. The polar organic solvent in the stock solution can be selected from the group consisting of: 1,3-dimethyl-2-imidazolinone (DMI), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (commonly referred to as tetramethylene sulfone or sulfolane), N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N-dimethylacetamide (DMAc), N,N′-dimethylacrylurea (DMPU), N,N-dimethylformamide (DMF), N-methylcaprolactam, N-ethylcaprolactam, tetrahydrothiophene-1-monoxide, and mixtures thereof. Preferably, the polar organic solvent in the stock solution is DMAc or NMP.

[0531] The total concentration of polar organic solvent in the stock solution can be at least 20 wt%, preferably at least 30 wt%, based on the total weight of the polymer solution. Typically, the concentration of solvent in the stock solution does not exceed 85 wt% based on the total weight of the stock solution; preferably, it does not exceed 75 wt%; more preferably, it does not exceed 70 wt%; even more preferably, it does not exceed 65 wt%; and most preferably, it does not exceed 60 wt%.

[0532] The total concentration of PAES in the stock solution is preferably at least 8 wt%, more preferably at least 12 wt%, based on the total weight of the stock solution. Typically, the concentration of PAES in the stock solution does not exceed 50 wt%, preferably not more than 40 wt%, and more preferably not more than 30 wt%, based on the total weight of the stock solution.

[0533] A concentration of PAES ranging from 15 wt% to 25 wt%, preferably 16 wt% to 22 wt%, relative to the total weight of the stock solution has been found to be particularly advantageous.

[0534] The polymer solution (SP) may further comprise at least one additional polymer different from the PAES described herein, such as another sulfone polymer such as polysulfone (PSU), polyethersulfone (PES), poly(diphenyl ether sulfone) (PPSU), or polyphenylene sulfide (PPS), poly(aryl ether ketone) (PAEK) such as poly(ether ether ketone) (PEEK), poly(ether ketone ketone) (PEKK), poly(ether ketone) (PEK), or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer), polyetherimide (PEI), and / or polycarbonate (PC). Other polymer components may also include, or have a molecular weight of at least 200 g / mol, polyvinylpyrrolidone and / or polyethylene glycol (PEG).

[0535] In this case, based on the total weight of the stock solution, the concentration of at least one other polymer and PAES in the stock solution does not exceed 50 wt%; preferably, it does not exceed 40 wt%; more preferably, it does not exceed 30 wt%.

[0536] For porous membranes, the feed solution may further contain pore-forming agents, such as polyvinylpyrrolidone or polyethylene glycol.

[0537] The stock solution may contain other components, such as nucleating agents and fillers.

[0538] The applicant has unexpectedly discovered that the PAES of the present invention, or the polymer compositions of the present invention, as detailed above, exhibit excellent properties useful in providing high-performance polymer films.

[0539] The original solution of the present invention, which contains PAES of the present invention, is preferably used for the manufacture of membranes.

[0540] Products

[0541] Another aspect of the invention relates to an article comprising the PAES of the invention or the polymer composition as described above.

[0542] The PAES of the present invention can be used to manufacture membranes or components thereof, coatings, thin films, sheets and three-dimensional molded parts (especially transparent or colored parts).

[0543] Among the applications in which injection-molded parts can be used, healthcare applications, particularly medical and dental applications, can be mentioned, wherein molded articles made from PAES according to the invention can be advantageously used in disposable and reusable instruments and devices as a substitute for metals, glass and other conventional materials.

[0544] The PAES comprising the present invention or certain molded articles made therefrom may be selected from the group consisting of: films, melt-processed films, solution-processed films, melt-processed monofilaments and fibers, solution-processed monofilaments, hollow fibers and solid fibers, coatings, printed articles, injection-molded articles and compression-molded articles.

[0545] The products can also be food contact products, such as pipe products (such as fittings, valves, manifolds or faucets), food trays, water bottles or baby bottles, and cookware.

[0546] The products can also be electronic components.

[0547] The product can also be a casing or cover for mobile electronic devices.

[0548] The products can also be medical trays or animal cages.

[0549] The PAES or polymer compositions of the present invention, as detailed above, can also be useful in optical applications. Articles can also be optical articles, such as, in particular, sunglasses lenses, eyeglass lenses, optical lenses, and optical discs.

[0550] The PAES or polymer compositions of the present invention, as detailed above, can also be used to manufacture sheets and films. These sheets and films are particularly useful as specialized optical films or sheets, and / or suitable for packaging.

[0551] The PAES and polymer compositions of the present invention contained in articles according to the present invention have the same characteristics as described above in all their embodiments as the PAES and polymer compositions of the present invention.

[0552] Membrane (as an article)

[0553] The product is preferably a membrane.

[0554] Membranes suitable for the purposes of this invention include, but are not limited to, isotropic or anisotropic membranes, porous or non-porous membranes, composite membranes, or symmetrical or asymmetrical membranes. Such membranes can be in the form of planar structures, corrugated structures (such as corrugated sheets), tubular structures, or hollow fibers. Membranes according to the invention can be manufactured using any conventionally known membrane preparation method, such as by solution casting or solution spinning.

[0555] Non-limiting examples of membrane applications include water purification, wastewater treatment, pharmaceutical manufacturing, blood purification (especially hemodialysis), and various industrial process separations such as food and beverage processing, electrocoating recovery, and gas separation.

