WO2025210173A1 - Polyarylethersulfone containing phosphorous and made from dihaloarylsulfone and acyclic diol - Google Patents

Polyarylethersulfone containing phosphorous and made from dihaloarylsulfone and acyclic diol

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Publication number
WO2025210173A1
WO2025210173A1 PCT/EP2025/059167 EP2025059167W WO2025210173A1 WO 2025210173 A1 WO2025210173 A1 WO 2025210173A1 EP 2025059167 W EP2025059167 W EP 2025059167W WO 2025210173 A1 WO2025210173 A1 WO 2025210173A1
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Prior art keywords
paes
ppm
group
diol
bisphenol
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PCT/EP2025/059167
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French (fr)
Inventor
Chantal Louis
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Syensqo Specialty Polymers USA LLC
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Syensqo Specialty Polymers USA LLC
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Publication of WO2025210173A1 publication Critical patent/WO2025210173A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4056—(I) or (II) containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/06—Polysulfones; Polyethersulfones

Definitions

  • PAES Poly(aryl ether sulfone) polymers
  • PAES polysulfone polymers identified herein as polysulfones, in short PSU.
  • PSU polymers contain recurring units made from the condensation of the dihydroxy monomer bisphenol A (BPA) and a dihalogen monomer, for example 4,4'-dichlorodiphenyl sulfone (DCDPS).
  • BPA dihydroxy monomer bisphenol A
  • DCDPS 4,4'-dichlorodiphenyl sulfone
  • PSU polymers are commercially available from Solvay Specialty Polymers USA, LLC (member of the SYENSQO group) under the trademark UDEL® PSU.
  • PAES poly ethersulfone polymers
  • PES polymers derive from the condensation of the dihydroxy monomer bisphenol S (BPS) and a dihalogen monomer, for example 4,4'-dichlorodiphenyl sulfone (DCDPS).
  • BPS dihydroxy monomer bisphenol S
  • DCDPS 4,4'-dichlorodiphenyl sulfone
  • PES polymers are commercially available from Solvay Specialty Polymers USA, LLC under the trademark VERADEL® PES.
  • PSU and PES polymers, respectively based on BPA and BPS are frequently used to prepare membranes to be used in contact with biological fluids, for example blood.
  • BPA and BPS are industrial chemicals that have been present in many articles, including plastic bottles and food and beverage cans since the 1960s. In recent years, concerns have been raised about BPA and BPS's safety. BPS and BPA are suspected to be endocrine disruptive in nature, albeit without conclusive research, and their impact on the environment and human health is still under investigation. In view of this controversy, the market is looking for economically viable alternatives to BPA and BPS.
  • EP0739925 (BAYER AG) describes polysulfone-poly ether block copolycondensates of formula (I): -(O-E-O-Arl-SO2-Ar2-)-W- , wherein E is a divalent diphenolate radical and W is a poly ether, polythioether or polyacetal possessing at least two hydroxyl groups and having an average molecular weight of from 400 to 30,000 and wherein the proportion of the radical W in the total polymer amounts to 5 to 99 weight percent.
  • Their synthesis is carried out by strong base chemistry, in which an alkali metal alkoxylate is used to deprotonate aliphatic polyetherdiol. In the examples, a weight fraction of polyethylene glycol of about 34-60 wt% is used.
  • US6365678B1 (BAYER AG) describes a process for the production of poly ether block copolysulfones, comprising reacting (A) at least one aromatic sulfone polymer, with (B) at least one aliphatic polyether having on average at least one terminal OH function.
  • the reaction is between a formed high molecular weight polysulfone with a poly ether in the presence of a basic catalyst to incorporate the polyether segment by transetherification.
  • bases such as carbonates, phosphates (notably NasPO-i. K3PO4 or K2HPO4), amines, hydroxides such as NaOH, are cited as being suitable, only potassium carbonate is exemplified as a base.
  • 1,4:3, 6-dianhydrohexitols can deliver advantageous features when incorporated into poly aryl ether sulfone structures. Also the innocuous character of the molecules opens the possibility of applications in packaging or medical devices, e.g., for hemodialysis membranes.
  • the 1,4:3, 6-dianhydrohexitols are composed of two cis-fused tetrahydrofuran rings, nearly planar and V-shaped with a 120° angle between rings.
  • the hydroxyl groups are situated at carbons 2 and 5 and positioned on either inside or outside the V-shaped molecule. They are designated, respectively, as endo or exo.
  • a summary of the manufacture of these l,4:3,6-dianhydrohexitols can be found in US 2015/0011446A1 (SOLVAY SPECIALTY POLYMERS ITALY, SpA).
  • 1,4:3, 6-dianhydrohexitols especially isosorbide
  • polymers such as notably polyesters, poly ethers, polyurethanes and polyamides.
  • 1,4:3, 6-dianhydrohexitols in polymers, and more specifically in poly condensates, can be motivated by several features: they are are rigid bicyclic chiral diols derived from sugars, chiral, and non-toxic.
  • isosorbide is obtained from the double dehydrogenation reaction of sorbitol, itself derived from the glucose hydrogenation reaction.
  • the highest apparent molecular weight polymer obtained had an inherent viscosity IV of 0.65 dL/g, said IV was measured according to following conditions : CHiCh/trifluoroacetic acid solution (9/1 v/v) at 20°C, 0.20 g/dL. The glass transition temperature of this polymer was reported as 245°C. No examples were described where the polymerization reaction with isosorbide was conducted with the less reactive dichlorodiphenylsulfone (DCDPS).
  • DCDPS dichlorodiphenylsulfone
  • WO 2014/072473 A2 (SOLVAY SPECIALTY POLYMERS USA, LLC) describes a method for the preparation of aromatic poly ethersulfones based on isosorbide. The method involves the reaction between difluorodiphenylsulfone or dichlorodiphenylsulfone, optionally in the presence of a fluorinating agent, and isosorbide in the presence of potassium carbonate at a temperature of 210° C.
  • poly(sulfone isosorbide) of Mw above 58 kDa.
  • the method involves the reaction between 4,4'- difluorodiphenylsulfone and a non-aromatic cyclic diol in the presence of potassium carbonate at a minimum temperature of 160° C, and the reaction between 4,4'- dichlorodiphenylsulfone and a non-aromatic cyclic diol in the presence of potassium carbonate at a minimum temperature of 210-215 °C.
  • the present invention aims to address several challenges linked to process economics and use of acyclic diol monomer(s) to either partially or completely replace bisphenols in order to lessen the impact of endocrine disruption potential.
  • a PAES from less-reactive acyclic diols, containing at least 2 hydroxy groups such as alkylene oxide or poly(alkylene oxide), and optionally from less-reactive alicyclic compounds, by using a more cost-effective chlorinated sulfone monomer (e.g., dichlorodiphenylsulfone (DCDPS) and/or sulfonated DCDPS) while still achieving reasonably high molecular weight (e.g., M w > 40 kDa, preferably > 50 kDa) for the PAES; and
  • a more cost-effective chlorinated sulfone monomer e.g., dichlorodiphenylsulfone (DCDPS) and/or sulfonated DCDPS
  • PAES materials such as those made from Bisphenol A (BP A) or Bisphenol S (BPS) - in order for their use in applications where contact with food, drugs, blood and/or water takes places, such as in membrane markets.
  • BP A Bisphenol A
  • BPS Bisphenol S
  • a second aspect of the invention relates to a process defined in any one of claims 11-24 for manufacturing the PAES.
  • heterocyclic defines a structure (such as a diol or moiety) which contains one or more rings with more than one type of atoms in the ring, one of which being a carbon atom and the other being a heteroatom (i.e., a noncarbon atom, such as oxygen atom, sulfur atom or nitrogen atom).
  • aliphatic diol means, for the purpose of the present invention, a non-aromatic organic compound comprising two hydroxyl functions.
  • An aliphatic diol may be linear, branched or cyclic.
  • the aliphatic diol may, in addition to the oxygen atoms of the two hydroxyl groups, comprise one or more heteroatoms (i.e., non-carbon atoms), for example atoms of oxygen, nitrogen and/or sulfur.
  • alicyclic defines a structure that is both aliphatic (meaning non-aromatic) and cyclic.
  • An alicyclic structure (such as a diol or moiety) may contain one or more non-aromatic rings.
  • An alicyclic structure may be unsaturated or saturated.
  • cycloaliphatic moiety or "alicyclic moiety” are interchangeable and are intended to denote any moiety being both aliphatic (i.e., not aromatic) and cyclic (i.e., where atoms are connected in a ring).
  • the cycloaliphatic moiety (M) may be either unsubstituted or substituted.
  • the cycloaliphatic moiety may be heterocyclic. When the cycloaliphatic moiety (or alicyclic moiety) does not comprise any heteroatoms in the ring, the backbone of the cycle of the cycloaliphatic (or alicyclic) moiety is made only of interconnected carbon atoms.
  • an alicyclic diol may be heterocyclic, in that at least one ring comprises one or more heteroatoms (i.e., noncarbon atoms) in a ring, for example atoms of oxygen, nitrogen and/or sulfur.
  • acyclic defines a structure which does not have any ring.
  • An acyclic structure (such as a diol or moiety) may be unsaturated or saturated.
  • linear aliphatic diols and “branched aliphatic diols” are acyclic diols.
  • an acyclic diol may comprise one or more heteroatoms (i.e., non-carbon atoms, for example atoms of oxygen, nitrogen and/or sulfur) connected to at least one carbon atom, or may have a backbone made only of connected carbon atoms.
  • aromatic defines a structure (such as a diol or moiety) which contains at least one aromatic ring.
  • l,4:3,6-dianhydrohexitol means a heterocyclic diol obtained by double dehydration of a hexitol such as mannitol, sorbitol and iditol.
  • the l,4:3,6-dianhydrohexitols are primarily in the form of stereoisomers: isosorbide, isomannide, and isoidide.
  • An l,4:3,6-dianhydrohexitol may be used in the present invention as at least one alicylic diol (BB’) for the formation of the PAES according to the invention.
  • the l,4:3,6-dianhydrohexitol used as alicylic diol (BB’) in the process of the invention is isosorbide.
  • total weight % monomers is defined as the weight of the monomers initially present in the reaction medium based on the total weights of monomers and solvent.
  • recurring unit designates the smallest unit of a PAES polymer which is repeating in the chain and which is composed of a condensation of a diol compound and a dihaloaryl compound.
  • recurring unit is synonymous to the terms “repeating unit” and “structural unit”.
  • the term “homopolymer” encompasses a polymer which only has one type of recurring unit.
  • the PAES homopolymer is obtained from the condensation of only one diol monomer and only one one dihaloaryl monomer.
  • copolymer encompasses a polymer which may have two or more different types of recurring units.
  • the PAES copolymer may be obtained from the condensation of at least two diol monomers and at least one dihaloaryl monomer, or from the condensation of at least one diol monomer and at least two dihaloaryl monomers.
  • the abbreviation “ISOSO” means isosorbide;
  • the abbreviation “BP A” means Bisphenol A or 4,4'-isopropylidenediphenol;
  • the abbreviation “BPS” means Bisphenol S or 4,4’ -dihydroxy diphenyl sulfone;
  • the abbreviation “BP” means 4,4’-biphenol;
  • the abbreviation “TMBPF” means tetramethyl Bisphenol F;
  • the abbreviations “daBPA”, “daBPS” and “daBP” refer to diallyl Bisphenol A, diallyl Bisphenol S and diallyl 4,4 ’-biphenol, respectively.
  • a polyethersulfone denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol. %, at least 95 mol.%, or at least 99 mol.% of recurring units (RPES) of formula (J):
  • PES can be prepared by known methods and is notably available as VERADEL® PES from Solvay Specialty Polymers USA, L.L.C.
  • a polysulfone denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 99 mol.% of recurring units (RPSU) of formula
  • PSU can be prepared by known methods and is notably available as Udel® PSU from Solvay Specialty Polymers USA, L.L.C.
  • a polyphenylsulfone denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least f
  • PPSU can be prepared by known methods and is notably available as RADEL® PPSU from Solvay Specialty Polymers USA, L.L.C.
  • weight average molecular weight (Mw) is hereby used according to its usual meaning and mathematically expressed:
  • M w (Z Ni» Mi 2 ) / S Ni*Mi wherein the summation S is over all the chain lengths from 1 to oo, Mi is the discrete value for the molecular weight of polymer molecule, and Ni is the number of polymer molecules with weight Mi.
  • substantially free of a component in a substance means that the concentration of the component is no more than 1 wt% or no more than 0.5 wt% based on the total weight of such substance.
  • acyclic aliphatic monomers which have low or no endocrine disruption potential can be used to successfully prepare, using an inorganic metal phosphate (preferably tripotassium phosphate) as a base in a polar aprotic solvent, a PAES homopolymer or copolymer with appropriate set of characteristics and properties (notably high molecular weight Mw > 40 kDa, preferably > 50 kDa).
  • an inorganic metal phosphate preferably tripotassium phosphate
  • PAES homopolymer or copolymer with appropriate set of characteristics and properties (notably high molecular weight Mw > 40 kDa, preferably > 50 kDa).
  • PAES homopolymer or copolymer incorporating such acyclic monomer, as well as articles comprising it or made from the PAES (such as membranes to be used for purifying water or biological fluids) should exhibit a low or reduced estrogenic activity compared to PAES polymers made from bisphenol A or bisphenol S, and therefore they should present lower risks for human health.
  • PAES homopolymer or copolymer according to the invention can also be effectively prepared using a less-expensive dichlorodiphenylsulfone monomer (DCDPS), thereby providing a more cost effective production, despite the fact that these acyclic diols tend to have poorer reactivity with DCDPS, when compared to more-reactive difluorodiphenylsulfone monomer (DFDPS).
  • DCDPS dichlorodiphenylsulfone monomer
  • DFDPS difluorodiphenylsulfone monomer
  • PAES Poly(arylether sulfone) polymer
  • PAES poly(arylethersulfone)
  • AA acyclic diol monomer
  • CC dihaloaryl sulfone monomer
  • M w high molecular weight
  • the PAES according to the invention has a higher M w compared to a PAES which is made by condensation of same monomers but in the presence of potassium carbonate used as sole base during polycondensation.
  • the PAES according to the invention may further have a narrower molecular weight distribution compared to a PAES made using a weak base.
  • the PAES according to the invention may be characterized by a higher M z /M w ratio compared to a PAES which is made by condensation of same monomers but in the presence of potassium carbonate used as sole base during polycondensation.
  • the Mz/Mw of the PAES according to the invention may be advantageously at least 1.5, preferably at least 1.51, more preferably at least 1.52 and/or the M z /M w of the PAES may be advantageously at most 1.8, preferably at most 1.75, more preferably at most 1.7, yet more preferably at most 1.65, wherein M z is the size average molecular weight of the PAES and M w is the weight average molecular weight of the PAES.
  • the M w and M z of the PAES are preferably determined by gelpermeation chromatography (GPC) calibrated with polystyrene standards and performed using DMAc as mobile phase.
  • a PAES having a phosphorous content of at least 3 ppm P, or at least 4 ppm P, or at least 5 ppm P, or at least 6 ppm P.
  • the ‘ppm P’ content in the PAES is based on weight, meaning that 6 ppm is equivalent to 6 microgram P per g of PAES.
  • the phosphorous content of the PAES according to the invention may be 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. At least a portion of the phosphorous in the PAES is not chemically bound to the PAES.
  • the phosphorous in the PAES originates at least in part from inorganic metal phosphate(s).
  • the phosphorous content is preferably measured by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) analysis after mineralization by ashing.
  • ICP-OES Inductively Coupled Plasma Optical Emission Spectroscopy
  • the phosphorous content in the PAES originates from free phosphorous- containing material such as residual inorganic metal phosphate (e.g., K3PO4, K2HPO4), and optionally from any phosphorous-containing material bound to the PAES polymer chains such as in pendant groups. At least a portion of the phosphorous in the PAES is not chemically bound to the PAES.
  • free P means that the phosphorous-containing material is not chemically bound to the PAES polymeric chain and end groups. For instance, the free P-containing material may be trapped in or adsorbed onto the PAES polymeric chains.
  • bound P means that the phosphorous-containing material is chemically bound to the PAES polymer chain (for example by way of phosphate-containing pendant groups) and//or phosphate-containing end groups.
  • more than 80 wt% and up to 100 wt% of the phosphorous content in the PAES originates from free phosphorous-containing material, preferably from residual inorganic metal phosphate, more preferably from residual potassium phosphate (tri-, di- or monobasic).
  • the PAES according to the present invention has a content in free (not chemically bound) phosphorous of at least 3 ppm P, or at least 4 ppm P, or at least 5 ppm P, or 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 phosphorous content is preferably measured by ICP-OES analysis after mineralization by ashing.
  • the at least one acyclic diol monomer (AA) may be represented by general formula (D): HO-Q-OH.
  • the acyclic diol (AA) is a poly(ethylene glycol) [“PEG”] and/or 2,2-dimethylpropane-l,3-diol [“DMP”] (also known as neopentyl glycol).
  • the PEG may have a molecular weight of less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
  • the divalent acyclic moiety Q may be represented by formula (V):
  • Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-l,3- propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,3-pentylene [CH(C(CH3)2)-C(CH 3 )2-CH 2 ], and any combination thereof; and z is 0 or an integer from 1 to 500.