[0556] Particularly preferred molded articles comprising PAES of the present invention or made therefrom may be membranes selected from membranes for use in bioprocessing and medical filtration (such as hemodialysis membranes), membranes for use in food and beverage processing, membranes for use in water purification, membranes for use in wastewater treatment, and / or membranes for use in industrial process separation involving aqueous media.

[0557] The membrane according to the invention can be manufactured using any conventionally known membrane preparation method, such as by solution casting or solution spinning.

[0558] Preferably, the membrane according to the invention is prepared by a phase inversion method occurring in the liquid phase, the method comprising the following steps:

[0559] (i) Prepare a PAES stock solution containing the PAES described herein and a polar solvent.

[0560] (ii) Processing the stock solution into a thin film;

[0561] (iii) Contact the film with a non-solvent bath.

[0562] The membrane of the present invention may contain at least 1 wt%, for example at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, or at least 30 wt% of the PAES described herein based on the total weight of the membrane.

[0563] The membrane of the present invention may contain more than 50 wt%, such as more than 55 wt%, more than 60 wt%, more than 65 wt%, more than 70 wt%, more than 75 wt%, more than 80 wt%, more than 85 wt%, more than 90 wt%, more than 95 wt%, or more than 99 wt% of the PAES described herein, wherein the wt% is based on the total weight of the membrane.

[0564] According to embodiments, the membrane of the present invention may contain an amount of PAES described herein ranging from 1 wt% to 99 wt%, such as 3 wt% to 96 wt%, 6 wt% to 92 wt%, or 12 wt% to 88 wt%, said wt% based on the total weight of the membrane.

[0565] The membrane of the present invention may further comprise at least one polymer different from PAES described herein, such as another sulfone polymer such as polysulfone (PSU), polyethersulfone (PES), poly(biphenyl ether sulfone) (PPSU), or polyphenylene sulfide (PPS), poly(aryl ether ketone) (PAEK) such as poly(ether ether ketone) (PEEK), poly(ether ketone ketone) (PEKK), poly(ether ketone) (PEK), or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer), polyetherimide (PEI), and / or polycarbonate (PC). Other polymer components may also be polyvinylpyrrolidone and / or polyethylene glycol.

[0566] The film may further contain at least one non-polymer component, such as solvent, filler, lubricant, release agent, antistatic agent, flame retardant, antifogging agent, matting agent, pigment, dye and / or optical brightener.

[0567] Suitable examples of methods for forming films from polyarylethersulfone polymers are described in US 2019 / 054429 A1 (Solvay Specialty Polymers, Inc.), which is incorporated herein by reference.

[0568] Applications of PAES in coatings

[0569] Another aspect of the present invention is a method for coating a substrate, the method comprising using PAES of the present invention as detailed above or a polymer composition of the present invention.

[0570] The choice of substrate is not particularly limited. Such coatings can be useful for protecting substrates, especially metals such as steel, particularly stainless steel, aluminum, copper and other metals, in applications such as food and beverage can coatings, marine hull protection, aerospace, automotive, wire coatings, electronics, optics and plastics.

[0571] The present disclosure will now be illustrated by working examples, which are intended to illustrate the work of the disclosure and are not intended to imply any limitation on the scope of the disclosure.

[0572] Example

[0573] The invention will now be described in more detail with reference to the following examples, which are illustrative in nature only and are not intended to limit the scope of the invention.

[0574] raw material

[0575] 4,4'-Dichlorodiphenyl sulfone (DCDPS) (99.7%) was obtained from Solvay Specialty Polymers, Inc. (a member of the Stratocate Group).

[0576] Isosorbide (99.5%) was obtained from Roquette Brothers. Moisture content was 0.2 wt%, as measured by the Karl Fischer method. Weights indicated in the examples include moisture.

[0577] 4,4'-Biphenyldiphenol (polymer grade) was obtained from SI, USA.

[0578] The cis and trans-1,4-cyclohexanediethanol (CHDM) mixture (99%) was obtained from Aldrich and used as received.

[0579] Tripotassium phosphate (K3PO4) (anhydrous, free-flowing, Redi-Dri™, reagent grade, ≥ 98%) was obtained from Sigma-Aldrich and dried under vacuum at 120°C for 12 h prior to use. The particle size measured on a Microtrac S3500 in drying mode (20 psi, injector position set to zero) was D. 50 = 62 µm and D 90 = 165 µm.

[0580] D 90 Potassium carbonate (K2CO3) with a diameter of < 45 µm was obtained from Armand Products and dried under vacuum at 120°C for 12 hours before use.

[0581] Sulfolane, N,N-dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP) were obtained from Sigma-Aldrich and used as received.

[0582] Analytical methods

[0583] Molecular weight (M) determined by gel permeation chromatography (GPC) n M w M z ) and ratio (M w / M n M z / M w )

[0584] Molecular weight (M) measured by GPC n M w M z The GPC used a Waters Alliance E2695 and a UV-Vis detector E2489 (detection at 270 nm), two full-size Agilent 5 µm MiniMixed-D columns (250 x 4.6 mm) and a guard column (50 x 4.6 mm) (both with a 5 µm particle size), and a 0.1 M LiBr solution in DMAc as the mobile phase.

[0585] Weigh the PAES polymer sample (30 mg) into a 20 ml vial and add 5 ml of mobile phase to dissolve the sample. Filter the resulting solution into a 4 ml vial using a 0.2 μm PTFE syringe filter. The injected sample volume is 10 µL.

[0586] Select a flow rate of 0.3 ml / min. Calibrate using 10 narrow polystyrene calibration standards (peak molecular weight range: 371,000 to 580) obtained from Agilent Technologies.

[0587] Using the calibration curve generated from the polystyrene standard, the GPC distribution values ​​of the PAES samples were calculated via Agilent OpenLab CDS: M w M n M z PDI (M) w / M n ) and ratio M z / M w .

[0588] Measurement of intrinsic viscosity (IV)

[0589] The intrinsic viscosity (IV) of the PAES samples was measured at 20°C using a Cannon-Fenske viscometer tube (N°50) in a solvent mixture of dichloromethane / trifluoroacetic acid (9 / 1 v / v) at a concentration of 0.2 g PAES / 100 mL, according to the procedure described by Kricheldorf and Chatti in High Performance Polymers, 2009, Vol. 21, pp. 105-118.

[0590] Determination of the glass transition temperature (Tg) of PAES

[0591] The glass transition temperature (Tg) of the PAES samples was determined using the midpoint method during the second thermal scan in a differential scanning calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, and E794-06. Details of the procedure used in this invention are as follows: A TA instrument DSC Q20 was used, with nitrogen (99.998% purity, 50 mL / min) as the carrier gas. Temperature and heat flow rate calibration was performed using indium. Sample amounts ranged from 5 to 7 mg. Weights were recorded as ± 0.01 mg. Heating cycles were:

[0592] - First heating cycle: 20.00°C / min, from 30.00°C to 350.00°C, isothermal at 350.00°C for 1 min;

[0593] - First cooling cycle: 20.00°C / min, from 350.00°C to 30.00°C, isothermal for 1 min;

[0594] - Second heating cycle: 20.00°C / min, from 30.00°C to 350.00°C, isothermal at 350.00°C for 1 min.

[0595] The chlorine content of PAES was determined using a chlorine analyzer.

[0596] Using tweezers, place a clean, dry combustion boat on a microbalance and zero the balance. Weigh one to five milligrams of PAES sample into the combustion boat and record the weight to 0.001 mg. Place the combustion boat and sample into the inlet port of the ThermoGLAS 1200 Total Organic Halogen Analyzer and cover the port. Enter the sample weight into the sample weight area of ​​the instrument computer. Then start the sample analysis cycle. The sample is burned in a mixture of argon and oxygen, and the combustion products are passed through a concentrated sulfuric acid scrubber to remove moisture and byproducts. Hydrogen chloride and chlorine oxides from the combustion process are absorbed from the gas stream into the acetic acid solution in the cell. The chloride entering the cell is titrated with silver ions generated by coulometric titration. The percentage of chlorine in the sample is calculated from the integrated current and sample weight.

[0597] Phosphorus content in PAES determined by ICP-OES

[0598] Place a clean, dry platinum crucible on an analytical balance and zero the balance. Weigh 0.5 to 3 g of PAES sample into a small dish and record the weight to 0.0001 g. Place the crucible containing the PAES sample in a muffle furnace (Thermo Scientific Thermolyne F6000 programmable furnace). Gradually heat the furnace to 525°C and maintain this temperature for 10 hours to allow the sample to dry ashed. After ashing, cool the furnace to room temperature and remove the crucible from the furnace and place it in a fume hood. Dissolve the ash in dilute hydrochloric acid. Transfer the solution to a 25 mL volumetric flask using a polyethylene pipette. Rinse the crucible twice with approximately 5 mL of ultrapure water (R < 18 MΩcm) and add the washings to the volumetric flask for quantitative transfer. Add ultrapure water to the flask to a total of 25 mL. Place the stopper on top of the flask and shake thoroughly to mix the contents.

[0599] Inductively coupled plasma optical emission spectrometry (ICP-OES) analysis was performed using a Perkin-Elmer Optima 8300 dual-view instrument. The spectrometer was calibrated using a set of NIST traceable multi-element mixture standards with analyte concentrations ranging from 0.0 to 10.0 mg / L. Linear calibration curves were obtained across a range of concentrations, with correlation coefficients better than 0.9999 for each of the 48 analytes. Standards were run before and after every ten samples to ensure instrument stability. Results were reported as the average of three replicates. The concentration of elemental impurities in the sample was calculated using the following formula: A = (B C) / (D)

[0600] in:

[0601] A = Element concentration in the sample, expressed in mg / kg (= wt.ppm);

[0602] B = Elements in the solution as measured by ICP-OES, expressed in mg / L;

[0603] C = the volume of the solution analyzed by ICP-OES in mL; and

[0604] D = The sample weight in grams used in the program.

[0605] Determination of residual polar aprotic solvent content in PAES

[0606] 0.25 g of PAES sample was dissolved in 5 mL of DMF, and the solution was filtered through a 0.22 μm syringe filter and analyzed by gas chromatography (GC) using a Restek RTX-200 ms (30 m x 250 μm x 0.25 μm) column with hydrogen as the carrier gas at a constant flow rate of 1.6 mL / min.