  • the divalent acyclic moiety Q is represented by any one of following formulae (V’), (V”), (V’”) and (V””):
  • HO-Q-OH is a poly(alkylene oxide), in which Q is represented by any one of the formulae (V), (V’), (V”), (V’”) and (V””), z in any of these formulae is selected such that the average molecular weight of the the acyclic diol (AA) does not exceed 30,000 g/mol.
  • the sulfone recurring unit (Ra) in the PAES is preferably of formula (la) shown below: wherein in formula (la):
  • each Ri 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium ;
  • - Q is represented by any of the formulae (V), (V’), (V”), (V’”), (V””) defined above.
  • each Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
  • i is preferably 0 for each Ri.
  • the sulfone recurring unit (Ra) in the PAES is more preferably of formula (lb) shown below: wherein in formula (lb), Q is a moiety represented by any one of formulae (V), (V’), (V”), and/or (V’”), preferably represented by any one of formulae (V’) and/or (V”).
  • the recurring units in the PAES according to the invention may comprise more than 10 wt%, preferably more than 30 wt%, more preferably more than 50 wt%, still more preferably more than 70 wt%, and most preferably more than 90 wt% of the sulfone recurring unit (R a ) as detailed above, said wt% being relative to the total weight of recurring units in the PAES.
  • the PAES according to the invention may be a homopolymer and its recurring units consist essentially of the sulfone recurring unit (Ra).
  • the sulfone recurring unit (Ra) is preferably represented by the formula (lb), in which Q is represented by any one of the formulae (V), (V’), (V”), (V’”), and (V””) defined herein, preferably represented by any one of the formulae (V’), (V”), (V””).
  • a PAES homopolymer in which substantially all of its recurring units are sulfone recurring unit (Ra), its preferred sulfone recurring unit (Ra) is represented by formula (lb), wherein Q in formula (lb) is derived from a branched aliphatic diol, such as but not limited to, 2-methyl-l,3-propanediol, 2,2- dimethylpropane-l,3-diol (also known as neopentyl glycol), 2,2,4-trimethyl-l,3- pentanediol, 2-ethyl-2-butyl-l,3-propanediol, propylene glycol, and/or polypropylene glycol), preferably derived from a branched aliphatic diol selected from 2-methyl-l,3-propanediol, 2,2-dimethylpropane-l,3-diol (neopentyl glycol), prop
  • the PAES according to the invention may be a copolymer comprising the sulfone recurring unit (Ra) as detailed above and at least one additional sulfone recurring unit (Rb) and/or (R c ).
  • the additional recurring unit (Rb) is a recurring unit made from the at least one dihaloaryl sulfone monomer (CC) and at least one aromatic diol (BB).
  • the additional recurring unit (R c ) is a recurring unit made from the at least one dihaloaryl sulfone monomer (CC) and at least one alicyclic diol (BB’).
  • its recurring units may comprise more than 10 wt%, preferably more than 30 wt%, more preferably more than 50 wt%, still more preferably more than 70 wt%, and most preferably more than 90 wt% of the sulfone recurring unit (Ra) as detailed above and of at least one additional sulfone recurring unit (Rb) and/or (R c ), said wt% being relative to the total weight of recurring units in the PAES.
  • the PAES When the PAES is a copolymer, its recurring units may consist essentially of the sulfone recurring unit (Ra) and at least one additional sulfone recurring unit (Rb) and/or (R c ).
  • the optional sulfone recurring unit (Rb) is made from the 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 least one acyclic diol (AA).
  • the at least one aromatic diol (BB) contains at least two hydroxyl groups.
  • the aromatic diol (BB) also encompasses any aromatic compound (BB*) with more than two hydroxyl groups.
  • An aromatic compound (BB*) which has 3 to 6 hydroxyl groups, particularly 3 or 4 hydroxyl groups, may be envisioned to use in the aromatic diol (BB), or as the aromatic diol (BB), to make the sulfone recurring unit (Rb) by reacting with the at least one dihaloaryl sulfone monomer (CC).
  • the aromatic diol (BB) may include, or may be, an aromatic triol, such as l,l,l-tris-(4- hydroxyphenyl)-ethane.
  • a suitable aromatic diol (BB) is preferably selected from the group consisting of bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, and any combination thereof; more preferably selected from the group consisting of 4,4 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, and combination thereof; most preferably being 4,4’-biphenol.
  • Ar 6 , Ar 7 are equal or different from each other and are aromatic moieties of the formula with any of the following formulae (H), (H’) and (H”) : consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, carboxylic acid, ester, amide, imide, alkali metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SO 3 H), alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and j’ in any of the formulae (H), (H’) and (H”) is 0, 1, 2, 3 or 4.
  • the divalent portion -[Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ]m- in the formula (II) of the sulfone recurring unit (Rb) is derived from the at least one dihaloaryl sulfone monomer (CC).
  • the divalent portion -O-W-O- in the formula (II) of the sulfone recurring unit (Rb) is derived from at least one aromatic diol (BB) of formula HO-W-OH.
  • W in formula (II) is defined by formula (IVa):
  • - T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -CH2- and any combination thereof, and
  • each of the Ar 6 and Ar 7 is an unsubstituted arylene group of formula (H), wherein J -0.
  • W in formula (II) is defined by formula (IVa):
  • - T is -CH2-
  • - T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, and any combination thereof, and
  • W in formula (II) is defined by formula (IVb):
  • the additional recurring unit (Rb) is preferably represented by formula (Ila) shown below: wherein :
  • each Ri 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
  • - i for each Ri is 0, 1, 2, 3 or 4; and - W is the same as defined in formula (II).
  • each Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
  • i is preferably 0 for each Ri.
  • the additional sulfone recurring unit (Rb) in the PAES is more preferably represented by any of the following formulae (Uh), (lie), (lid), (lie), (Ilf), (Ilg): wherein each Ri and i in any of the formulae (lib), (lie), (lid), (lie), (Ilf), (Ilg) are the same as defined for the formula (Ila), and wherein T in formula (Ilg) is selected from the group consisting of a bond, -SO2-, - C(CH3)2-, and any combination thereof.
  • the Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
  • i is preferably 0 for each Ri.
  • the additional sulfone recurring unit (Rb) in the PAES is yet more preferably of the formula (lib).
  • the additional sulfone recurring unit (Rb) in the PAES is even more preferably of the formula (lib) in which i is 0 for each Ri.
  • the molar ratio rb of sulfone recurring units (R a ) to sulfone recurring units (Rb) may be : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40, or yet even more preferably at least 65:35.
  • Q in the formula (lb) may have a molecular weight of less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
  • the PAES according to the invention may further comprise at least one sulfone recurring unit (R c ) made from the condensation from the at least one dihaloaryl sulfone monomer (CC) and at least one alicyclic diol (BB’) comprising at least one cycloaliphatic moiety (M).
  • R c sulfone recurring unit
  • BB alicyclic diol
  • the cycloaliphatic moiety (M) may comprise only one non-aromatic ring.
  • the at least one cycloaliphatic moiety (M) does not comprise any heteroatoms in a ring.
  • E comprises the at least one cycloaliphatic moiety (M) and is a group which comprises from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms or from 4 to 10 carbon atoms; wherein n and m are independently 0, 1, 2, 3 or 4; wherein Ar 3 , Ar 4 are equal or different from each other and are aromatic moieties of the formula: wherein Ar 5 is selected from the group consisting of: wherein each of R in any of Ar 3 , Ar 4 , Ar 5 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
  • n and m are preferably independently 0, 1 or 2; more preferably n and m are 0 or 1.
  • each R corresponding to such an i is preferably independently selected from the group consisting of halogens, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, and sulfonic acid (-SO3H).
  • each i in any of Ar 3 , Ar 4 , Ar 5 is 0, and none of the aromatic rings in Ar 3 , Ar 4 , Ar 5 is substituted by R. That is to say, Ar 3 , Ar 4 , Ar 5 have only unsubstituted arylene groups.
  • the portion -[Ar 3 -SO2-Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO2-Ar 4 ]m- in formula (III) of the sulfone recurring unit (R c ) is made from the at least one dihaloaryl sulfone monomer (CC).
  • the portion -O-E-O- in formula (III) of the sulfone recurring unit (R c ) is derived from the at least one alicyclic diol (BB’).
  • the sulfone recurring unit (R c ) is preferably of formula (Illa) as shown below :
  • each Ri 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;
  • each Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
  • i is preferably 0 for each Ri.
  • the sulfone recurring unit (R c ) is more preferably represented by formula (Illb) shown below : (Illb), wherein E, each of Ri and each of i are the same as defined in formula (Illa).
  • i is preferably 0 for each Ri.
  • the sulfone recurring unit (Rc) is yet more preferably represented by formula (IIIc) shown below : wherein E is the same as defined in formula (Illa).
  • E is preferably selected from the group consisting of those of formulae (El) to (Ell):
  • each sign * in the formulae (El) to (El 1) denotes where E is bonded to an oxygen atom of the -O-E-O- formula; and wherein each Q’, being the same or different in the formula (El 1), is an acyclic moiety.
  • the -O-E-O- group in any of the formulae (III), (Illa), (Illb), (IIIc) may be derived from an alicyclic diol (BB’) containing acyclic aliphatic diol end groups.
  • the alicyclic diol (BB’) may comprise or may be isosorbide with acyclic aliphatic end groups (diol (Dll) represented by the formula HO-E11-OH).
  • the acyclic moiety Q’ in formula (El 1) may be derived from an acyclic diol selected from alkylene oxides and/or poly(alkylene oxide)s, 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-l,3-propanediol; 2,2-dimethylpropane-l,3- diol; 2,2,4-trimethyl-l,3-pentanediol; 2-ethyl-2-butyl-l,3-propanediol; poly(ethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof
  • the acyclic moiety Q’ in formula (Ell) may be represented by formula (VI): -[ Rk-O-]z-Rk- , in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2 -butyl- 1,3- propylene [CH2-C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-l,3-pentylene [CH(C(CH3)2)-C(CH 3 )2-CH 2 ], 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, yet more preferably
  • 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, yet more preferably an integer from 2 to 50.
  • the optional sulfone recurring unit (Rc) for the PAES copolymer according to the invention may be represented by any one of following formulae (IIIb-1) to (Illb- 5):
  • the PAES preferably may be substantially free (i.e., less than 500 ppm) of polar aprotic solvent.
  • Mw weight average molecular weight
  • M n a number average molecular weight (M n ) of at least 15 000 g/mol, and preferably at most 80 000 g/mol;
  • Ra sulfone recurring units
  • CC dihaloaryl sulfone monomer
  • AA acyclic diol monomer
  • M cycloaliphatic moiety
  • the process preferably comprises reacting the at least one acyclic diol (AA), any optional co-diol (BB) and/or (BB’), and the at least one dihaloaryl sulfone monomer (CC) in a reaction medium comprising a polar aprotic solvent and a base.
  • the reaction is preferably conducted in one stage. This means that the deprotonation of the acyclic diol (AA) and optional co-diols (BB) and/or (BB’) with the base and the condensation reaction between the acyclic diol (AA) and optional co-diols (BB) and/or (BB’) and the dihaloaryl sulfone monomer (CC) takes place in a single reactor vessel without isolation of intermediate products.
  • the initial monomers concentration (total wt% monomers) in the reaction medium may be from 55 wt% to 45 wt% (in the first stage), while the final monomers concentration (total wt% monomers) in the reaction medium may be from 30 wt%to 44 wt%, preferably from 33 wt% to 40 wt% (in the final stage).
  • the difference between the initial total wt% monomers in the first stage and the final total wt% monomers 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 successive polymerization stages are generally carried out in a same reaction vessel, but not necessarily.
  • the dilution of the reaction medium with solvent may be repeated in one or more additional successive polymerisation stages again when a target viscosity of the reaction medium (preferably ranging from 5000 to 8000 cP) is reached. That is to say, a further amount of solvent is added to the reaction medium to start a subsequent polymerisation stage but with a reduced monomers concentration compared to that of the previous stage.
  • a target viscosity of the reaction medium preferably ranging from 5000 to 8000 cP
  • the anhydrous alkali metal carbonate or co-base may be selected from the group consisting of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, preferably selected from sodium carbonate and/or potassium carbonate, more preferably potassium carbonate.
  • the molar ratio rk of K2CO3 over KaPC may be : at most 75:25, or at most 70:30, or at most 67:33, and/or at least 10:90, or at least 12:88, or at least 13:87.
  • the base used in the reaction medium is preferably anhydrous.
  • the co-base such as an alkali metal carbonate (preferably K2CO3) is used in conjunction with the inorganic metal phosphate (preferably K3PO4) in the reaction medium
  • the co-base preferably K2CO3 is anhydrous.
  • anhydrous refers to a substance containing less than 2 wt% moisture, preferably less than 1 wt% moisture, more preferably less than 0.5 wt% moisture, most preferably less than 0.25 wt% moisture as measured by Karl-Fisher titration or by loss on drying test.
  • the base does not include a strong hindered potassium base, such as potassium trimethylsilanolate.
  • a strong hindered potassium base such as potassium trimethylsilanolate.
  • the strong hindered base disclosed in W02020/201522 (Roquette Freres) is not present in the base.
  • no other phosphorous-containing material is used in the reaction medium.
  • no phosphorous-containmg solvent such as hexamethyltnamide phosphate is used during the PAES polymerisation.
  • n, m, Ar 3 , Ar 4 and Ar 5 are the same as defined for recurring unit (Ra) of general formula (I); and wherein X and X’, equal to or different from each other in formula (C), are independently a halogen atom, preferably Cl or F, more preferably Cl.
  • the dihalo sulfone monomer (CC) is preferably of formula (Cl): wherein:
  • each of Ri is 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
  • each i is independently zero or an integer from 1 to 4, preferably is independently zero or 1, more preferably is zero.
  • Ri is preferably independently selected from the group consisting of alkali metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SOsH), alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium.
  • i is preferably 0 for each Ri.
  • the dihaloaryl sulfone monomer (CC) more preferably consists essentially of at least one 4,4-dihalodiphenylsulfone selected from the group consisting of: 4,4’- di chlorodiphenyl sulfone (DCDPS), monosulfonated 4,4’ -di chlorodiphenyl sulfone (msDCDPS), disulfonated 4,4’ -di chlorodiphenyl sulfone (dsDCDPS), 4,4’ difluorodiphenyl sulfone (DFDPS), monosulfonated 4,4’ difluorodiphenyl sulfone (msDFDPS), disulfonated 4,4’ difluorodiphenyl sulfone (dsDFDPS), and any combination thereof.
  • DCDPS 4,4’- di chlorodiphenyl sulfone
  • msDCDPS monosulfonated 4,4’
  • the dihaloaryl sulfone monomer (CC) yet more preferably consists essentially of DCDPS and/or disodium bis(4-chloro-3-sulfophenyl)sulfone (dsDCDPS), most preferably consists essentially of DCDPS.
  • the acyclic diol (AA) is selected from linear aliphatic diols or branched aliphatic diols.
  • linear aliphatic diols mention may be made of 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.
  • branched aliphatic diols mention may be made of 2-methyl-l,3-propanediol, 2,2-dimethylpropane-l,3-diol (also known as neopentyl glycol), 2,2,4-trimethyl-l,3-pentanediol, 2-ethyl-2-butyl- 1,3-propanediol, propylene glycol, and/or polypropylene glycol).
  • the acyclic diol (AA) may be represented by formula (D): HO-Q-OH, in which Q is an acyclic moiety.
  • the acyclic diol (AA) may be an alkylene oxide or a poly(alkylene oxide) represented by formula (Da):
  • Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-l,3- propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,3-pentylene [CH(C(CH3)2)-C(CH 3 )2-CH 2 ], and any combination thereof; and z is 0 or an integer from 1 to 500.
  • the acyclic diol (AA) is represented by any of following formulae (Dal), (Da2), (Da3) or (Da4):
  • z in any of the formulae (Da), (Dal), (Da2), (Da3) and (Da4) is an integer from 1 to 500, preferably an integer from 2 to 200, more preferably an integer from 2 to 100, yet more preferably an integer from 2 to 50.
  • the acyclic diol (AA) is a poly(alkylene oxide), it preferably has an average molecular weight (Mn) of from 160 to 30,000 g/mol.
  • Mn average molecular weight
  • z in the acyclic diol (AA) represented by any of the formulae (Da), (Dal), (Da2), (Da3) and (Da4) is preferably selected such that its average molecular weight (Mn) does not exceed 30,000 g/mol.
  • z in any of the formulae (Da), (Dal), (Da2), (Da3) or (Da4) is preferably selected such that the molecular weight of the acyclic diol (AA) is less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
  • the at least one co-diol may comprise or consist of an aromatic diol (BB) and/or an alicyclic diol (BB’).
  • the molar ratio r of the at least one acyclic diol (AA) to the at least one co-diol may be : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or
  • reaction medium may further comprise at least one dihydroxyaryl monomer [ hereinafter “aromatic diol (BB)”] as co-diol.
  • aromatic diol (BB) aromatic diol
  • the at least one aromatic diol (BB) contains at least two hydroxyl groups.
  • the aromatic diol (BB) also encompasses any aromatic compound (BB*) with more than two hydroxy groups.