[0607] GC conditions are:

[0608] •syringe:

[0609] Injection volume: 1.5 µL

[0610] •Entrance:

[0611] Mode: Traffic splitting

[0612] Temperature: 270°C

[0613] Pressure: 8.5744 psi

[0614] Flow split ratio: 10:1

[0615] shunt flow rate 16 mL / min

[0616] • Detector: FID

[0617] Replenishment gas: N2

[0618] Temperature: 310°C

[0619] H2 flow rate: 40 mL / min

[0620] Air flow rate: 400 mL / min

[0621] Supplemental gas flow rate: 15 mL / min

[0622] Constant replenishment gas and fuel flow rates

[0623] • Column oven:

[0624] Initial temperature: 30°C

[0625] • Heat up to 30°C and hold for 4 minutes.

[0626] Increase the temperature to 105°C at a rate of 40°C / min and hold for 1 min.

[0627] Increase the temperature to 175°C at a rate of 40°C / min and hold for 0 min.

[0628] Increase the temperature to 300°C at a rate of 30°C / min and hold for 0 min.

[0629] The residual levels of solvent were determined using external standards of DMAc, sulfolane, and NMP in DMF.

[0630] Determination of residual BPS content in PAES

[0631] 0.5-g of PAES sample was dissolved in 10 mL of DMF. After dissolution, 10 mL of acetonitrile was added with stirring to precipitate the polymer. The solution was filtered through a 0.22-µm syringe filter and analyzed by liquid chromatography using a Supelco Discovery® C18 HPLC column (4.6 mm x 25 mm, 5 µm particle size) (20 µL injection volume).

[0632] The mobile phase has the following gradient composition:

[0633]

[0634] The detector was a UV detector set at 254 nm. The concentration of BPS was determined using an external standard.

[0635] Determination of residual BPA content in PAES

[0636] Dissolve 0.25-g PAES sample in 5 mL of chloroform. Filter the solution through a 0.22-micron syringe filter and analyze by gas chromatography using a Restek™ RTX™-5MS capillary column (30 m long, 0.25 mm ID, 0.25 µm film thickness) and helium at a constant pressure of 14.5 psi.

[0637] GC conditions are:

[0638] •syringe:

[0639] Injection volume: 2 µL

[0640] •Entrance:

[0641] Mode: Traffic splitting

[0642] Temperature: 290°C

[0643] Flow split ratio: 3:1

[0644] • Detector: FID

[0645] Replenishment gas: Helium

[0646] Temperature: 300°C

[0647] H2 flow rate: 30 mL / min

[0648] Air flow rate: 400 mL / min

[0649] Supplemental gas flow rate: 35 mL / min

[0650] Constant replenishment gas and fuel flow rates

[0651] • Column oven:

[0652] Initial temperature: 35°C

[0653] • Heat up to 35°C and hold for 1 minute.

[0654] Increase the temperature to 325°C at a rate of 20°C / min and hold for 10 min.

[0655] The concentration of BPA was determined using an external standard for BPA.

[0656] Examples CE1, CE2, E1-E9

[0657] A general procedure for preparing PAES homopolymers made from ISOSO and DCDPS

[0658] A 1-L four-necked round-bottom flask (reactor vessel) equipped with a mechanical stirrer, a Dean-Stark or Barrett water separator, a condenser, and a nitrogen inlet is loaded with isosorbide (ISOSO) and / or 1,4-cyclohexanediethanol (CHDM) as an alicyclic diol (AA), 4,4'-dichlorodiphenyl sulfone (DCDPS) as a dihaloaryl sulfone monomer (CC), and potassium carbonate (K2CO3) and / or tripotassium phosphate (K3PO4) as a base. A polar aprotic solvent (DMAc, sulfolane, or NMP) is then added to form the reaction medium.

[0659] The total wt% monomers contained in the reaction medium are 44 wt% to 50 wt%, based on the total weight of monomers + solvent.

[0660] The amount of monomer is selected to achieve 40 to 45 wt% total wt% polymer in the reaction medium at the end of polymerization, said wt% based on the total weight of PAES + solvent.

[0661] When used as the sole base in the reaction medium, the amount of potassium phosphate is expressed as a molar ratio of 2.5 of K3PO4 to ISOSO.

[0662] When used as the sole base in the reaction medium, the amount of potassium carbonate is expressed as a molar ratio of 3:1 to 3:1 (K₂CO₃ to ISOSO₄).

[0663] When used together as a base in the reaction medium, the amounts of tripotassium phosphate and potassium carbonate are expressed as a molar ratio of K3PO4 to ISOSO of 1 to 1.875 and a molar ratio of K2CO3 to ISOSO of 2 to 0.29.

[0664] The molar ratio between the total amount of hydroxyl groups from ISOSO [alicyclic diol (AA)] and the total amount of halogen groups from DCDPS [dihaloaryl sulfone monomer (CC)] is 0.997 to 1.007.

[0665] The reactor vessel was purged with nitrogen for 15 minutes, and then the reaction was initiated. The reaction medium containing the monomer was stirred with a top-mounted mechanical stirrer and heated using a heating mantle controlled at the target internal reaction temperature until the reaction was initiated to a suitable reaction temperature (167°C to 200°C as indicated in Tables 1 and 2 below). The reaction medium temperature was increased from room temperature (e.g., 20°C–21°C) to the suitable reaction temperature over approximately 30–60 minutes. In the case of reaction with K₂CO₃, water (a byproduct of the polymerization reaction) was continuously vaporized from the reactor vessel and collected in a Dean-Stark water separator, and the reaction medium was stirred with a top-mounted mechanical stirrer and heated to the suitable reaction temperature indicated in Tables 1 and 2 below. After reaching the target reaction temperature, the reaction medium was maintained at that temperature for a suitable reaction time until the desired M was achieved. w (It is usually measured by viscosity). The reaction time can vary from 12 to 24 hours, and is typically about 13 to 21 hours.