  • An aromatic compound (BB*) which has 3 to 6 hydroxy groups, particularly 3 or 4 hydroxy groups, may be envisioned to use in the aromatic diol (BB), or as the aromatic diol (BB), to make the sulfone recurring unit (Rb) by reacting with the at least one halo sulfone monomer (CC).
  • Non-limiting aromatic compound (BB*) containing three or more than three hydroxy groups may be selected from: phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxy-5 phenyl)-heptene-2 (trimeric isopropenylphenol), 4,6-dimethyl-2,4,6-(4-hydroxyphenyl)-heptane (hydrogenated trimeric isopropenyl phenol), l,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1 -tris-(4-hy droxyphenyl)-ethane, 1,1,1 -tris-(4-hy droxyphenyl)-propane, tetra-(4- hydroxyphenyl)-methane, l,4-bis-(4', 4 "-dihydroxytriphenyl)-methyl] -benzene and 2,2-bis-[4,4'-bis-(4-hydroxyphenyl)
  • the at least one aromatic diol (BB) may be of general formula (D’):
  • W in formula (D’) is defined by general formula (IV): -Ar 6 -(T-Ar 7 ) y -, in which
  • Ar 6 , Ar 7 are equal or different from each other and are aromatic moieties of any of the
  • R’ in any of the formulae (H), (H’), (H”) being 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 (- SO 3 H), alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium, and j’ in any of the formulae (H), (H’), (H”) being 0, 1, 2, 3 or 4. When the aromatic ring in the moieties of formulae (H), (H’) and (H”) is not substituted, j’ is 0.
  • W in formula (D’) is defined by formula (IVa): -Ar 6 -T-Ar 7 - , in which:
  • - T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -CH2-; and any combination thereof, and
  • W in formula (D’) may be defined by formula (IVb): -Ar 6 - , in which the Ar 6 is an unsubstituted arylene group of formula (H) or (H’) wherein J -0.
  • W in formula (D’) may be defined by formula (IVa): -Ar 6 -T-Ar 7 - , in which:
  • - T is -CH2-
  • the 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 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, bisphenol F, hydroquinone, resorcinol, an aromatic triol such as l,l,l-tris-(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 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, and any combination thereof; yet more preferably selected from the group consisting of 4,4’ -biphenol, diallyl bi phenol, tetramethyl bisphenol F, and combination thereof; most preferably being 4,4’-biphenol.
  • the molar ratio rb of acyclic diol(s) (AA) : aromatic diol(s) (BB) in the reaction medium is : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40.
  • BB* aromatic triol
  • BB* aromatic triol
  • BB* aromatic triol
  • the reaction medium may further comprise at least one aliphatic (non-aromatic) and cyclic dihydroxy monomer [hereinafter “alicyclic diol (BB’)”] as co-diol.
  • the alicyclic diol (BB’) is different from the at least one acyclic diol (AA) and the at least one aromatic diol (BB).
  • the at least one alicyclic diol (BB’) comprises at least one cycloaliphatic moiety (M).
  • cycloaliphatic moiety is intended to denote any moiety being both aliphatic (i.e., not aromatic) and cyclic (i.e., where the carbon atoms and optional heteroatoms are connected in a ring).
  • the cycloaliphatic moiety (M) may comprise from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms or from 4 to 10 carbon atoms or from 4 to 8 carbon atoms, or from 4 to 6 carbon atoms.
  • the cycloaliphatic moiety (M) may be either unsubstituted or substituted.
  • the cycloaliphatic moiety (M) may comprise at least one heteroatom in the ring, such as at least one oxygen atom.
  • the cycloaliphatic moiety (M) does not comprise any heteroatoms in the ring, meaning that the backbone of the cycle of the cycloaliphatic moiety (M) is made only of interconnected carbon atoms.
  • More than one cycloaliphatic moiety (M) can be present in the alicyclic diol (BB’). If more than one cycloaliphatic moiety (M) is present in the alicyclic diol (BB’), they can be the same or different.
  • the alicyclic diol (BB’) may comprise a polycyclic cycloaliphatic moiety, said polycyclic cycloaliphatic moiety comprising more than one condensed cycloaliphatic moieties (M).
  • the polycyclic cycloaliphatic moiety comprises two condensed cycloaliphatic moieties (M), three condensed cycloaliphatic moieties (M) or even four condensed cycloaliphatic moieties (M).
  • Each condensed cycloaliphatic moiety (M) typically comprises from 4 to 8 carbon atoms, preferably from 4 to 6 carbon atoms.
  • alicyclic diol (BB’) may exist in different stereochemical and regiochemical arrangements.
  • the two hydroxyl groups in the alicyclic diol (AA) may have a cis or trans configuration towards each other.
  • E comprises the at least one cycloaliphatic moiety (M) and is a group comprising from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms.
  • the at least one alicyclic diol (BB’) is more preferably a diol of formula (D”), in which E is at least one group selected from groups of formulae (El) to (El 1), described earlier in relation to any of formulae (III), (Illa), (Illb).
  • the at least one alicyclic diol (BB’) is selected from the group consisting of diols complying with any of formulae (DI) to (DI 1) :
  • each Q’ being the same or different in formula (DI 1), is an acyclic moiety.
  • the acyclic moiety Q’ in formula (Dl l) may be derived from an acyclic diol selected from alkylene oxides and/or poly(alkylene oxide)s, 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-l,3-propanediol; 2,2-dimethylpropane-l,3- diol; 2,2,4-trimethyl-l ,3-pentanediol; 2-ethyl-2-butyl- 1 ,3-propanediol; polyethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination
  • Q’ in formula (DI 1) may be represented by formula (VI): -[Rk-O-] z -Rk- , in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-l,3- propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,3-pentylene [CH(C(CH3)2)-C(CH 3 )2-CH 2 ], 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, yet more preferably an integer from 2
  • Q’ in formula (Dll) is represented by any one of following formulae (VI’), (VI”), (VI’”) and (VI””):
  • z is 0 or an integer from 1 to 500, preferably from 2 to 200, more preferably from 2 to 100, yet more preferably from 2 to 50.
  • the alicyclic diol (BB’) may be selected from l,4:3,6-dianhydrohexitols and/or l,4:3,6-dianhydrohexitols with acyclic aliphatic end groups.
  • the alicyclic diol (BB’) is more preferably selected from the group consisting of 1,4:3, 6-dianhydrohexitols such as isosorbide (“ISOSO”) (DI), isomannide (D2), isoidide (D3); 2,3-di-O-alkylene-l-threitols such as 2,3-O-isopropylidene-l- threitol (D4) and/or 2,3-di-O-methylene-l-threitol; tetrahydrofurandimethanol (D5); tetramethylcyclobutanediol (“CBDO”) (D6); cis-l,5-cyclooctanediol (“CODO”) (D7); cyclohexanedimethanol (“CHDM”) (D8); hydrogenated bisphenols such as hydrogenated Bisphenol A (“H-BPA”) (D9); decalindiols such as 2,6-decal
  • the alicyclic diol (BB’) is most preferably isosorbide (DI).
  • the reaction medium comprises the base comprising an inorganic metal phosphate and optionally an alkali metal carbonate
  • the reaction medium is preferably free of any organic phosphorous base.
  • the strong hindered base disclosed in W02020/201522 (Roquette Freres) is not present in the reaction medium.
  • the reaction medium preferably does not comprise a catalyst.
  • the crown-ether catalyst disclosed in EP3653661 (Korea Research Institute of Chemical Technology) is not present in the reaction medium.
  • Preferred temperature of the reaction medium may be from about 110°C to about 175°C, preferably from about 115°C to about 175°C, when DMAc is used as solvent.
  • the process to manufacture the PAES is such that the reaction conversion is at least 90%, preferably at least 95%.
  • the time for reaction to prepare the PAES may be from about 3 hours to 24 hours, or from about 4 hours to 21 hours, or from 5 hours to 20 hours, or from 5 hours to 18 hours.
  • the boiling temperature of the solvent selected usually limits the temperature of the reaction.
  • the reaction may be conveniently carried out in an inert atmosphere, e. g., nitrogen, at atmospheric pressure, although higher or lower pressures may also be used.
  • the PAES of the invention can be recovered by methods well known and widely employed in the art such as, for example, coagulation, solvent evaporation and the like. After polymerization the resulting PAES is in the form of a solution.
  • the PAES polymer may be isolated from the PAES solution by precipitation and/or coagulation by contacting the reaction medium, optionally after salt removal by filtration, with a non-solvent for the PAES polymer such as a Cl - C5 alcohol, water, or any mixture thereof.
  • the precipitate/coagulate may be rinsed and/or washed with demineralized water or C1-C5 alcohol prior to drying at a temperature ranging from at least 70 °C to about 170 °C. While a vacuum may be applied during drying, drying is generally performed at ambient pressure.
  • no phosphoric acid is used to acidify or neutralize the PAES solution after separation of salts and during rinsing and/or washing of the PAES solid.
  • the PAES according to the present invention features all the benefits of the currently sold polyarylethersulfones while also unexpectedly featuring a reduced content in potential endocrine disruptors, potentially a higher renewable content especially when a bio-sourced diol is used in making such a PAES.
  • the present invention also concerns polymer compositions that include at least one PAES of the present invention and at least one other ingredient.
  • Such other ingredient can be on or more PAES polymers, such as a commercially available PPSU, PSU and/or PES polymers.
  • Such other ingredient can also be a polymer other than a PAES polymer such as polyvinylpyrrolidone or a polyethylene glycol.
  • Such other ingredient can also be a non polymeric ingredient such as a solvent, a filler, a lubricant, a mold release agent, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye and an optical brightener.
  • a non polymeric ingredient such as a solvent, a filler, a lubricant, a mold release agent, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye and an optical brightener.
  • the polymer solution (SP) may further comprise at least one additional polymer distinct form the PAES described herein, for example another sulfone polymer, e.g., poly sulfone (PSU), polyethersulfone (PES), poly(biphenylene ether sulfone) (PPSU), or a polyphenylene sulfide (PPS), a poly(aryl ether ketone) (PAEK), e.g., a poly(ether ether ketone) (PEEK), a poly(ether ketone ketone) (PEKK), a poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer), a poly etherimide (PEI), and/or a polycarbonate (PC).
  • the other polymeric ingredient can also include or be a polyvinylpyrrolidone and/or a polyethylene
  • the dope solution may further comprise a poreforming agent, such as polyvinylpyrrolidone or a polyethylene glycol.
  • the dope solution may contain additional components, such as nucleating agents, fillers and the like.
  • the Applicant has surprisingly found that the PAES of the present invention or the polymer composition of the present invention as detailed above, exhibiting excellent properties which are useful in providing high performance polymer membranes.
  • the dope solution of the present invention comprising the PAES of the present invention is preferably used for fabrication of membranes.
  • the PAES of the present invention may be used for the manufacture of membranes or a component thereof, coatings, films, sheets, and three-dimensional molded parts, in particular transparent or coloured parts.
  • Particular shaped articles which comprise, or are made from, the PAES of the present invention may be selected from the group consisting of membranes, melt processed films, solution processed films, melt process monofilaments and fibers, solution processed monofilaments, hollow fibers and solid fibers, coatings, printed objects, injection molded objects and compression molded objects.
  • the article may also be a food contact article such as a plumbing article such as a fitting, a valve, a manifold or a faucet, a food tray, a water bottle or a baby bottle, a cookware.
  • a food contact article such as a plumbing article such as a fitting, a valve, a manifold or a faucet, a food tray, a water bottle or a baby bottle, a cookware.
  • the article may also be an electronic part.
  • the article may also be a housing or cover for a mobile electronic device.
  • the article may also be a medical tray or an animal cage.
  • the PAES of the invention or the polymer composition of the present invention as detailed above may be also useful in optical applications.
  • the article may also be optical articles such as notably sunglass lenses, eyeglass lenses, optical lenses, optical discs.
  • PAES of the invention or the polymer composition of the present invention as detailed above may be also useful used for manufacturing of sheets and films. These are particularly useful as specialized optical films or sheets, and/or suitable for packaging.
  • PAES of the present invention and the polymer composition comprised in the article according to the present invention have the same characteristics respectively as the PAES of the present invention and the polymer composition according to the present invention, in all their embodiments, as above detailed.
  • the article is preferably a membrane.
  • Membranes suitable for the purpose of the invention include, without limitation, isotropic or anisotropic membranes, porous or non-porous membranes, composite membranes, or symmetric or non-symmetric membranes. Such membranes may be in the form of flat structures, corrugated structures, (such as corrugated sheets), tubular structures, or hollow fibers.
  • the membranes according to the present invention can be manufactured using any of the conventionally known membrane preparation methods, for example, by a solution casting or solution spinning method.
  • Non limitative examples of membrane applications include water purification, wastewater treatment, pharmaceutical production, blood purification, in particular hemodialysis and a variety of industrial process separations, such as food and beverage processing, electropaint recovery and gas separation.
  • Particular preferred shaped articles which comprise, or are made from, the PAES of the present invention may be membranes being selected from membranes for bioprocessing and medical filtrations (such as hemodialysis membranes), membranes for food and beverage processing, membranes for water purification, membranes for waste water treatment, and/or membranes for industrial process separations involving aqueous media.
  • membranes for bioprocessing and medical filtrations such as hemodialysis membranes
  • membranes for food and beverage processing membranes for water purification
  • membranes for waste water treatment membranes for waste water treatment
  • membranes for industrial process separations involving aqueous media such as hemodialysis membranes
  • the membranes according to the present invention can be manufactured using any of the conventionally known membrane preparation methods, for example, by a solution casting or solution spinning method.
  • the membranes according to the present invention are prepared by a phase inversion method occurring in the liquid phase, said method comprising the following steps:
  • the membrane of the present invention may comprise the PAES described herein in an amount of 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%, based on the total weight of the membrane.
  • the membrane of the present invention may comprise the PAES described herein in an amount of more than 50 wt%, for example more than 55 wt%, more than 60 wt%, more than 65 wt%, more than 70 wt%, more than 75 wt%, more than 80 wt. %, more than 85 wt%, more than 90 wt%, more than 95 wt% or more than 99 wt%, said wt% being based on the total weight of the membrane.
  • the membrane of the present invention may comprise the PAES described herein in an amount ranging from 1 wt% to 99 wt%, for example from 3 wt% to 96 wt%, from 6 wt% to 92 wt% or from 12 wt% to 88 wt%, said wt% being based on the total weight of the membrane.
  • the membrane of the present invention may further comprise at least one polymer distinct form the PAES described herein, for example another sulfone polymer, e.g., polysulfone (PSU), polyethersulfone (PES), poly(biphenyl ether sulfone) (PPSU), or a polyphenylene sulfide (PPS), a poly(aryl ether ketone) (PAEK), e.g., a poly(ether ether ketone) (PEEK), a poly(ether ketone ketone) (PEKK), a poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer), poly etherimide (PEI), and/or polycarbonate (PC).
  • the other polymeric ingredient can also be polyvinylpyrrolidone and/or polyethylene glycol.
  • the membrane may also further comprise at least one non-polymeric ingredient such as a solvent, a filler, a lubricant, a mold release, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye and/or an optical brightener.
  • a non-polymeric ingredient such as a solvent, a filler, a lubricant, a mold release, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye and/or an optical brightener.
  • substrates are not particularly limited. Such coatings may be useful for protecting substrates such as notably metals such as steel, in particular stainless steel, aluminum, copper, and other metals in applications such as food and beverage can coatings, marine-hull protection, aerospace, automotive, wire coating, electronics, optical and plastics.
  • substrates such as notably metals such as steel, in particular stainless steel, aluminum, copper, and other metals in applications such as food and beverage can coatings, marine-hull protection, aerospace, automotive, wire coating, electronics, optical and plastics.
  • DCDPS 4,4 ’-di chlorodiphenylsulfone
  • DMP 2,2-dimethyl-l,3-propanediol
  • PEG300 polyethyleneglycol
  • Potassium carbonate (K2CO3) with a D90 ⁇ 45 pm was procured from Armand products and was dried at 120°C under vacuum for 12 hours before use.
  • Sulfolane, N,N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) were procured from Sigma- Aldrich and used as received.
  • the molecular weights (Mn, M w , M z ) were measured by GPC using as Waters Alliance E2695 with UV-Vis detector E2489 (detection at 270 nm) using two full size Agilent 5um MiniMixed-D columns (250 x 4.6mm) and one Guard column (50 x 4.6mm)(both have 5 pm particle sizes) using 0. IM LiBr solution in DMAc as mobile phase.
  • a sample (30 mg) of PAES polymer was weighed into a 20 ml vial and 5 ml of the mobile phase were added to dissolve the sample. The resulting solution was filtered using a 0.2 um PTFE syringe filter into a 4 ml vial. The sample volume injected was 10 pL.
  • a flow rate of 0.3 ml/min was selected.
  • Calibration was performed using 10 narrow calibration standards of Polystyrene obtained from Agilent Technologies (Peak molecular weight range: 371000 to 580).
  • the GPC Distribution Values for the PAES Sample Mw, Mn, Mz, PDI (Mw/Mn), and ratio Mz/M w were calculated by Agilent OpenLab CDS using the calibration curve for the polystyrene standards that was generated.
  • Inherent viscosity IV of the PAES samples was measured in a solvent mixture dichloromethane/trifluoroacetic acid (9/1 v/v), at a concentration of 0.2g PAES/lOOmL at 20 °C using a Cannon-Fenske viscometer tube (N°50) according to the procedure as described by Kricheldorf and Chatti in High Performance Polymers, 2009, vol. 21, pages 105-118.
  • the glass transition temperature (Tg) of PAES samples was determined using the mid-point method on the 2 nd heat scan in Differential Scanning Calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06. Details of the procedure as used in this invention were as follows: a TA Instruments DSC Q20 was used with nitrogen as carrier gas (99.998% purity, 50 mL/min). Temperature and heat flow calibrations were done using indium. Sample size was 5 to 7 mg. The weight was recorded ⁇ 0.01 mg. The heat cycles were:
  • a clean, dry platinum crucible is placed onto an analytical balance, and the balance was zeroed.
  • One half to 3 grams of PAES sample was weighed into a boat and its weight was recorded to 0.0001 g.
  • the crucible with PAES sample was placed in a muffle furnace (Thermo Scientific Thermolyne F6000 Programmable Furnace). The furnace was gradually heated to 525°C and held at that temperature for 10 hours to dry ash the sample. Following ashing, the furnace was cooled down to room temperature, and the crucible was taken out of the furnace and placed in a fume hood. The ash was dissolved in diluted hydrochloric acid. The solution was transferred to a 25 mL volumetric flask, using a polyethylene pipette.
  • the crucible was rinsed twice with approximately 5 mL of ultrapure water (R ⁇ 18 MQcm) and the washes were added to a volumetric flask to effect a quantitative transfer. Ultrapure water was added to total 25 mL in the flask. A stopper was put on the top of the flask and the contents are shaken well to mix.
  • ICP-OES Inductively Coupled Plasma Optical Emission Spectroscopy
  • a 0.25 g sample of PAES is dissolved into 5 mL DMF and the solution is filtered through a 0.22 um syringe filter and analyzed by Gas Chromatography (GC) using a Restek RTX-200ms (30m X 250pm X 0.25pm) column, a constant Flow of hydrogen as carrier gas of 1.6 mL/min.
  • GC Gas Chromatography
  • a 0.5-g sample of PAES is dissolved in 10 mL DMF. After dissolution, 10 mL of acetonitrile are added under agitation to precipitate the polymer. The solution is filtered through a 0.22-pm syringe filter and analyzed (20pL injection volume) by Liquid Chromatography using a Supelco Discovery® C18 HPLC column (4.6 mm x 25 mm, 5 pm particle size).
  • the mobile phase has the following gradient composition:
  • the detector is a UV detector set at 254 nm.
  • the concentration of BPS is determined using external standards of BPS.
  • a 0.25-g sample of PAES is dissolved into 5 mL trichloromethane.
  • the solution is filtered through a 0.22 -micron syringe filter and analyzed by Gas Chromatography using a RestekTM RTXTM-5MS capillary column (30m length, 0.25mm ID, 0.25 pm film thickness), a constant pressure of 14.5 psi of helium.
  • the GC conditions are :
  • the concentration of BP A is determined using external standards of BP A.
  • the molar ratio of the overall amount of the overall amount of halogen groups from DCDPS [as monomer (CC)] to the hydroxyl groups from the acyclic diol (AA) and any optional co-diols (BB) is from 0.995 to 1.000.
  • the reactor vessel was purged with nitrogen for 15 minutes before initiating the reaction.
  • the reaction medium comprising the monomers was stirred with the overhead mechanical agitator and heated up to initiate reaction up to a suitable reaction temperature (110 °C to 200 °C) using an heating mantle controlled at the target internal reaction temperature.
  • the reaction medium temperature was increased from room temperature (e.g., 20-21 °C) to the appropriate reaction temperature over about 30-60 minutes.
  • room temperature e.g., 20-21 °C
  • water, a byproduct of the polymerization reaction was continuously stripped out of the reactor vessel and collected in the dean-stark trap, and the reaction medium is stirred with an overhead mechanical agitator and heated up to the suitable reaction temperature).
  • reaction medium Upon reaching the target reaction temperature, the reaction medium was held at that temperature for a period of reaction time suitable until a desired M w was achieved, generally measured by viscosity.
  • the reaction time period may vary from 5 to 24 hours, and was generally from about 14.5 hours to 21.5 hours.
  • the polymerization was terminated by bubbling 50 g of gaseous methyl chloride through the reaction medium over 30 minutes. Because the reaction medium became viscous and difficult to stir at the end of the reaction, the reaction medium was diluted with DMAc to obtain 20 wt% PAES polymer and was cooled to a temperature which was less than the reaction temperature, preferably less than 130 °C, more preferably less than 120 °C, yet more preferably less than 110 °C.
  • the cooled medium was filtered through a 2.7-pm glass fiber filter pad under pressure to remove salts.
  • the polymer was then coagulated from the filtered solution by pouring it into a Waring blender containing 2.5-L of non-solvent (methanol, water or a blend of water/methanol) using a weight ratio of 1 :5 PAES solution to non-solvent to precipitate the PAES and obtain a white solid.
  • the resulting solid was then isolated by filtration, and washed five times with 2.5 L of methanol at room temperature. The resulting solid was dried in a vacuum oven overnight at 120 °C.
  • Each PAES sample was analysed to measure its inherent viscosity IV, its Mw, Mn, Mz by GPC, its Tg by DSC (2 nd heat), its phosphorous content by ICP-OES, and its chlorine content by Chlorine analyser.
  • the ratios: M w /M n (PDI) and M z /M w for each PAES sample were also calculated.

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Abstract

A poly(aryl ether sulfone) polymer ("PAES") made from condensation of at least one acyclic diol, optional aromatic and/or alicyclic co-diols, 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 phosphorous content of at least 3 ppm. Preferably the Mw of the PAES is greater than 40 000 g/mol. A process for manufacturing such a PAES, use of such a PAES for manufacturing an article, an article such as a membrane or a part thereof comprising or made from such a PAES, and a dope solution for manufacture of membrane comprising such a PAES.

Description

Polyarylethersulfone containing phosphorous and made from dihaloarylsulfone and acyclic diol
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. application No. 63/575367 filed on April 5, 2024 and to European application No. 24179287.8 filed on May 31, 2024, the entire content of these applications being incorporated herein by reference for all purposes.
TECHNICAL FIELD
The present invention pertains to a polyarylethersulfone polymer (“PAES”) containing phosphorous and made from at least one acyclic diol monomer and at least one dihaloaryl sulfone monomer, to a process for manufacturing such a PAES, to its use for the manufacture of articles and to articles comprising or made from such PAES.
BACKGROUND
Poly(aryl ether sulfone) polymers (PAES) are a class of thermoplastic polymers characterized by high glass-transition temperatures, good mechanical strength and stiffness, and outstanding thermal and oxidative resistance. By virtue of their mechanical, thermal, and other desirable characteristics, these polymers are used increasingly making products for a wide and diversified range of commercial applications, for instance in coatings, in membranes for wide field of use including medical market, due to their excellent mechanical and thermal properties, coupled with outstanding hydrolytic stability. PAES is a generic term used to describe any polymer containing at least one sulfone group (-SO2-), at least one ether group (-O-) and at least one arylene group.
A commercially important group of PAES includes polysulfone polymers identified herein as polysulfones, in short PSU. PSU polymers contain recurring units made from the condensation of the dihydroxy monomer bisphenol A (BPA) and a dihalogen monomer, for example 4,4'-dichlorodiphenyl sulfone (DCDPS). Such PSU polymers are commercially available from Solvay Specialty Polymers USA, LLC (member of the SYENSQO group) under the trademark UDEL® PSU.
Another important group of PAES includes poly ethersulfone polymers, in short PES. PES polymers derive from the condensation of the dihydroxy monomer bisphenol S (BPS) and a dihalogen monomer, for example 4,4'-dichlorodiphenyl sulfone (DCDPS). Such PES polymers are commercially available from Solvay Specialty Polymers USA, LLC under the trademark VERADEL® PES. PSU and PES polymers, respectively based on BPA and BPS, are frequently used to prepare membranes to be used in contact with biological fluids, for example blood.
BPA and BPS are industrial chemicals that have been present in many articles, including plastic bottles and food and beverage cans since the 1960s. In recent years, concerns have been raised about BPA and BPS's safety. BPS and BPA are suspected to be endocrine disruptive in nature, albeit without conclusive research, and their impact on the environment and human health is still under investigation. In view of this controversy, the market is looking for economically viable alternatives to BPA and BPS.
Because polymeric materials in contact with food and drugs must meet certain requirements mandated by for instance the FDA, the European Food Safety Agency and the Environmental Protection Agency (EP A), it is important to continue developing polymeric materials that are safe both for humans and environment for applications requiring contact with water, food, drugs and/or blood.
Manufacturers have thus turned their attention to partially or totally substituting these aromatic diols such as bisphenol A with aliphatic diols.
EP0739925 (BAYER AG) describes polysulfone-poly ether block copolycondensates of formula (I): -(O-E-O-Arl-SO2-Ar2-)-W- , wherein E is a divalent diphenolate radical and W is a poly ether, polythioether or polyacetal possessing at least two hydroxyl groups and having an average molecular weight of from 400 to 30,000 and wherein the proportion of the radical W in the total polymer amounts to 5 to 99 weight percent. Their synthesis is carried out by strong base chemistry, in which an alkali metal alkoxylate is used to deprotonate aliphatic polyetherdiol. In the examples, a weight fraction of polyethylene glycol of about 34-60 wt% is used.
US6365678B1 (BAYER AG) describes a process for the production of poly ether block copolysulfones, comprising reacting (A) at least one aromatic sulfone polymer, with (B) at least one aliphatic polyether having on average at least one terminal OH function. The reaction is between a formed high molecular weight polysulfone with a poly ether in the presence of a basic catalyst to incorporate the polyether segment by transetherification. While various bases such as carbonates, phosphates (notably NasPO-i. K3PO4 or K2HPO4), amines, hydroxides such as NaOH, are cited as being suitable, only potassium carbonate is exemplified as a base. The synthesis of the polyether block copolysulfones using polyethylene glycol (PEG 8000) or poly tetrahydrofuran was carried out without a dihalo monomer in DMSO with an azeotrope-forming agent (toluene) and using mild reaction temperature (140-155 °C). The weight fraction of polyethylene glycol (PEG) in examples is around 3.6-12.9 wt%. The PSU-b-PEG of Example 1 has a Mw of 37 kDa.
Previous efforts in developing new polymeric materials made from monomers which have weak binding affinity for estrogen receptors can be found for example in US 2014/0113093 (SOLVAY SPECIALTY POLYMERS USA) and by work done by Sundell and coworkers (Polymer (2014) vol. 55(22), pp. 5623-5634).
The development of renewable polymers derived from bio-based feed-stocks is also of particular interest. This is part of efforts oriented towards reduction of the amount of petroleum consumed in the chemical industry and to open new high- value-added markets to agriculture; 1,4:3, 6-dianhydrohexitols are examples of such chemicals used as bio-based feed-stock.
Because of their bicyclic constrained geometry and their oxygenated rings, 1,4:3, 6-dianhydrohexitols can deliver advantageous features when incorporated into poly aryl ether sulfone structures. Also the innocuous character of the molecules opens the possibility of applications in packaging or medical devices, e.g., for hemodialysis membranes.
Depending on the chirality, three isomers of the 1,4: 3, 6-dianhydrohexitols sugar diol exist, namely isosorbide (DI), isomannide (D2) and isoidide (D3):
The 1,4:3, 6-dianhydrohexitols are composed of two cis-fused tetrahydrofuran rings, nearly planar and V-shaped with a 120° angle between rings. The hydroxyl groups are situated at carbons 2 and 5 and positioned on either inside or outside the V-shaped molecule. They are designated, respectively, as endo or exo. A summary of the manufacture of these l,4:3,6-dianhydrohexitols can be found in US 2015/0011446A1 (SOLVAY SPECIALTY POLYMERS ITALY, SpA).
Interest in the production of 1,4:3, 6-dianhydrohexitols, especially isosorbide, has been generated by potential industrial applications including the synthesis of polymers such as notably polyesters, poly ethers, polyurethanes and polyamides. The use of 1,4:3, 6-dianhydrohexitols in polymers, and more specifically in poly condensates, can be motivated by several features: they are are rigid bicyclic chiral diols derived from sugars, chiral, and non-toxic. In particular, isosorbide is obtained from the double dehydrogenation reaction of sorbitol, itself derived from the glucose hydrogenation reaction.
Kricheldorf et al. first reported the preparation and characterization of poly(ether sulfone)s containing isosorbide from silylated isosorbide and difluorodiphenylsulfone (DFDPS) in 1995 (H. Kricheldorf, M. Al Masri, J. Polymer Sci., Pt A: Polymer Chemistry, 1995, 33, 2667-2671). Since the silylation step adds significant cost, Kricheldorf and Chatti (High Performance Polymers, 2009, 21, 105-118) modified their polymerization conditions and reported that poly(ether sulfone)s containing isosorbide could be made from nonfunctionalized isosorbide and difluorodiphenylsulfone in the presence of potassium carbonate. The highest apparent molecular weight polymer obtained had an inherent viscosity IV of 0.65 dL/g, said IV was measured according to following conditions : CHiCh/trifluoroacetic acid solution (9/1 v/v) at 20°C, 0.20 g/dL. The glass transition temperature of this polymer was reported as 245°C. No examples were described where the polymerization reaction with isosorbide was conducted with the less reactive dichlorodiphenylsulfone (DCDPS).
WO 2014/072473 A2 (SOLVAY SPECIALTY POLYMERS USA, LLC) describes a method for the preparation of aromatic poly ethersulfones based on isosorbide. The method involves the reaction between difluorodiphenylsulfone or dichlorodiphenylsulfone, optionally in the presence of a fluorinating agent, and isosorbide in the presence of potassium carbonate at a temperature of 210° C. However there are no examples of poly(sulfone isosorbide) of Mw above 58 kDa.
US 2015/0129487 Al (SOLVAY SPECIALTY POLYMERS USA, LLC) describes a method for the preparation of semi-aromatic polyethersulfones based on non-aromatic cyclic diols such as cyclohexanedimethanol, 1,5-cyclooctanediol or tetramethylcyclobutanediol. The method involves the reaction between 4,4'- difluorodiphenylsulfone and a non-aromatic cyclic diol in the presence of potassium carbonate at a minimum temperature of 160° C, and the reaction between 4,4'- dichlorodiphenylsulfone and a non-aromatic cyclic diol in the presence of potassium carbonate at a minimum temperature of 210-215 °C.
However due to their lower reactivity than standard bisphenols (e.g. bisphenol A), these cycloaliphatic and acyclic diols typically require the use of activated monomer 4,4 ’-difluorodiphenylsulfone (DFDPS) which is much more expensive than DCDPS, or the use of high temperatures (210-215° C) in the presence of a weak base such as K2CO3 at which some side reactions like polymer cleavage can be observed, or the use of a strong base such as NaH, which makes it possible to moderate the temperatures. Nevertheless, strong bases are known to cause secondary hydrolysis reactions of the dihalogenated diphenyl sulfone (R. N. Johnson and A. G. Farnham, J. Polym. Sci. A-l Polym. Chem., vol. 5, no. 9, p. 2415-2427, 1967).
Regarding the low reactivity of alicyclic and acyclic diols, in contrast of the OH group in bisphenol monomers, the OH groups in the alicyclic and acyclic diols which participate in the PAES polymerization are not phenol groups and have a high pKa > 11, which makes them very difficult to react due to their low acidity. SUMMARY
The present invention aims to address several challenges linked to process economics and use of acyclic diol monomer(s) to either partially or completely replace bisphenols in order to lessen the impact of endocrine disruption potential.
The particular advantages of the present process are as follows:
- reducing the economic constraint of making a PAES from less-reactive acyclic diols, containing at least 2 hydroxy groups such as alkylene oxide or poly(alkylene oxide), and optionally from less-reactive alicyclic compounds, by using a more cost-effective chlorinated sulfone monomer (e.g., dichlorodiphenylsulfone (DCDPS) and/or sulfonated DCDPS) while still achieving reasonably high molecular weight (e.g., Mw > 40 kDa, preferably > 50 kDa) for the PAES; and
- reducing or eliminating the endocrine disruption potential of commercially available PAES materials - such as those made from Bisphenol A (BP A) or Bisphenol S (BPS) - in order for their use in applications where contact with food, drugs, blood and/or water takes places, such as in membrane markets.
The various aspects of the present invention is set out in the appended set of claims.
A first aspect of the invention relates to a polyarylethersulfone polymer (“PAES”) defined in any one of claims 1-10 or 25.
A second aspect of the invention relates to a process defined in any one of claims 11-24 for manufacturing the PAES.
Other aspects of the invention relate to the use of the PAES, a solution or article comprising such a PAES, defined in any one of claims 26-28.
More precisions and details about various embodiments, advantages, and features of the invention will be more readily understood and appreciated by reference to the detailed description and examples.
DETAILED DESCRIPTION
Definitions In the present descriptive specification, some terms are intended to have the following meanings.