[0666] Once the desired molecular weight was achieved, polymerization was terminated by bubbling 50 g of gaseous chloromethane through the reaction medium over 30 minutes. Because the reaction medium became viscous and difficult to stir at the end of the reaction, it was diluted with DMAc to obtain a 20 wt% PAES polymer and cooled to less than 130°C.

[0667] The cooled medium was filtered under pressure through a 2.7-μm glass fiber filter pad to remove salts. The polymer was then condensed from the filtered solution by pouring the solution into a Warin mixer containing 2.5-L of a non-solvent (methanol) (using a 1:5 weight ratio of PAES solution to non-solvent) to precipitate PAES and obtain a white solid. The resulting solid was then separated by filtration and washed five times with 2.5 L of methanol at room temperature. The resulting solid was dried overnight in a vacuum oven at 120°C.

[0668] Each PAES sample was further analyzed to measure its intrinsic viscosity (IV), and its M w M n M z (via GPC), its Tg (via DSC (second heating), its phosphorus content (via ICP-OES), and its chlorine content (via chlorine analyzer). The ratio for each PAES sample was also calculated: M w / M n (PDI) and M z / M w All reaction conditions and test results are summarized in Table 1.

[0669] The data in Table 1 show that using K3PO4 as the sole base in various solvents (sulfolane, NMP, and DMAc) prepared a high M... w (M) w Examples of PAES homopolymers E4-E9 made from ISOSO and DCDPS (>59 kDa).

[0670] When polycondensed in sulfolane, example E3, a homopolymer of PAES made from ISOSO and DCDPS using a blend of K3PO4 and K2CO3 (1:2 molar ratio), also achieved high M. w (M) w > 59 kDa).

[0671]

[0672] In contrast, the PAES homopolymers (CE1, CE2) prepared in sulfolane using K2CO3 as the sole base from ISOSO and DCDPS showed a M value of 41 kDa before depolymerization (pyrolysis) began. w It reached its peak at that point.

[0673] Examples E10-E11

[0674] A general procedure for preparing PAES copolymers made from ISOSO / BP (75 / 25 mol / mol) and DCDPS

[0675] For PAES copolymer examples E10 and E11, the general procedure used for examples CE1 to E9 was followed, except that 4,4'-biphenyl (BP) as an aromatic diol (BB) was used together with isosorbide (ISOSO) as an alicyclic diol (AA) in the reaction with DCDPS as a dihaloaryl sulfone monomer (CC). The reaction conditions and test results are summarized in Table 2.

[0676] The data in Table 2 show that using K3PO4 alone (the sole base) or a blend of K3PO4 and K2CO3 as the base achieved high M values ​​for PAES copolymers E10 and E11 made from isosorbide and bisphenol (with an ISOSO / BP molar ratio of 75 / 25) and DCDPS. w .

[0677] Table 2: PAES copolymers based on DCDPS, isosorbide and 4,4'-biphenyl

[0678]

[0679] wt ppm = ppm based on weight

[0680] The Tg of these PAES copolymers E10 and E11 is higher than the typical Tg (220°C) of PPSU (a homopolymer made from DCDPS and BP).

[0681] Examples CE12-E13

[0682] Preparation of PAES copolymers made from 1,4-cyclohexanediethanol / BP (80 / 20-90 / 10 mol / mol) and DCDPS

[0683] For PAES copolymer examples CE12-E13, the general procedure used for examples CE1 to E9 is followed, except that 1,4-cyclohexanediethanol “CHDM” (a mixture of cis and trans isomers) with formula (D8) is used instead of isosorbide as an alicyclic diol (AA), and 4,4'-biphenyl (BP) is used as an aromatic diol (BB) for the reaction with DCDPS as a dihaloaryl sulfone monomer (CC).

[0684] The reaction conditions and test results are summarized in Table 3. For Example E13, K3PO4 was used as the sole base. For Comparative Example CE12, K2CO3 was used as the sole base.

[0685] Table 3: PAES copolymers made from DCDPS, 1,4-c-cyclohexanediethanol and 4,4'-biphenyl

[0686]

[0687] wt ppm = ppm based on weight

[0688] The data in Table 3 show that the PAES homopolymer example E13, prepared in sulfolane from CHDM and DCDPS using K3PO4 as the sole base, exhibits high M... w (M) w > 59 kDa). Its M w (66 kDa) is significantly higher than that of PAES homopolymer prepared in sulfolane from the same amounts of CHDM and DCDPS but using potassium carbonate (K2CO3) as the sole base, compared to Example E12. w (8.4kDa).

[0689] Examples E14-E15

[0690] PAES homopolymer prepared by diluting wt% monomers from isosorbide and DCDPS during polymerization

[0691] For PAES copolymer examples E14-E15, the general procedure used for examples CE1 to E9 is followed, except that during polymerization, solvent is added to the reaction medium in three separate (continuous) stages to provide gradual dilution of the reaction medium, thereby gradually reducing the wt% monomer concentration. For the first polymerization stage, an initial amount of solvent is added to dissolve the monomer. When the target viscosity of the reaction medium (approximately 5000-8000 cP) is reached, another fixed amount of solvent is added to the reaction medium to begin the second polymerization stage. When the target viscosity of the reaction medium (approximately 5000-8000 cP) is reached during this second stage, yet another additional amount of solvent is added to the reaction medium to begin the third polymerization stage.

[0692] The data in Table 4 show that high-M precipitates were obtained by polycondensation of ISOSO and DCDPS when the reaction medium was gradually diluted with solvent during the polymerization process, that is, when the wt% monomer concentration was reduced from 54.5-54.6 wt% (stage 1) to 34 wt% or 39.8 wt% (stage 3) to provide an optimal balance between reactivity and viscosity of the reaction medium. w PAES homopolymers (71 kDa; 90 kDa).

[0693] Table 4: PAES homopolymers prepared from ISOSO and DCDPS using wt% monomer dilution in three consecutive polymerization stages

[0694]

[0695] wt ppm = ppm based on weight Acquired after the third stage

[0696] While preferred embodiments of the invention have been shown and described, those skilled in the art can modify them without departing from the spirit or teachings of the invention. The embodiments described herein are merely exemplary and non-limiting. Various changes and modifications to the systems and methods are possible and within the scope of the invention. Therefore, the scope of protection is not limited by the foregoing description, but only by the following claims, which include all equivalents of the subject matter of the claims. Each claim is incorporated herein by reference as an embodiment of the invention. Therefore, the claims are further descriptions and appendices to the preferred embodiments of the invention.

Claims

1. A polyarylether sulfone (PAES) prepared by condensation of the following: - At least one alicyclic diol (AA) comprising at least one cyclic aliphatic moiety (M), and -At least one dihaloaryl sulfone monomer (CC) containing at least one -S(=O)2- group, The PAES has a phosphorus content of at least 6 ppm, where ppm is based on the total weight of the PAES.

2. The PAES as described in claim 1, wherein, The PAES contains repeating units (R) with the following formula (Ia). a ): (I), in: - Each R1 is independently selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammoniums; - For each R1, i is 0, 1, 2, 3, or 4; and -E contains at least one cyclic aliphatic moiety (M) and is a group containing 4 to 30 carbon atoms, preferably 4 to 15 carbon atoms.

3. The PAES as described in claim 2, wherein, E is selected from the following groups: those that have equations (E1) to (E11): , and any combination thereof, Each symbol in these equations (E1) to (E11) Indicates the position of the E bond to the oxygen atom in the -OEO- pattern; and In equation (E11), each Q' that is the same or different is a non-cyclic part.

4. The PAES as claimed in any one of claims 1 to 3, wherein, The PAES has the following M z / M w : - At least 1.5, preferably at least 1.51, more preferably at least 1.52, and / or - Up to 1.8, preferably up to 1.75, more preferably up to 1.7, and even more preferably up to 1.

65. Where M z It is the size-average molecular weight of the PAES and M w It is the weight-average molecular weight of the PAES, and the M of the PAES w and M z It was determined by gel permeation chromatography (GPC) calibrated with polystyrene standards and using DMAc as the mobile phase.

5. The PAES as claimed in any one of claims 1 to 4, wherein, The PAES has an M of at least 60,000 g / mol, and preferably at most 120,000 g / mol. w .

6. The PAES as claimed in any one of claims 1 to 5, wherein, The PAES has an intrinsic viscosity (IV) of at least 0.40 dL / g, and preferably at most 1.5 dL / g.

7. The PAES as claimed in any one of claims 2 to 6, wherein, E is selected from the following groups: those that have the formulas (E1), (E2), (E3), (E4), (E5), and (E11): , and any combination thereof, Each symbol in these equations (E1), (E2), (E3), (E4), (E5), and (E11) This indicates the position of the E atom bonded to the oxygen atom in the -OEO configuration. In equation (E11), each identical or different Q' is a non-cyclic part, and The PAES has the following glass transition temperature (Tg): - At least 215°C, preferably at least 218°C, more preferably at least 220°C, even more preferably at least 222°C, and even more preferably at least 225°C; and / or - Up to 255°C, preferably up to 250°C, more preferably up to 245°C.

8. The PAES as claimed in any one of claims 1 to 7, wherein, The PAES further has at least one of the following characteristics: - A number-average molecular weight (Mn) of at least 21,000 g / mol, and preferably at most 80,000 g / mol. n ); - Characteristic M is at least 1.5 and at most 1.8 z / M w Molecular weight distribution; -The following chlorine content: At least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm, and even more preferably at least 300 ppm, and / or Up to 3000 ppm, preferably up to 2900 ppm, more preferably up to 2800 ppm; - Bisphenol A in amounts less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm; - Bisphenol S in amounts less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm; - Not exceeding 2 wt% of oligomer fractions with a molecular weight of less than 3000 g / mol; and / or - Residual polar aprotic solvent content of less than 3000 ppm, preferably less than 2500 ppm, more preferably less than 2000 ppm; The ppm and wt% are based on the total weight of the PAES.