As used herein, the term “heterocyclic” defines a structure (such as a diol or moiety) which contains one or more rings with more than one type of atoms in the ring, one of which being a carbon atom and the other being a heteroatom (i.e., a noncarbon atom, such as oxygen atom, sulfur atom or nitrogen atom).
As used herein, the term “aliphatic diol” means, for the purpose of the present invention, a non-aromatic organic compound comprising two hydroxyl functions. An aliphatic diol may be linear, branched or cyclic. The aliphatic diol may, in addition to the oxygen atoms of the two hydroxyl groups, comprise one or more heteroatoms (i.e., non-carbon atoms), for example atoms of oxygen, nitrogen and/or sulfur.
As used herein, the term “alicyclic” defines a structure that is both aliphatic (meaning non-aromatic) and cyclic. An alicyclic structure (such as a diol or moiety) may contain one or more non-aromatic rings. An alicyclic structure may be unsaturated or saturated.
For the purpose of the present invention, the terms "cycloaliphatic moiety" or "alicyclic moiety" are interchangeable and are intended to denote any moiety being both aliphatic (i.e., not aromatic) and cyclic (i.e., where atoms are connected in a ring). The cycloaliphatic moiety (M) may be either unsubstituted or substituted. The cycloaliphatic moiety may be heterocyclic. When the cycloaliphatic moiety (or alicyclic moiety) does not comprise any heteroatoms in the ring, the backbone of the cycle of the cycloaliphatic (or alicyclic) moiety is made only of interconnected carbon atoms.
Similarly, for the purpose of the present invention, the terms “cyclic aliphatic diol” and “alicyclic diol” can be used interchangeably. In addition to the oxygen atoms of the two hydroxyl groups, an alicyclic diol may be heterocyclic, in that at least one ring comprises one or more heteroatoms (i.e., noncarbon atoms) in a ring, for example atoms of oxygen, nitrogen and/or sulfur.
As used herein, the term “acyclic” defines a structure which does not have any ring. An acyclic structure (such as a diol or moiety) may be unsaturated or saturated. For the purposes of the present invention, “linear aliphatic diols” and “branched aliphatic diols” are acyclic diols. In addition to the oxygen atoms of the two hydroxyl groups, an acyclic diol may comprise one or more heteroatoms (i.e., non-carbon atoms, for example atoms of oxygen, nitrogen and/or sulfur) connected to at least one carbon atom, or may have a backbone made only of connected carbon atoms. As used herein, the term “aromatic” defines a structure (such as a diol or moiety) which contains at least one aromatic ring.
As used herein, the term “l,4:3,6-dianhydrohexitol” means a heterocyclic diol obtained by double dehydration of a hexitol such as mannitol, sorbitol and iditol. The l,4:3,6-dianhydrohexitols are primarily in the form of stereoisomers: isosorbide, isomannide, and isoidide. An l,4:3,6-dianhydrohexitol may be used in the present invention as at least one alicylic diol (BB’) for the formation of the PAES according to the invention. Preferably, the l,4:3,6-dianhydrohexitol used as alicylic diol (BB’) in the process of the invention is isosorbide.
As used herein, the term “total weight % monomers” is defined as the weight of the monomers initially present in the reaction medium based on the total weights of monomers and solvent.
The term "solvent" is used herein in its usual meaning, that is to say, it indicates a substance capable of dissolving another substance (solute) to form a uniformly dispersed mixture at the molecular level. In the case of a polymeric solute it is common practice to refer to a solution of the polymer in a solvent when the resulting mixture is transparent and no phase separation is visible in the system. Phase separation is taken to be the point, often referred to as "cloud point", at which the solution becomes turbid or cloudy due to the formation of polymer aggregates.
In the present disclosure, the term “recurring unit” designates the smallest unit of a PAES polymer which is repeating in the chain and which is composed of a condensation of a diol compound and a dihaloaryl compound. The term “recurring unit” is synonymous to the terms “repeating unit” and “structural unit”.
As used herein, the term “homopolymer” encompasses a polymer which only has one type of recurring unit. The PAES homopolymer is obtained from the condensation of only one diol monomer and only one one dihaloaryl monomer.
As used herein, the term “copolymer” encompasses a polymer which may have two or more different types of recurring units. The PAES copolymer may be obtained from the condensation of at least two diol monomers and at least one dihaloaryl monomer, or from the condensation of at least one diol monomer and at least two dihaloaryl monomers.
As used herein, the abbreviation “ISOSO” means isosorbide; the abbreviation “BP A” means Bisphenol A or 4,4'-isopropylidenediphenol; the abbreviation “BPS” means Bisphenol S or 4,4’ -dihydroxy diphenyl sulfone; the abbreviation “BP” means 4,4’-biphenol; the abbreviation “TMBPF” means tetramethyl Bisphenol F; and the abbreviations “daBPA”, “daBPS” and “daBP” refer to diallyl Bisphenol A, diallyl Bisphenol S and diallyl 4,4 ’-biphenol, respectively. As used herein, a polyethersulfone (PES) denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol. %, at least 95 mol.%, or at least 99 mol.% of recurring units (RPES) of formula (J):
(J), (the mol.% being based on the total number of moles of recurring units in the PES polymer). PES can be prepared by known methods and is notably available as VERADEL® PES from Solvay Specialty Polymers USA, L.L.C.
As used herein, a polysulfone (PSU) denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least 90 mol.%, at least 95 mol.%, or at least 99 mol.% of recurring units (RPSU) of formula
(the mol.% being based on the total number of moles of recurring units in the PSU polymer). PSU can be prepared by known methods and is notably available as Udel® PSU from Solvay Specialty Polymers USA, L.L.C.
As used herein, a polyphenylsulfone (PPSU) denotes any polymer comprising at least 50 mol.%, at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, at least f
(the mol.% being based on the total number of moles of recurring units in the PPSU polymer). PPSU can be prepared by known methods and is notably available as RADEL® PPSU from Solvay Specialty Polymers USA, L.L.C.
The expression “weight average molecular weight (Mw)” is hereby used according to its usual meaning and mathematically expressed:
Mw = (Z Ni» Mi2) / S Ni*Mi wherein the summation S is over all the chain lengths from 1 to oo, Mi is the discrete value for the molecular weight of polymer molecule, and Ni is the number of polymer molecules with weight Mi.
The expression “number average molecular weight (Mn)” is hereby used according to its usual meaning and mathematically expressed as:
Mn = (Z Ni*Mi) I S Ni wherein the summation S is over all the chain lengths from 1 to oo, and Mi and Ni are the same as defined in the expression “Mw”.
The expression “size average molecular weight (Mz)” is hereby used according to its usual meaning and mathematically expressed as:
Mz = (S Ni* Mi3) I S Ni*Mi2 wherein the summation S is over all the chain lengths from 1 to oo, and Mi and Ni are the same as defined in the expression “Mw”.
As used herein and unless explicitly stated otherwise, the poly dispersity index (PDI) is hereby expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). This parameter gives an indication of how broad a range of molecular weights are in the PAES.
As used herein and unless explicitly stated otherwise, “substantially free of’ a component in a substance (such as reaction medium, monomers mixture, a polymer, ... ) means that the concentration of the component is no more than 1 wt% or no more than 0.5 wt% based on the total weight of such substance.
As used herein and unless explicitly stated otherwise, “free of’ a component in a substance (such as reaction medium, monomers mixture, a polymer, ... ) means that the concentration of the component is no more than 0.1 wt% or no more than 0.05 wt%, based on the total weight of such a substance.
For the purpose of the present invention, the expression “substantially all” in combination with a recited amount of recurring unit(s) is hereby intended to mean that minor amounts, generally below 1 mol.%, preferably below 0.5 mol.%, of other recurring units may be tolerated, e.g., as a result of lower purity in monomers used.
For the purpose of the present invention, the expression “substantially equimolar” used with reference to the overall amount of hydroxyl groups from diol mononer(s) and halogen groups from dihalo monomer(s) in the reaction medium is to be understood that the molar ratio between the overall amount of hydroxyl groups from the acyclic diol (AA) and any optional co-diols (BB) and/or (BB’) and the overall amount of halogen groups from the dihaloaryl sulfone monomer (CC) is from 0.95 to 1.05, preferably from 0.98 to 1.02, more preferably from 0.99 to 1.01, yet more preferably from 0.995 to 1.008. In the present specification, the choice of an element from a group of elements (such as a Markush group) also explicitly describes:
- the choice of two or the choice of several elements from the group,
- the choice of an element from a subgroup of elements consisting of the group of elements from which one or more elements have been removed.
In the passages of the present specification which will follow, any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. Each embodiment thus defined may be combined with another embodiment, unless otherwise indicated or clearly incompatible. In addition, it should be understood that the elements and/or the characteristics of a polymer, a reaction medium, a composition, a solution, a product or article, a process or a use, described in the present specification, may be combined in all possible ways with the other elements and/or characteristics of the polymer, reaction medium, composition, solution, product or article, process or use, explicitly or implicitly, this being done without departing from the scope of the present description.
In the present application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components. Any element or component recited in a list of elements or components may be omitted from such list. Further, it should be understood that elements, embodiments, and/or features of polymers, processes or methods described herein can be combined in a variety of ways without departing from the scope and disclosure of the present teaching, whether explicit or implicit herein.
In the present specification, the description of a range of values for a variable, defined by a bottom limit, or by a top limit, or by a bottom limit and a top limit, also comprises the embodiments where the variable is chosen, respectively, within the range of values: excluding the bottom limit, or excluding the top limit, or excluding the bottom limit and the top limit. Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents.
The term "comprising" (or “comprise”) includes "consisting essentially of' (or “consist essentially of’) and also "consisting of' (or “consist of’). The term “consisting essentially of’ in relation to a polymer, composition, product, polymer, solution, process, method, etc is intended to mean that any additional element or feature which may not be explicitly described herein and which does not materially affect the basic and novel characteristics of such a polymer, composition, product, polymer, solution, process, method, etc can be included in such an embodiment. For example, when a polymer, composition, compound, product, polymer, or solution “consists essentially of’ required elements, it is generally understood that any additional element may be present in not more than 1 wt% based on the total weight of the polymer, composition, compound, product, polymer, solution, etc or not more than 1 mol.% based on the total number of moles of the polymer, composition, compound, product, polymer or solution. In the particular context of the PAES polymer, the expression ‘consisting essentially of is used for defining constituents of the PAES polymer to take into account end chains, defects, irregularities and monomer rearrangements which might be comprised in said PAES polymer in minor amounts, without this modifying essential properties of the PAES polymer.
The use of the singular ‘a’ or ‘one’ herein includes the plural unless specifically stated otherwise.
The disclosure of all patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein. Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
Description of various aspects of the invention
The inventor has surprisingly found that certain acyclic aliphatic monomers which have low or no endocrine disruption potential can be used to successfully prepare, using an inorganic metal phosphate (preferably tripotassium phosphate) as a base in a polar aprotic solvent, a PAES homopolymer or copolymer with appropriate set of characteristics and properties (notably high molecular weight Mw > 40 kDa, preferably > 50 kDa).
The PAES homopolymer or copolymer incorporating such acyclic monomer, as well as articles comprising it or made from the PAES (such as membranes to be used for purifying water or biological fluids) should exhibit a low or reduced estrogenic activity compared to PAES polymers made from bisphenol A or bisphenol S, and therefore they should present lower risks for human health. These PAES homopolymer or copolymer according to the invention can also be effectively prepared using a less-expensive dichlorodiphenylsulfone monomer (DCDPS), thereby providing a more cost effective production, despite the fact that these acyclic diols tend to have poorer reactivity with DCDPS, when compared to more-reactive difluorodiphenylsulfone monomer (DFDPS).
This is an improvement over previous PAES polymers made, using potassium carbonate as sole base in a polar aprotic solvent, from acyclic aliphatic diols which typically require the use of the expensive and more corrosive DFDPS. The process operating with DFDPS poses a challenge for scaling up of manufacturing plants in term of material of construction (e.g., Hasteloy® alloys) and also making the economics of such manufacturing plants less favorable due to higher operational costs.
Poly(arylether sulfone) polymer (PAES)
The Applicant has now found that a poly(arylethersulfone) [PAES] according to the invention which is made by condensation of at least one acyclic diol monomer (AA) and at least one dihaloaryl sulfone monomer (CC) in the presence of a base containing an inorganic metal phosphate exhibits high molecular weight (Mw > 40 kDa, preferably > 50 kDa).
In particular, the PAES according to the invention has a higher Mw compared to a PAES which is made by condensation of same monomers but in the presence of potassium carbonate used as sole base during polycondensation.
Moreover the PAES according to the invention may further have a narrower molecular weight distribution compared to a PAES made using a weak base.
In particular, the PAES according to the invention may be characterized by a higher Mz/Mw ratio compared to a PAES which is made by condensation of same monomers but in the presence of potassium carbonate used as sole base during polycondensation.
The Mz/Mw of the PAES according to the invention may be advantageously at least 1.5, preferably at least 1.51, more preferably at least 1.52 and/or the Mz/Mw of the PAES may be advantageously at most 1.8, preferably at most 1.75, more preferably at most 1.7, yet more preferably at most 1.65, wherein Mz is the size average molecular weight of the PAES and Mw is the weight average molecular weight of the PAES. The Mw and Mz of the PAES are preferably determined by gelpermeation chromatography (GPC) calibrated with polystyrene standards and performed using DMAc as mobile phase.
Phosphorous Content One aspect of the present invention thus relates to a PAES having a phosphorous content of at least 3 ppm P, or at least 4 ppm P, or at least 5 ppm P, or at least 6 ppm P. The ‘ppm P’ content in the PAES is based on weight, meaning that 6 ppm is equivalent to 6 microgram P per g of PAES. The phosphorous content of the PAES according to the invention may be 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. At least a portion of the phosphorous in the PAES is not chemically bound to the PAES. Preferably, the phosphorous in the PAES originates at least in part from inorganic metal phosphate(s). The phosphorous content is preferably measured by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) analysis after mineralization by ashing. A particular suitable ICP-OES method is detailed in the examples section below.
The phosphorous content in the PAES originates from free phosphorous- containing material such as residual inorganic metal phosphate (e.g., K3PO4, K2HPO4), and optionally from any phosphorous-containing material bound to the PAES polymer chains such as in pendant groups. At least a portion of the phosphorous in the PAES is not chemically bound to the PAES. The term “free P” means that the phosphorous-containing material is not chemically bound to the PAES polymeric chain and end groups. For instance, the free P-containing material may be trapped in or adsorbed onto the PAES polymeric chains. The term “bound P” means that the phosphorous-containing material is chemically bound to the PAES polymer chain (for example by way of phosphate-containing pendant groups) and//or phosphate-containing end groups. Preferably, more than 80 wt% and up to 100 wt% of the phosphorous content in the PAES originates from free phosphorous-containing material, preferably from residual inorganic metal phosphate, more preferably from residual potassium phosphate (tri-, di- or monobasic).
Preferably, the PAES according to the present invention has a content in free (not chemically bound) phosphorous of at least 3 ppm P, or at least 4 ppm P, or at least 5 ppm P, or 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 phosphorous content is preferably measured by ICP-OES analysis after mineralization by ashing.
Sulfone recurring unit (Ra) of PAES
The PAES according to the invention preferably comprises at least one sulfone recurring unit (Ra) made from the at least one dihaloaryl sulfone monomer (CC) comprising at least one -S(=O)2- group and at least one acyclic diol monomer (AA). The at least one acyclic diol monomer (AA) may be represented by general formula (D): HO-Q-OH.
The at least one acyclic diol (AA) may be a linear or branched aliphatic diol.
In addition to the oxygen atoms of the two hydroxyl groups, the at least one acyclic diol (AA) may comprise one or more heteroatoms (i.e., non-carbon atoms, for example atoms of oxygen, nitrogen and/or sulfur) connected to at least one carbon atom.
Alternatively, the at least one acyclic diol (AA) may have a backbone made only of connected carbon atoms.
Non-limiting examples of acyclic diols (AA) may be selected from alkylene oxides and/or poly (alkylene oxide)s, 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-l,3-propanediol; 2,2-dimethylpropane-l,3-diol (also known as neopentyl glycol); 2,2,4-trimethyl-l,3-pentanediol; 2-ethyl-2-butyl- 1,3-propanediol; polyethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.
Non-limiting examples of acyclic diols (AA) which are linear 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.
Non-limiting examples of acyclic diols (AA) which are branched aliphatic diols are 2-methyl- 1,3 -propanediol, 2,2-dimethylpropane-l,3-diol, 2,2,4-trimethyl- 1,3 -pentanediol, 2-ethyl-2-butyl- 1,3-propanediol, propylene glycol, and/or polypropylene glycol).
A suitable acyclic diol (AA) advantageously has a molecular weight of at least 60 g/mol and less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol. .
Preferably, the acyclic diol (AA) is a poly(ethylene glycol) [“PEG”] and/or 2,2-dimethylpropane-l,3-diol [“DMP”] (also known as neopentyl glycol). The PEG may have a molecular weight of less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
The sulfone recurring unit (Ra) may be of general formula (I) as shown below : -[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m-O-Q-O- (I), wherein Q is an acyclic moiety derived from the at least one acyclic diol (AA); wherein n and m are independently 0, 1, 2, 3 or 4; wherein Ar3, Ar4 are equal or different from each other and are aromatic moieties of the formula: wherein Ar5 is selected from the group consisting of: wherein each of R in any one of Ar3, Ar4, Ar5 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. In the sulfone recurring unit (Ra) of general formula (I), n and m are preferably independently 0, 1 or 2; more preferably n and m are 0 or 1.