9. The PAES according to any one of claims 1 to 8, wherein it is a copolymer produced by condensation of the following: - at least one alicyclic diol (AA), -The at least one dihaloaryl sulfone monomer (CC) containing at least one -S(=O)2- group, and - At least one co-diol selected from aromatic diols (BB) and / or noncyclic diols (BB'), The aromatic diol (BB) is preferably selected from the group consisting of: bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4'-biphenyl, diallyl biphenyl, bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, hydroquinone, resorcinol, aromatic triols such as 1,1,1-tris-(4-hydroxyphenyl)-ethane, and any combination of two or more thereof; more preferably selected from the group consisting of: bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4'-biphenyl, diallyl biphenyl, bisphenol F, tetramethyl bisphenol F, and any combination of two or more thereof; even more preferably selected from the group consisting of: 4,4'-biphenyl, diallyl biphenyl, tetramethyl bisphenol F, and any combination of two or more thereof; most preferably 4,4'-biphenyl. The acyclic diol (BB') is preferably selected from epoxides and / or poly(epoxides), more preferably from the group consisting of: ethylene glycol, propylene glycol [HO-CH2-CH(CH3)-OH], 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, poly(ethylene glycol), poly(propylene glycol), poly(tetramethylene oxide), and any combination of two or more thereof; and The molar ratio r of the at least one alicyclic diol (AA) to the at least one co-diol is: - Up to 95:5, preferably up to 90:10, more preferably up to 85:15, and even more preferably up to 80:20, and / or - At least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, even more preferably at least 50:50, and even more preferably at least 60:

40.

10. A method for manufacturing a polyarylether sulfone polymer [hereinafter "PAES"], the method comprising: The following reaction is carried out in a reaction medium containing a polar aprotic solvent and a base containing an inorganic metal phosphate: - At least one alicyclic diol (AA) comprising at least one cyclic aliphatic moiety (M), and -At least one dihaloaryl sulfone monomer (CC) containing at least one -S(=O)2- group, The inorganic metal phosphate contains metals selected from Group 1, 2 or 3 of the IUPAC periodic table.

11. The method of claim 10, wherein, This inorganic metal phosphate is an alkali metal phosphate. Its characteristic is that the pKa of its conjugate acid is greater than 10.5 and less than 15.

12. The method of claim 10 or 11, wherein, The inorganic metal phosphate is a ternary alkali metal phosphate, wherein the alkali metal is K, Na, Cs and / or Li; preferably tripotassium phosphate (K3PO4) and / or trisodium phosphate (Na3PO4); more preferably K3PO4.

13. The method of claim 12, wherein, The ternary alkali metal phosphate, preferably tripotassium phosphate (K3PO4) and / or trisodium phosphate (Na3PO4), more preferably K3PO4, has a median particle size (D) of 10 micrometers to 400 micrometers. 50 ), the D 50 It was measured by light scattering in dry mode.

14. The method according to any one of claims 10 to 13, wherein, The alkali further comprises an alkali metal carbonate selected from the group consisting of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, preferably selected from sodium carbonate and / or potassium carbonate, and more preferably potassium carbonate.

15. The method according to any one of claims 10 to 14, wherein, The at least one alicyclic diol (AA) is represented by formula (D): HO-E-OH(D), Wherein E contains at least one cyclic aliphatic moiety (M) and is a group containing 4 to 30 carbon atoms, preferably 4 to 15 carbon atoms.

16. The method of claim 15, wherein, E is selected from the following groups: those that have equations (E1) to (E11): , and any combination thereof, Each symbol in these equations (E1) to (E11) Indicates the position of the E bond to the oxygen atom in the -OEO- pattern; and In equation (E11), each Q' that is the same or different is a non-cyclic part.

17. The method according to any one of claims 10 to 16, wherein, The at least one dihalogenated sulfone monomer (CC) is represented by formula (C1): (C1)， in: - Each R1—whether identical or different from each other—is selected from the group consisting of: halogens, alkyl, alkenyl, alkynyl, aryl, carboxylic acids, esters, amides, imides, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, alkali metal phosphonates, alkaline earth metal phosphonates, alkyl phosphonates, amines, and quaternary ammoniums. - Each i—whether the same or different from each other—is independently zero or an integer from 1 to 4, preferably independently zero or 1, more preferably zero; and -X and X' – which may be the same as or different from each other – are independently halogen atoms, preferably Cl or F, more preferably Cl.

18. The method according to any one of claims 10 to 17, wherein, The at least one dihalosulfone monomer (CC) is selected from the group consisting of: dichlorodiphenyl sulfone (DCDPS), difluorodiphenyl sulfone (DFDPS), monosulfonated dichlorodiphenyl sulfone (msDCDPS), disulfonated dichlorodiphenyl sulfone (dsDCDPS), and any combination of two or more thereof; preferably selected from the group consisting of: DCPS, msDCDPS, dsDCDPS, and any combination of two or more thereof.

19. The method according to any one of claims 10 to 18, wherein, The reaction medium further comprises at least one co-diol selected from aromatic diols (BB) and / or noncyclic diols (BB'), and The molar ratio r of the at least one alicyclic diol (AA) to the at least one co-diol is: - Up to 95:5, preferably up to 90:10, more preferably up to 85:15, and even more preferably up to 80:20, and / or At least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, even more preferably at least 50:50, and even more preferably at least 60:

40.