In addition, when i in any one of Ar3, Ar4, Ar5 is 1, 2, 3 or 4, each R corresponding to such an i is preferably independently selected from the group consisting of halogens, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, and sulfonic acid (-SO3H).
More preferably, each i in Ar3, Ar4, Ar5 is 0, and none of the aromatic rings in Ar3, Ar4, Ar5 in the sulfone recurring unit (Ra) of general formula (I) is substituted by R.
The portion -[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m- in formula (I) of the sulfone recurring unit (Ra) is derived from the at least one dihaloaryl sulfone monomer (CC).
The portion -O-Q-O- in formula (I) of the sulfone recurring unit (Ra) is derived from the at least one acyclic diol (AA) of formula (D): HO-Q-OH.
Non-limiting examples of suitable acyclic diols (AA) from which the acyclic moiety Q may be derived are selected from alkylene oxides and/or poly(alkylene oxide)s, 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-l,3-propanediol; 2,2- dimethylpropane-l,3-diol (neopentyl glycol); 2,2,4-trimethyl-l,3-pentanediol; 2- ethyl-2-butyl-l,3-propanediol; polyethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.
The divalent acyclic moiety Q may be represented by formula (V):
-[Rk-O-]z-Rk- (V), in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-l,3- propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,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, the divalent acyclic moiety Q is represented by any one of following formulae (V’), (V”), (V’”) and (V””):
-[CH2-CH2-O]Z-CH2-CH2- (V’),
-[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (V”),
-[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (V’”),
-[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (V””), in which z is 0 or an integer from 1 to 500.
When the acyclic moiety Q is derived from a poly(alkylene oxide) and represented by any one of the formulae (V), (V’), (V”), (V’”) and (V””), z is preferably an integer from 2 to 200, more preferably an integer from 2 to 100, yet more preferably an integer from 2 to 50.
When the acyclic diol (AA) of formula (D): HO-Q-OH is a poly(alkylene oxide), in which Q is represented by any one of the formulae (V), (V’), (V”), (V’”) and (V””), z in any of these formulae is selected such that the average molecular weight of the the acyclic diol (AA) does not exceed 30,000 g/mol. Preferably, z in any of the formulae (V), (V’), (V”), (V’”) and (V””) is preferably selected such that the molecular weight of the acyclic diol (AA) is less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
The sulfone recurring unit (Ra) in the PAES is preferably of formula (la) shown below: wherein in formula (la):
- each Ri 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium ;
- i for each Ri is 0, 1, 2, 3 or 4; and
- Q is represented by any of the formulae (V), (V’), (V”), (V’”), (V””) defined above.
When i is not zero in formula (la), each Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
In formula (la), i is preferably 0 for each Ri. The sulfone recurring unit (Ra) in the PAES is more preferably of formula (lb) shown below: wherein in formula (lb), Q is a moiety represented by any one of formulae (V), (V’), (V”), and/or (V’”), preferably represented by any one of formulae (V’) and/or (V”).
The recurring units in the PAES according to the invention may comprise more than 10 wt%, preferably more than 30 wt%, more preferably more than 50 wt%, still more preferably more than 70 wt%, and most preferably more than 90 wt% of the sulfone recurring unit (Ra) as detailed above, said wt% being relative to the total weight of recurring units in the PAES.
The PAES according to the invention may be a homopolymer and its recurring units consist essentially of the sulfone recurring unit (Ra). In such instance, the sulfone recurring unit (Ra) is preferably represented by the formula (lb), in which Q is represented by any one of the formulae (V), (V’), (V”), (V’”), and (V””) defined herein, preferably represented by any one of the formulae (V’), (V”), (V””).
Particularly advantageous, a PAES homopolymer in which substantially all of its recurring units are sulfone recurring unit (Ra), its preferred sulfone recurring unit (Ra) is represented by formula (lb), wherein Q in formula (lb) is derived from a branched aliphatic diol, such as but not limited to, 2-methyl-l,3-propanediol, 2,2- dimethylpropane-l,3-diol (also known as neopentyl glycol), 2,2,4-trimethyl-l,3- pentanediol, 2-ethyl-2-butyl-l,3-propanediol, propylene glycol, and/or polypropylene glycol), preferably derived from a branched aliphatic diol selected from 2-methyl-l,3-propanediol, 2,2-dimethylpropane-l,3-diol (neopentyl glycol), propylene glycol, and/or polypropylene glycol).
Optional sulfone aromatic recurring units (Rb) and/or (Rc)
The PAES according to the invention may be a copolymer comprising the sulfone recurring unit (Ra) as detailed above and at least one additional sulfone recurring unit (Rb) and/or (Rc).
The additional recurring unit (Rb) is a recurring unit made from the at least one dihaloaryl sulfone monomer (CC) and at least one aromatic diol (BB).
The additional recurring unit (Rc) is a recurring unit made from the at least one dihaloaryl sulfone monomer (CC) and at least one alicyclic diol (BB’). When the PAES according to the invention is a copolymer, its recurring units may comprise more than 10 wt%, preferably more than 30 wt%, more preferably more than 50 wt%, still more preferably more than 70 wt%, and most preferably more than 90 wt% of the sulfone recurring unit (Ra) as detailed above and of at least one additional sulfone recurring unit (Rb) and/or (Rc), said wt% being relative to the total weight of recurring units in the PAES.
When the PAES is a copolymer, its recurring units may consist essentially of the sulfone recurring unit (Ra) and at least one additional sulfone recurring unit (Rb) and/or (Rc).
Optional sulfone recurring unit (Rb)
The optional sulfone recurring unit (Rb) is made from the 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 least one acyclic diol (AA).
It should be understood that the at least one aromatic diol (BB) contains at least two hydroxyl groups. This means that, in the context of the present invention, the aromatic diol (BB) also encompasses any aromatic compound (BB*) with more than two hydroxyl groups. An aromatic compound (BB*) which has 3 to 6 hydroxyl groups, particularly 3 or 4 hydroxyl groups, may be envisioned to use in the aromatic diol (BB), or as the aromatic diol (BB), to make the sulfone recurring unit (Rb) by reacting with the at least one dihaloaryl sulfone monomer (CC). For example, the aromatic diol (BB) may include, or may be, an aromatic triol, such as l,l,l-tris-(4- hydroxyphenyl)-ethane.
As non-limiting examples of suitable aromatic diols (BB) used to make the optional sulfone recurring unit (Rb) by condensation with at least one dihaloaryl sulfone monomer (CC), mention may be made of bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4’ -biphenol, diallyl biphenol, bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, hydroquinone, resorcinol, an aromatic triol such as l,l,l-tris-(4-hydroxyphenyl)-ethane, or any combination thereof.
A suitable aromatic diol (BB) is preferably selected from the group consisting of bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, and any combination thereof; more preferably selected from the group consisting of 4,4 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, and combination thereof; most preferably being 4,4’-biphenol.
The sulfone recurring unit (Rb) may be of general formula (II) as shown below : -[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m-O-W-O- (II), wherein n, m, Ar3, Ar4 and Ar5 are the same as defined for recurring unit (Ra) of general formula (I); and wherein W is defined by general formula (IV): -Ar6-(T-Ar7)y- (IV), in which
- T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CC13)2-, -C(=CC12)-, -CH2-, -O-, -C(O)-, -S-, -so-, -C(CH3)(CH2CH2COOH)-, and any combination thereof; preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -CH2-, -C(O)-, and any combination thereof; more preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -CH2-, and any combination thereof,
- y is 0 or 1, and
- Ar6, Ar7 are equal or different from each other and are aromatic moieties of the formula with any of the following formulae (H), (H’) and (H”) : 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 j’ in any of the formulae (H), (H’) and (H”) is 0, 1, 2, 3 or 4.
When the aromatic ring in the moieties represented by any of the formulae (H), (H’) and (H”) is not substituted, j’ is 0.
The divalent portion -[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m- in the formula (II) of the sulfone recurring unit (Rb) is derived from the at least one dihaloaryl sulfone monomer (CC).
The divalent portion -O-W-O- in the formula (II) of the sulfone recurring unit (Rb) is derived from at least one aromatic diol (BB) of formula HO-W-OH.
Preferably, W in formula (II) is defined by formula (IVa):
-Ar6-T-Ar7- (IVa), in which: - T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -CH2- and any combination thereof, and
- each of the Ar6 and Ar7 is an unsubstituted arylene group of formula (H), wherein J -0.
Alternatively, W in formula (II) is defined by formula (IVa):
-Ar6-T-Ar7- (IVa), in which:
- T is -CH2-, and
- each of Ar6 and Ar7 is an unsubstituted arylene group of the formula (H) wherein j’=0, or a substituted arylene group of formula (H) wherein j ’=2 and R’ is methyl; or in which:
- T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, and any combination thereof, and
- each of Ar6 and Ar7 is an unsubstituted arylene group of the formula (H), wherein j’=0, or a substituted arylene group of formula (H), wherein j’=l and each R’ is an allyl group of either of the following formulae:
-(CH2)k-CH=CH-CH3 or -(CH2)k+i-CH=CH2, wherein k is 0 or an integer from 1 to 4.
Yet alternatively, W in formula (II) is defined by formula (IVb):
-Ar6- (IVb), in which the Ar6 is an unsubstituted arylene group of the formula (H) or (H’) wherein J -0.
The additional recurring unit (Rb) is preferably represented by formula (Ila) shown below: wherein :
- each Ri 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- i for each Ri is 0, 1, 2, 3 or 4; and - W is the same as defined in formula (II).
When i is not zero in formula (Ila), each Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
In formula (Ila), i is preferably 0 for each Ri.
The additional sulfone recurring unit (Rb) in the PAES is more preferably represented by any of the following formulae (Uh), (lie), (lid), (lie), (Ilf), (Ilg): wherein each Ri and i in any of the formulae (lib), (lie), (lid), (lie), (Ilf), (Ilg) are the same as defined for the formula (Ila), and wherein T in formula (Ilg) is selected from the group consisting of a bond, -SO2-, - C(CH3)2-, and any combination thereof.
When i is not zero in any of the formulae (lib), (lie), (lid), (lie), (Ilf), (Ilg), the Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
In any of the formulae (Uh), (lie), (lid), (lie), (Ilf), (Ilg), i is preferably 0 for each Ri.
The additional sulfone recurring unit (Rb) in the PAES is yet more preferably of the formula (lib).
The additional sulfone recurring unit (Rb) in the PAES is even more preferably of the formula (lib) in which i is 0 for each Ri.
When the PAES comprises both sulfone recurring units (Ra) and (Rb), the molar ratio rb of sulfone recurring units (Ra) to sulfone recurring units (Rb) may be : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40, or yet even more preferably at least 65:35.
When the PAES according to the invention is a copolymer in which substantially all of its recurring units are sulfone recurring units (Ra) and (Rb), its preferred sulfone recurring unit (Rb) is represented by any of the formulae (Uh), (lie), (lid), (lie), (Ilf), (Ilg), and its preferred sulfone recurring unit (Ra) is represented by the formula (lb), wherein Q in formula (lb) is represented by any one of the formulae (V), (V’), (V”), (V’”), (V””), preferably represented by any of formulae (V’), (V”), (V’”), (V””), more preferably represented by any of formulae (V’), (V”), (V””). Particularly advantageous, a PAES copolymer in which substantially all of its recurring units are sulfone recurring units (Ra) and (Rb), its preferred sulfone recurring unit (Rb) is represented by any of the formulae (lib), (lie), (lid), (lie), (Ilf), (Ilg), more preferably formula (lib), and its preferred sulfone recurring unit (Ra) is represented by formula (lb), wherein Q in formula (lb) is derived from a branched aliphatic diol, such as but not limited to, 2-methyl-l,3-propanediol, 2,2- dimethylpropane-l,3-diol (also known as neopentyl glycol), 2,2,4-trimethyl-l,3- pentanediol, 2-ethyl-2-butyl- 1,3 -propanediol, propylene glycol, and/or polypropylene glycol), preferably derived from a branched aliphatic diol selected from 2-methyl-l,3-propanediol, 2,2-dimethylpropane-l,3-diol (neopentyl glycol), propylene glycol, and/or polypropylene glycol).
Advantageously, Q in the formula (lb) may have a molecular weight of less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
Optional sulfone recurring unit (Rc)
The PAES according to the invention may further comprise at least one sulfone recurring unit (Rc) made from the condensation from the at least one dihaloaryl sulfone monomer (CC) and at least one alicyclic diol (BB’) comprising at least one cycloaliphatic moiety (M).
The cycloaliphatic moiety (M) may comprise only one non-aromatic ring.
Alternatively, the cycloaliphatic moiety (M) may comprise two or more non- aromatic rings. The two or more non-aromatic rings may be fused together by sharing two or more neighboring ring carbon atoms, or which may be connected by a single bond or a linking alkylene group such as -(CH2)P- with p>l or -C(CHs)2-.
The cycloaliphatic moiety (M) may comprise at least one heteroatom in a ring, such as at least one oxygen atom and/or at least one nitrogen atom.
Alternatively, the at least one cycloaliphatic moiety (M) does not comprise any heteroatoms in a ring.
The sulfone recurring unit (Rc) of the PAES according to the invention may be represented by general formula (III) as shown below :
-[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m-O-E-O- (III), wherein E comprises the at least one cycloaliphatic moiety (M) and is a group which comprises from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms or from 4 to 10 carbon atoms; wherein n and m are independently 0, 1, 2, 3 or 4; wherein Ar3, Ar4 are equal or different from each other and are aromatic moieties of the formula: wherein Ar5 is selected from the group consisting of: wherein each of R in any of Ar3, Ar4, Ar5 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.
In the sulfone recurring unit (Rc) of general formula (III), n and m are preferably independently 0, 1 or 2; more preferably n and m are 0 or 1.
In addition, when i in any of Ar3, Ar4, Ar5 is 1, 2, 3 or 4, each R corresponding to such an i is preferably independently selected from the group consisting of halogens, alkali metal sulfonates, alkaline earth metal sulfonates, alkyl sulfonates, and sulfonic acid (-SO3H).
More preferably, each i in any of Ar3, Ar4, Ar5 is 0, and none of the aromatic rings in Ar3, Ar4, Ar5 is substituted by R. That is to say, Ar3, Ar4, Ar5 have only unsubstituted arylene groups.
The portion -[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m- in formula (III) of the sulfone recurring unit (Rc) is made from the at least one dihaloaryl sulfone monomer (CC).
The portion -O-E-O- in formula (III) of the sulfone recurring unit (Rc) is derived from the at least one alicyclic diol (BB’).
In particular, the sulfone recurring unit (Rc) is preferably of formula (Illa) as shown below :
(Illa), wherein :
- each Ri 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;
- i for each Ri is 0, 1, 2, 3 or 4; and
- E comprises the at least one cyclic aliphatic moiety (M) and is a group which comprises from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms.
When i is not zero in formula (Illa), each Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
In formula (Illa), i is preferably 0 for each Ri.
The sulfone recurring unit (Rc) is more preferably represented by formula (Illb) shown below : (Illb), wherein E, each of Ri and each of i are the same as defined in formula (Illa).
When i is not zero in formula (Illb), each Ri corresponding to such an i is preferably independently selected from the group consisting of 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.
In formula (Illb), i is preferably 0 for each Ri.
The sulfone recurring unit (Rc) is yet more preferably represented by formula (IIIc) shown below : wherein E is the same as defined in formula (Illa).
In any of the formulae (III), (Illa), (Illb), (IIIc), E is preferably selected from the group consisting of those of formulae (El) to (Ell):
(EH), and any combination thereof, wherein each sign * in the formulae (El) to (El 1) denotes where E is bonded to an oxygen atom of the -O-E-O- formula; and wherein each Q’, being the same or different in the formula (El 1), is an acyclic moiety.
The E represented by any of the formulae (E4) to (E10) may exist in different stereochemical arrangements. For the sake of simplicity, the stereochemistry of the bonds, in particular the stereochemical arrangement of the C-* bonds in formulae (E4) to (E10) is not indicated in the present specification. It has to be understood that all stereoisomers, each one singly as well as their mixtures, are encompassed by each formula (E4) to (E10).
Although not preferred, the -O-E-O- group in any of the formulae (III), (Illa), (Illb), (IIIc) may be derived from an alicyclic diol (BB’) containing acyclic aliphatic diol end groups. For example, the alicyclic diol (BB’) may comprise or may be isosorbide with acyclic aliphatic end groups (diol (Dll) represented by the formula HO-E11-OH).
The acyclic moiety Q’ in formula (El 1) may be derived from an acyclic diol selected from alkylene oxides and/or poly(alkylene oxide)s, 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-l,3-propanediol; 2,2-dimethylpropane-l,3- diol; 2,2,4-trimethyl-l,3-pentanediol; 2-ethyl-2-butyl-l,3-propanediol; poly(ethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.
The acyclic moiety Q’ in formula (Ell) may be represented by formula (VI): -[ Rk-O-]z-Rk- , in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2 -butyl- 1,3- propylene [CH2-C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-l,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, yet more preferably an integer from 2 to 50; preferably, represented by any one of formulae (VI’), (VI”), (VI’”) and (VI””):
-[CH2-CH2-O]Z-CH2-CH2- (VI’),
-[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (VI”),
-[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (VI’”),
-[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (VI””), in which 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, yet more preferably an integer from 2 to 50.
The optional sulfone recurring unit (Rc) for the PAES copolymer according to the invention may be represented by any one of following formulae (IIIb-1) to (Illb- 5):
(IIIb-5).
The optional sulfone recurring unit (Rc) for the PAES copolymer may be alternatively represented by following formula (IIIb-6) and/or (IIIb-8):
When the PAES comprises both sulfone recurring units (Ra) and (Rc), the molar ratio rc of sulfone recurring unit (Ra) to sulfone recurring unit (Rc) is : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, more preferably at least 30:70, yet more preferably at least 40:60, even more preferably at least 50:50; or yet even more preferably at least 60:40.
When the PAES according to the invention is a copolymer in which substantially all of its recurring units are sulfone recurring units (Ra) and (Rc), its preferred sulfone recurring unit (Rc) is represented by the formula (IIIb-1) and its preferred sulfone recurring unit (Ra) is represented by the formula (lb), wherein Q in formula (lb) is represented by any one of the formulae (V), (V’), (V”), (V’”), (V””) defined herein, preferably represented by any one of formulae (V’), (V”), (V’”), (V””). For example, the molar ratio rb of recurring unit (Ra) of formula (lb) to recurring unit (Rc) of formula (IIIb-1) may be from 10:90 to 90:10.
Inherent Viscosity of the PAES
The PAES according to the invention may have an inherent viscosity IV of at least 0.25 dL/g and/or at most 1.5 dL/g. The inherent viscosity IV of the PAES is preferably measured at 0.2 g/100 mL at 20 °C in dichloromethane/trifluoroacetic acid (9/1 v/v).
Halogen content of the PAES
The PAES according to the invention may have a halogen content greater than 0 ppm (>0 ppm) and less than or equal to 4000 ppm (< 4000 ppm), said ppm being based on the PAES weight. 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 < 2300 ppm, or even < 2200 ppm.
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.
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 up to 4000 ppm), said ppm being based on the PAES weight. 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 < 2300 ppm, or even < 2200 ppm.
The ‘ppm’ value in the halogen content (preferably chlorine content) is based on weight, meaning 100 ppm halogen (Cl) is equivalent to 100 microgram halogen/g PAES. The halogen content, particularly chlorine content, may be measured by IC- combustion, by a halogen analyzer or by XRF. A particular suitable method using a Chlorine analyzer for measuring chlorine content in the PAES is detailed in the examples below.
The halogen content of the PAES preferably includes the concentration of halogen end groups of the PAES. Other sources of halogen content in the PAES may be free halogen and/or any free halogenated compound, “free” meaning unbound to the PAES’s polymer chain and end groups. Yet another source of halogen in the PAES may be Cl and/or any chlorinated compound bound to the PAES polymer chains such as in pendant groups (e.g., halogen from the Ri pendant groups in formula (la) of recurring unit (Ra), in any of the formula (Ila) to (Ilg) of optional recurring unit (Rb) and in the formula (Illa) or (Illb) of optional recurring unit (Rc)).
The halogen content of the PAES may consist essentially of the content of halogen end groups in the PAES.
Physical and thermal properties of the PAES
The PAES according to the invention is advantageously transparent and amorphous. The amorphous PAES may have a heat of fusion of less than about 5 J/g, preferably less than about 3 J/g, said heat of fusion being measured using differential scanning calorimetry (“DSC”).
Molecular weights and molecular weight distribution of the PAES
The PAES according to the invention has advantageously a weight average molecular weight (Mw) above 40000 g/mol, preferably at least 45000 g/mol, more preferably at least 50000 g/mol. Upper limit for the number average molecular weight (Mw) of the PAES is not particularly critical and will be selected by the person skilled in the art in view of intended field of use. In general, the PAES according to the invention may have a weight average molecular weight (Mw) equal to or below 120000 g/mol, preferably equal to or below 110000 g/mol, or more preferably equal to or below 100000 g/mol, yet more preferably equal to or below 95000 g/mol.
The PAES has advantageously a weight average molecular weight (Mw) in the range of more than 40000 g/mol and up to 120000 g/mol, preferably ranging from 45000 g/mol to 110000 g/mol, more preferably ranging from 50000 g/mol to 100000 g/mol.
The PAES according to the invention has advantageously a number average molecular weight (Mn) above 15000 g/mol, preferably at least 18000 g/mol, more preferably at least 20000 g/mol. Upper limit for the number average molecular weight (Mn) of the PAES is not particularly critical and will be selected by the person skilled in the art in view of intended field of use. In general, the PAES according to the invention may have a number average molecular weight (Mn) equal to or below 100000 g/mol, preferably equal to or below 90000 g/mol or equal to or below 80000 g/mol, more preferably equal to or below 70000 g/mol or equal to or below 68000 g/mol, yet more preferably equal to or below 60 000 g/mol or equal to or below 55000 g/mol, even more preferably equal to or below 50000 g/mol.
The PAES has advantageously a number average molecular weight (Mn) in the range from 15000 g/mol to 80000 g/mol, preferably ranging from 18000 g/mol to 60000 g/mol, more preferably ranging from 20000 g/mol to 50000 g/mol, still more preferably ranging from 22000 g/mol to 45000 g/mol, even more preferably ranging from 25000 g/mol to 40000 g/mol.
Any suitable method may be used to determine the molecular weight for the PAES. For example, 1H- NMR and gel-permeation chromatography (GPC), also known as size exclusion chromatography (SEC), may be used. Unless explicitly stated otherwise, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the size average molecular weight (Mz) of the PAES are estimated by GPC, preferably calibrated with polystyrene standards and performed using a mobile phase. The mobile phase may be selected from any solvent for the PAES described herein, such as N-Methyl-2-pyrrolidone (NMP), N,N'-dimethylacetamide (DMAc), tetrahydrofuran (THF), sulfolane, or methylene chloride, preferably NMP or DMAc, more preferably DMAc. Mw, Mn and Mz of the PAES are preferably determined by GPC, calibrated with polystyrene standards and performed using DMAc as mobile phase. A particular suitable GPC method is detailed in the examples below.
The molecular weight distribution (MWD) of the PAES may be characterized by a poly dispersity index (PDI) expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The PDI of the PAES may be advantageously at least 1.8, preferably at least 1.85, and/or the PDI of the PAES may be advantageously at most 2.5, preferably at most 2.3.
The molecular weight distribution (MWD) of the PAES may be characterized by the ratio (Mz/Mw) of the size average molecular weight (Mz) to the weight average molecular weight (Mw). The Mz/Mw of the PAES may be advantageously at least 1.5, preferably at least 1.51, more preferably at least 1.52 and/or the Mz/Mw of the PAES may be advantageously at most 1.8, preferably at most 1.75, more preferably at most 1.7, yet more preferably at most 1.65.
To calculate the ratio (Mz/Mw) and PDI (Mw/Mn) of the PAES, the Mw, Mn and Mz of the PAES are preferably determined by gel-permeation chromatography (GPC) calibrated with polystyrene standards and performed using DMAc as mobile phase.
Other properties / characteristics of the PAES
The PAES contains advantageously less than 10 ppm, preferably less than 5 ppm of Bisphenol A (BPA), more preferably less than 1 ppm of BP A, said ppm being based on total weight of the PAES.
The PAES contains advantageously less than 10 ppm, preferably less than 5 ppm Bisphenol S (BPS), more preferably less than 1 ppm of BPS, said ppm being based on total weight of the PAES.
The PAES preferably is preferably free (i. e. , less than 1 ppm by weight) of BPA and BPS.
The BPS content in the PAES may be measured by liquid chromatography analysis of a solution of the PAES in N,N-dimethylformamide (DMF) after precipitation of the polymer by acetonitrile. A suitable analytical method for measuring BPS content in the PAES is described in the examples.
The BPA content in the PAES may be measured by gas chromatography analysis of a solution of the PAES in DMF or trichloromethane. A suitable analytical method for measuring BPA content in the PAES is described in the examples.
The PAES contains advantageously no more than 10 wt%, preferably no more than 8 wt%, more preferably no more than 5 wt%, most preferably no more than 2 wt%, of an oligomer fraction having a number molecular weight of less than 3000 g/mol, said wt% being based on the total weight of the PAES.
The content of such an oligomer fraction having a number molecular weight of less than 3000 g/mol in the PAES may be measured from slice data of GPC chromatogram by help of gel-permeation chromatography software which is calibrated with polystyrene standards, in which case it corresponds to :
M = 3000 wherein AU (detector response in mV) is the y-axis unit and log M (logarithm of molecular weight) is the x-axis unit.
The PAES has advantageously a residual polar aprotic solvent content of less than 3000 ppm, preferably less than 2500 ppm, more preferably less than 2000 ppm of, most preferably less than 1000 ppm and most preferably less than 500 ppm, said ppm being based on total weight of the PAES.
The PAES preferably may be substantially free (i.e., less than 500 ppm) of polar aprotic solvent.
The content of residual polar aprotic solvent in the PAES may be measured by gas chromatography (GC) analysis of a solution of the PAES in a solvent like N,N-dimethylformamide (DMF) or a different solvent if DMF is the solvent that needs to be quantified. A suitable method for measuring content of residual polar aprotic solvent in the PAES is described in the examples.
Advantageously, the PAES according to the invention has a phosphorous content of at least 3 ppm P, or at least 4 ppm P, or at least 5 ppm P, or at least 6 ppm, and preferably at most 150 ppm P, wherein the phosphorous in the PAES originates at least in part from inorganic metal phosphate(s), and preferably the PAES further has at least one of the following characteristics:
- a weight average molecular weight (Mw) of > 40 000 g/mol, and preferably at most 120 000 g/mol;
- a number average molecular weight (Mn) of at least 15 000 g/mol, and preferably at most 80 000 g/mol;
- a molecular weight distribution characterized by a ratio Mz/Mw of at least 1.5 and at most 1.8;
- a chlorine content of : at least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm, yet more preferably at least 300 ppm, and/or at most 3000 ppm, preferably at most 2900 ppm, more preferably at most 2800 ppm;
- an amount of less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm of Bisphenol A;
- an amount of less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm of Bisphenol S;
- an amount of no more than 10 wt%, preferably no more than 8 wt%, more preferably no more than 5 wt%, most preferably no more than 2 wt%, of an oligomer fraction having a number molecular weight of less than 3000 g/mol; and/or
- 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 and wt% being based on the total weight of the PAES.
Process for making the PAES
The present invention further relates to a process for making the PAES comprising sulfone recurring units (Ra) made from condensation of at least one dihaloaryl sulfone monomer (CC) comprising at least one -S(=O)2- group and at least one acyclic diol monomer (AA) and optionally further comprising other sulfone recurring units made from condensation of the dihaloaryl sulfone monomer (CC) and at least one aromatic co-diol monomer (BB) and/or alicyclic co-diol monomer (BB’) comprising at least one cycloaliphatic moiety (M), said co-diol monomer being different than the acyclic diol (AA).
The process preferably comprises reacting the at least one acyclic diol (AA), any optional co-diol (BB) and/or (BB’), and the at least one dihaloaryl sulfone monomer (CC) in a reaction medium comprising a polar aprotic solvent and a base.
The reaction is preferably conducted in one stage. This means that the deprotonation of the acyclic diol (AA) and optional co-diols (BB) and/or (BB’) with the base and the condensation reaction between the acyclic diol (AA) and optional co-diols (BB) and/or (BB’) and the dihaloaryl sulfone monomer (CC) takes place in a single reactor vessel without isolation of intermediate products.
Alternatively, the reaction can also be conducted in two or more stages.
For example the reaction may be conducted in two stages:
- by pre-mixing the monomers [ (AA), (CC) and optional (BB), (BB’) ] with the polar aprotic solvent in a reactor vessel and then adding the base to that premixture, or
- by pre-mixing the base with the polar aprotic solvent in a reactor vessel and then adding one or more of the monomers later to that pre-mixture.
Alternatively, the reaction may be conducted in two or more successive polymerization stages, in which the reaction medium is gradually diluted with solvent so as to progressively decrease the concentration (wt%) of monomers (i.e., the acyclic diol (AA), optional co-diols (BB) and/or (BB’), the dihaloaryl sulfone monomer (CC)) in the reaction medium during the course of the polymerization. Such progressive solvent dilution allows for an optimization between reactivity and viscosity of the reaction medium. Preferably, the initial monomers concentration (total wt% monomers) in the reaction medium may be from 55 wt% to 45 wt% (in the first stage), while the final monomers concentration (total wt% monomers) in the reaction medium may be from 30 wt%to 44 wt%, preferably from 33 wt% to 40 wt% (in the final stage). More preferably, the difference between the initial total wt% monomers in the first stage and the final total wt% monomers 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 successive polymerization stages are generally carried out in a same reaction vessel, but not necessarily.
For illustrative purposes, the base, the monomers and an initial amount of solvent (to dissolve the monomers) are loaded and mixed into a vessel to obtain an initial monomers concentration in the reaction medium, and a first polymerisation stage is started once the reaction medium is heated to a suitable reaction temperature. As the polymerisation progresses, the polymer molecular weight builds up resulting in an increase in the reaction medium’s viscosity. When a target viscosity (preferably ranging from 5000 to 8000 cP) of the reaction medium is reached, another amount of solvent is added to the reaction medium inside the same vessel to start a subsequent (second) polymerisation stage, but with a reduced monomers concentration compared to the initial monomers concentration in the first stage. The dilution of the reaction medium with solvent may be repeated in one or more additional successive polymerisation stages again when a target viscosity of the reaction medium (preferably ranging from 5000 to 8000 cP) is reached. That is to say, a further amount of solvent is added to the reaction medium to start a subsequent polymerisation stage but with a reduced monomers concentration compared to that of the previous stage.
Base
The reaction medium comprises a base.
The base comprises an inorganic metal phosphate, said metal being selected from Groups 1, 2 or 3 of the IUPAC periodic table.
The inorganic metal phosphate is preferably an alkali metal phosphate characterized by a pKa of its conjugated acid greater than 10.5 and less than 15 (10.5 < pKa < 15).
The inorganic metal phosphate is preferably a tribasic alkali metal phosphate in which the alkali metal is K, Na, Cs and /or Li; preferably is tripotassium phosphate (K3PO4) and/or trisodium phosphate (NasPO-i): more preferably is K3PO4. The use of the tribasic alkali metal phosphate (preferably K3PO4 and/or NasPO4, more preferably K3PO4) having an average particle size D50 of at least 10 microns and at most 400 microns is particularly preferred. More preferably, the tribasic alkali metal phosphate’s average particle size of at most 200 microns is used. Still more preferably, a tribasic alkali metal phosphate’s average particle size of at most 160 microns is used. Even more preferably, the average particle size of the tribasic alkali metal phosphate may be at least 20 microns and at most 100 microns, or at least 20 microns and at most 80 microns. While the average particle size may be measured by any suitable method, the average particle size D50 is preferably measured by light scattering in dry mode.
The use of a tribasic alkali metal phosphate having such an average particle size permits the synthesis of the PAES to be carried out at a relatively low reaction temperature, such as > 110 °C up to 200 °C.
The molar amount in the reaction medium of the tribasic alkali metal phosphate, relative to the molar amount in the reaction medium of the acyclic diol (AA) and any optional co-diols (such as diols (BB) and/or (BB’)), is:
- 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
- at most 3.0, or at most 2.8, or at most 2.75, or at most 2.5, or at most 2.4.
The base may further comprise an anhydrous alkali metal carbonate. The anhydrous alkali metal carbonate may be sometimes referred to a “co-base”.
The anhydrous alkali metal carbonate or co-base may be selected from the group consisting of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, preferably selected from sodium carbonate and/or potassium carbonate, more preferably potassium carbonate.
When the base comprises a mixture of tribasic potassium phosphate (K3PO4) and sodium carbonate (K2CO3), the molar ratio rk of K2CO3 over KaPC may be : at most 75:25, or at most 70:30, or at most 67:33, and/or at least 10:90, or at least 12:88, or at least 13:87.
The average particle size (Dso) of the alkali metal carbonate may be at least 10 microns and at most 400 microns, preferably at least 15 microns and at most 200 microns, more preferably at least 20 microns and at most 100 microns. Even more preferably, the alkali metal carbonate’s average particle size (Dso) of at least 20 microns and at most 50 microns is used.
When the process of the present invention is carried out in the presence of anhydrous K2CO3, the anhydrous K2CO3 may have a volume-averaged particle size (D[4,3]) of less than about 100 pm, for example less than 45 pm, less than 30 pm or less than 20 pm. In particular, the process of the present invention is carried out in in the presence of a carbonate component comprising not less than 50 wt% of K2CO3 having a volume-averaged particle size of less than about 100 pm, for example less than 45 pm, less than 30 pm or less than 20 pm, based on the overall weight of the carbonate component in the reaction medium. The volume-averaged particle size of the carbonate used can for example be determined with a Mastersizer 2000 from Malvern on a suspension of the particles in chlorobenzene/sulfolane (60/40).