20. The method of claim 19, wherein, The glycol is: -Aromatic diols (BBs), selected from the group consisting of: bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4'-biphenyl, diallyl biphenyl, bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, hydroquinone, resorcinol, aromatic triols such as 1,1,1-tris-(4-hydroxyphenyl)-ethane, and any combination of two or more thereof; preferably selected from the group consisting of: bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4'-biphenyl, diallyl biphenyl, bisphenol F, tetramethyl bisphenol F, and any combination of two or more thereof; more preferably selected from the group consisting of: 4,4'-biphenyl, diallyl biphenyl, tetramethyl bisphenol F, and any combination of two or more thereof; most preferably 4,4'-biphenyl. and / or Acyclic diol (BB') selected from epoxides and / or poly(epoxides); preferably selected from the group consisting of: ethylene glycol, propylene glycol [HO-CH2-CH(CH3)-OH], 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, poly(ethylene glycol), poly(propylene glycol), poly(tetramethylene oxide), and any combination of two or more thereof.

21. The method according to any one of claims 10 to 20, wherein, The molar amount of the inorganic metal phosphate in the reaction medium is relative to the molar amounts of the at least one alicyclic diol (AA) and any optional codiol in the reaction medium: - at least 1.00, or at least 1.04, or at least 1.10, or at least 1.15, or at least 1.20, or at least 1.25, or at least 1.30, and / or - Up to 3.0, or up to 2.8, or up to 2.75, or up to 2.5, or up to 2.

4.

22. The method according to any one of claims 10 to 21, wherein, The reaction is carried out based on the following total weight % monomer concentration [hereinafter "total wt% monomer"] based on the total weight of the alicyclic diol (AA), dihalogenated monomer (CC), any optional co-diol, and the polar aprotic solvent: - At least 30 wt%, preferably at least 35 wt%, more preferably at least 38 wt%, and / or - Up to 60 wt%, preferably up to 55 wt%, more preferably up to 50 wt%.

23. The method according to any one of claims 10 to 22, wherein, The reaction proceeds at the following reaction temperatures: - Above 110°C, preferably at least 115°C, preferably at least 160°C, and - Less than 210°C, preferably up to 200°C, more preferably up to 190°C, even more preferably up to 180°C, and even more preferably up to 175°C.

24. The method according to any one of claims 10 to 23, wherein, The molar ratio between the total amount of hydroxyl groups from the at least one alicyclic diol (AA) and any optional co-diol in the reaction medium and the total amount of halogen groups from the dihalosulfone monomer (CC) is 0.95 to 1.05, preferably 0.98 to 1.02, more preferably 0.985 to 1.015, even more preferably 0.99 to 1.01, and even more preferably 0.995 to 1.

007.

25. The method according to any one of claims 10 to 24, wherein, The polar aprotic solvent is selected from the group consisting of: 1,3-dimethyl-2-imidazolinone (DMI), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), diphenyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrothiophene-1,1-dioxide (sulfolane), N-methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N-dimethylacetamide (DMAc), and N,N′-dimethylacrylurea (DMPU). The solvents are: DMI, NMP, NBP, NEP, DMAc, DMF, sulfolane, and any mixture of two or more of these solvents; preferably selected from the group consisting of: DMI, NMP, DMAc, sulfolane, and any mixture of two or more of these solvents; more preferably selected from the group consisting of: DMI, NMP, DMAc, sulfolane, and any mixture of two or more of these solvents.

26. A PAES obtained by the method of any one of claims 10 to 25, wherein the PAES contains at least 6 ppm, and preferably at most 150 ppm, phosphorus. Preferably, the PAES further has at least one of the following features: - A weight-average molecular weight (M) of at least 60,000 g / mol, and preferably at most 120,000 g / mol. w ); - A number-average molecular weight (Mn) of at least 21,000 g / mol, and preferably at most 80,000 g / mol. n ); - Characteristic M is at least 1.5 and at most 1.8 z / M w The molecular weight distribution of the ratio; -The following chlorine content: At least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm, and even more preferably at least 300 ppm, and / or Up to 3000 ppm, preferably up to 2900 ppm, more preferably up to 2800 ppm; - Bisphenol A in amounts less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm; - Bisphenol S in amounts less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm; - An amount of oligomer fraction having a molecular weight of less than 3000 g / mol, not exceeding 10 wt%, preferably not exceeding 8 wt%, more preferably not exceeding 5 wt%, and most preferably not exceeding 2 wt%; and / or - Residual polar aprotic solvent content of less than 3000 ppm, preferably less than 2500 ppm, more preferably less than 2000 ppm, most preferably less than 1000 ppm and most preferably less than 500 ppm; The ppm and wt% are based on the total weight of the PAES.

27. Use of PAES as claimed in any one of claims 1 to 9 or 26 for the manufacture of films, coatings, thin films, sheets and / or three-dimensional molded parts.

28. A polymer stock solution for preparing a membrane, the polymer stock solution comprising PAES as described in any one of claims 1 to 9 or 26 in a polar organic solvent.

29. A molded article manufactured by PAES as claimed in any one of claims 1 to 9 or 26, selected from the group consisting of: membranes, melt-processed films, solution-processed films, melt-processed monofilaments and fibers, solution-processed monofilaments, hollow fibers and solid fibers, coatings, printed articles, and injection-molded and compression-molded articles, preferably membranes selected from membranes for bioprocessing and medical filtration (such as 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.

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