The tribasic alkali metal phosphate salt may be used to provide a PAES polymer having desirable molecular weight characteristics and distribution. It was surprisingly found that higher molecular weight PAES homopolymers and copolymers may be obtained when tribasic potassium phosphate (K3PO4) is used in the reaction or when a combination of tribasic potassium phosphate (K3PO4) and potassium carbonate (K2CO3) (as co-base) is employed during the condensation reaction.
The base used in the reaction medium is preferably anhydrous.
Preferably the inorganic metal phosphate, specifically the tribasic alkali metal phosphate salt, used in the reaction medium is anhydrous.
Preferably when a co-base such as an alkali metal carbonate (preferably K2CO3) is used in conjunction with the inorganic metal phosphate (preferably K3PO4) in the reaction medium, the co-base (preferably K2CO3) is anhydrous.
As used herein, the term “anhydrous” refers to a substance containing less than 2 wt% moisture, preferably less than 1 wt% moisture, more preferably less than 0.5 wt% moisture, most preferably less than 0.25 wt% moisture as measured by Karl-Fisher titration or by loss on drying test.
The base does not include a strong hindered potassium base, such as potassium trimethylsilanolate. For example, the strong hindered base disclosed in W02020/201522 (Roquette Freres) is not present in the base.
The base preferably does not include an organic base.
Other than the inorganic metal phosphate and the optional alkali metal carbonate present in the base which participate(s) in the polycondensation reaction, the base does not comprise any organic catalyst. For example, the crown-ether catalyst disclosed in EP3653661 (Korea Research Institute of Chemical Technology) is not present in the base.
Other than the inorganic metal phosphate used in the base, preferably no other phosphorous-containing material is used in the reaction medium. For example, no phosphorous-containmg solvent (such as hexamethyltnamide phosphate) is used during the PAES polymerisation.
Dihaloaryl sulfone monomer (CC)
The reaction medium comprises at least one dihaloaryl sulfone monomer
(CC) of general formula (C):
X-[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m-X’ (C), wherein n, m, Ar3, Ar4 and Ar5 are the same as defined for recurring unit (Ra) of general formula (I); and wherein X and X’, equal to or different from each other in formula (C), are independently a halogen atom, preferably Cl or F, more preferably Cl.
The dihalo sulfone monomer (CC) is preferably of formula (Cl): wherein:
- X and X’, equal to or different from each other in formula (Cl), are independently a halogen atom, preferably Cl or F, more preferably Cl;
- each of Ri, equal to or different from each other, is 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
- each i, equal to or different from each other, is independently zero or an integer from 1 to 4, preferably is independently zero or 1, more preferably is zero.
When i is not zero in formula (Cl), Ri is preferably independently selected from the group consisting of alkali metal sulfonate, alkaline earth metal sulfonate, alkyl sulfonate, sulfonic acid (-SOsH), alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium.
In formula (Cl), i is preferably 0 for each Ri.
The dihaloaryl sulfone monomer (CC) more preferably consists essentially of at least one 4,4-dihalodiphenylsulfone selected from the group consisting of: 4,4’- di chlorodiphenyl sulfone (DCDPS), monosulfonated 4,4’ -di chlorodiphenyl sulfone (msDCDPS), disulfonated 4,4’ -di chlorodiphenyl sulfone (dsDCDPS), 4,4’ difluorodiphenyl sulfone (DFDPS), monosulfonated 4,4’ difluorodiphenyl sulfone (msDFDPS), disulfonated 4,4’ difluorodiphenyl sulfone (dsDFDPS), and any combination thereof.
The dihaloaryl sulfone monomer (CC) yet more preferably consists essentially of DCDPS and/or disodium bis(4-chloro-3-sulfophenyl)sulfone (dsDCDPS), most preferably consists essentially of DCDPS.
Acyclic diol (AA)
The acyclic diol (AA) is selected from linear aliphatic diols or branched aliphatic diols.
As non-limiting examples of linear aliphatic diols, mention may be made of 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.
As non-limiting examples of branched aliphatic diols, mention may be made of 2-methyl-l,3-propanediol, 2,2-dimethylpropane-l,3-diol (also known as neopentyl glycol), 2,2,4-trimethyl-l,3-pentanediol, 2-ethyl-2-butyl- 1,3-propanediol, propylene glycol, and/or polypropylene glycol).
The acyclic diol (AA) may be represented by formula (D): HO-Q-OH, in which Q is an acyclic moiety.
Advantageously, the acyclic diol (AA) of formula (D) may have a molecular weight of less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
The acyclic diol (AA) may be an alkylene oxide or a poly(alkylene oxide) represented by formula (Da):
HO-[Rk-O]z-Rk-OH (Da), wherein Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-l,3- propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,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, the acyclic diol (AA) is represented by any of following formulae (Dal), (Da2), (Da3) or (Da4):
HO-[(CH2)2-O]Z-(CH2)2-OH (Dal),
HO-[CH2-CH(CH3)-O]Z-CH2-CH(CH3)-OH (Da2), HO-[(CH2)4-O]Z-(CH2)4-OH (Da3),
HO-[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2-OH (Da4), wherein z is 0 or an integer from 1 to 500.
When the acyclic diol (AA) is an alkylene oxide or poly(alkylene oxide), it has at least two free hydroxyl groups (-OH).
When the acyclic diol (AA) is a poly(alkylene oxide), z in any of the formulae (Da), (Dal), (Da2), (Da3) and (Da4) is an integer from 1 to 500, preferably an integer from 2 to 200, more preferably an integer from 2 to 100, yet more preferably an integer from 2 to 50.
When the acyclic diol (AA) is a poly(alkylene oxide), it preferably has an average molecular weight (Mn) of from 160 to 30,000 g/mol. In such a case, z in the acyclic diol (AA) represented by any of the formulae (Da), (Dal), (Da2), (Da3) and (Da4) is preferably selected such that its average molecular weight (Mn) does not exceed 30,000 g/mol. z in any of the formulae (Da), (Dal), (Da2), (Da3) or (Da4) is preferably selected such that the molecular weight of the acyclic diol (AA) is less than 2000 g/mol, preferably of at most 1800 g/mol, more preferably of at most 1500 g/mol, still more preferably of at most 1300 g/mol, yet more preferably of at most 1100 g/mol, most preferably of at most 900 g/mol.
Optional co-diol(s)
In addition to the acyclic diol (AA), the reaction medium may further comprise at least one co-diol which is different from the at least one acyclic diol (AA).
The at least one co-diol may comprise or consist of an aromatic diol (BB) and/or an alicyclic diol (BB’).
The molar ratio r of the at least one acyclic diol (AA) to the at least one co-diol may be : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or
- at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40.
Aromatic diol (BB) as optional co-diol
In particular, the reaction medium may further comprise at least one dihydroxyaryl monomer [ hereinafter “aromatic diol (BB)”] as co-diol.
It should be understood that the at least one aromatic diol (BB) contains at least two hydroxyl groups. This means that, in the context of the present invention, the aromatic diol (BB) also encompasses any aromatic compound (BB*) with more than two hydroxy groups. An aromatic compound (BB*) which has 3 to 6 hydroxy groups, particularly 3 or 4 hydroxy groups, may be envisioned to use in the aromatic diol (BB), or as the aromatic diol (BB), to make the sulfone recurring unit (Rb) by reacting with the at least one halo sulfone monomer (CC). Non-limiting aromatic compound (BB*) containing three or more than three hydroxy groups may be selected from: phloroglucin, 4,6-dimethyl-2,4,6-tri-(4-hydroxy-5 phenyl)-heptene-2 (trimeric isopropenylphenol), 4,6-dimethyl-2,4,6-(4-hydroxyphenyl)-heptane (hydrogenated trimeric isopropenyl phenol), l,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1 -tris-(4-hy droxyphenyl)-ethane, 1,1,1 -tris-(4-hy droxyphenyl)-propane, tetra-(4- hydroxyphenyl)-methane, l,4-bis-(4', 4 "-dihydroxytriphenyl)-methyl] -benzene and 2,2-bis-[4,4'-bis-(4-hydroxyphenyl)-cyclohexyl]-propane. For example, the aromatic diol (BB) may include, or may be, an aromatic triol, such as l,l,l-tris-(4- hydroxyphenyl)-ethane.
The at least one aromatic diol (BB) may be of general formula (D’):
HO - W - OH (D’).
W in formula (D’) is defined by general formula (IV): -Ar6-(T-Ar7)y-, in which
- T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -C(CC13)2-, -C(=CC12)-, -CH2-, -O-, -C(O)-, -S-, -so-, -C(CH3)(CH2CH2COOH)-, and any combination thereof, preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -C(CF3)2-, -CH2-,
C(O)-, and any combination thereof, more preferably selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -CH2-, and any combination thereof,
- y is 0 or 1, and
- Ar6, Ar7 are equal or different from each other and are aromatic moieties of any of the
R’ in any of the formulae (H), (H’), (H”) being 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 j’ in any of the formulae (H), (H’), (H”) being 0, 1, 2, 3 or 4. When the aromatic ring in the moieties of formulae (H), (H’) and (H”) is not substituted, j’ is 0.
Preferably, W in formula (D’) is defined by formula (IVa): -Ar6-T-Ar7- , in which:
- T is selected from the group consisting of a bond, -SO2-, -C(CH3)2-, -CH2-; and any combination thereof, and
- the Ar6 and Ar7 are unsubstituted arylene groups of formula (H) wherein j’=0.
Alternatively, W in formula (D’) may be defined by formula (IVb): -Ar6- , in which the Ar6 is an unsubstituted arylene group of formula (H) or (H’) wherein J -0.
Yet alternatively, W in formula (D’) may be defined by formula (IVa): -Ar6-T-Ar7- , in which:
- T is -CH2-; and
- the Ar6 and Ar7 are unsubstituted arylene groups of formula (H) wherein j’=0, or substituted arylene groups of formula (H) wherein j ’=2 and R’ is methyl.
The 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 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, bisphenol F, hydroquinone, resorcinol, an aromatic triol such as l,l,l-tris-(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 ’-biphenol, diallyl biphenol, tetramethyl bisphenol F, and any combination thereof; yet more preferably selected from the group consisting of 4,4’ -biphenol, diallyl bi phenol, tetramethyl bisphenol F, and combination thereof; most preferably being 4,4’-biphenol.
When at least one aromatic diol(s) (BB) is employed in the reaction medium, the molar ratio rb of acyclic diol(s) (AA) : aromatic diol(s) (BB) in the reaction medium is : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40.
When an aromatic triol (BB*) such as l,l,l-tris-(4-hydroxyphenyl)-ethane is used as co-diol (BB) in the reaction medium, it is generally advantageously to use from 0.5 mol.% to 5 mol.% of the aromatic triol (BB*), said mol.% being based on the total amount of moles of diols in the reaction medium. Alicyclic diol (BB’) as optional co-diol
In addition to the at least one acyclic diol (AA), the reaction medium may further comprise at least one aliphatic (non-aromatic) and cyclic dihydroxy monomer [hereinafter “alicyclic diol (BB’)”] as co-diol.
The alicyclic diol (BB’) is different from the at least one acyclic diol (AA) and the at least one aromatic diol (BB).
The at least one alicyclic diol (BB’) comprises at least one cycloaliphatic moiety (M). The term “cycloaliphatic moiety” is intended to denote any moiety being both aliphatic (i.e., not aromatic) and cyclic (i.e., where the carbon atoms and optional heteroatoms are connected in a ring). The cycloaliphatic moiety (M) may comprise from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms or from 4 to 10 carbon atoms or from 4 to 8 carbon atoms, or from 4 to 6 carbon atoms. The cycloaliphatic moiety (M) may be either unsubstituted or substituted.
The cycloaliphatic moiety (M) may comprise at least one heteroatom in the ring, such as at least one oxygen atom.
Alternatively, the cycloaliphatic moiety (M) does not comprise any heteroatoms in the ring, meaning that the backbone of the cycle of the cycloaliphatic moiety (M) is made only of interconnected carbon atoms.
More than one cycloaliphatic moiety (M) can be present in the alicyclic diol (BB’). If more than one cycloaliphatic moiety (M) is present in the alicyclic diol (BB’), they can be the same or different.
The alicyclic diol (BB’) may comprise a polycyclic cycloaliphatic moiety, said polycyclic cycloaliphatic moiety comprising more than one condensed cycloaliphatic moieties (M). Typically, the polycyclic cycloaliphatic moiety comprises two condensed cycloaliphatic moieties (M), three condensed cycloaliphatic moieties (M) or even four condensed cycloaliphatic moieties (M). Each condensed cycloaliphatic moiety (M) typically comprises from 4 to 8 carbon atoms, preferably from 4 to 6 carbon atoms.
It is further understood that the alicyclic diol (BB’) may exist in different stereochemical and regiochemical arrangements. Thus, for example, the two hydroxyl groups in the alicyclic diol (AA) may have a cis or trans configuration towards each other.
The at least one alicyclic diol (BB’) is preferably of general formula (D”):
HO - E - OH (D”), wherein E comprises the at least one cycloaliphatic moiety (M) and is a group comprising from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms. The at least one alicyclic diol (BB’) is more preferably a diol of formula (D”), in which E is at least one group selected from groups of formulae (El) to (El 1), described earlier in relation to any of formulae (III), (Illa), (Illb).
That is to say, the at least one alicyclic diol (BB’) is selected from the group consisting of diols complying with any of formulae (DI) to (DI 1) :
, and any combination thereof, wherein each Q’, being the same or different in formula (DI 1), is an acyclic moiety.
The acyclic moiety Q’ in formula (Dl l) may be derived from an acyclic diol selected from alkylene oxides and/or poly(alkylene oxide)s, 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-l,3-propanediol; 2,2-dimethylpropane-l,3- diol; 2,2,4-trimethyl-l ,3-pentanediol; 2-ethyl-2-butyl- 1 ,3-propanediol; polyethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.
Q’ in formula (DI 1) may be represented by formula (VI): -[Rk-O-]z-Rk- , in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-l,3- propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,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, yet more preferably an integer from 2 to 50.
Preferably, Q’ in formula (Dll) is represented by any one of following formulae (VI’), (VI”), (VI’”) and (VI””):
-[CH2-CH2-O]Z-CH2-CH2- (VF),
-[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (VI”),
-[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (VI’”),
-[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (VI””), in which z is 0 or an integer from 1 to 500, preferably from 2 to 200, more preferably from 2 to 100, yet more preferably from 2 to 50.
The alicyclic diol (BB’) may be selected from l,4:3,6-dianhydrohexitols and/or l,4:3,6-dianhydrohexitols with acyclic aliphatic end groups.
The alicyclic diol (BB’) is more preferably selected from the group consisting of 1,4:3, 6-dianhydrohexitols such as isosorbide (“ISOSO”) (DI), isomannide (D2), isoidide (D3); 2,3-di-O-alkylene-l-threitols such as 2,3-O-isopropylidene-l- threitol (D4) and/or 2,3-di-O-methylene-l-threitol; tetrahydrofurandimethanol (D5); tetramethylcyclobutanediol (“CBDO”) (D6); cis-l,5-cyclooctanediol (“CODO”) (D7); cyclohexanedimethanol (“CHDM”) (D8); hydrogenated bisphenols such as hydrogenated Bisphenol A (“H-BPA”) (D9); decalindiols such as 2,6-decalindiol (D10); and 1,4:3, 6-dianhydrohexitols with acyclic aliphatic end groups, such as isosorbide with acyclic aliphatic end groups (DI 1).
The alicyclic diol (BB’) is yet more preferably selected from the group consisting of isosorbide (DI), 2,3-O-isopropylidene-l-threitol (D4), tetrahydrofurandimethanol (D5), and isosorbide with acyclic aliphatic end groups (DU). The alicyclic diol (BB’) is yet even more preferably selected from the group consisting of isosorbide (DI) and isosorbide with acyclic aliphatic end groups (DU).
The alicyclic diol (BB’) is most preferably isosorbide (DI).
The alicyclic diol (BB’) which is selected from isosorbide (DI), isomannide (D2), isoidide (D3), 2,3-O-isopropylidene-l-threitol (D4), tetrahydrofurandimethanol (D5), and/or isosorbide with acyclic aliphatic end groups (Dll) may be used in conjunction with the at least one acyclic diol (AA) to provide PAES copolymers having improved hydrophilicity and/or higher Tg. The improvement in hydrophilicity and/or the increase in Tg are in comparison to commercial poly arylethersulfones: PSU, PES and PPSU.
The improved properties thus allows to provide similar or improved performance relative to current commercial PAES grades made from DCDPS and a biphenol selected from BP A, BPS or BP for applications such as membranes, coatings, additive manufacturing and 3-D printing.
A good hydrophilicity is particularly advantageous in filtration applications, e.g., for reducing overpressure required for filtrating aqueous media.
Since isosorbide, isomannide, isoidide, isosorbide with acyclic aliphatic end groups, 2,3-O-isopropylidene-l-threitol, and/or tetrahydrofurandimethanol are sugar-based diols which are derived from biomass, the resulting PAES copolymer thus is at least partially bio-based.
When at least one alicyclic diol (BB’) is employed in the reaction medium, the molar ratio rc of the at least one acyclic diol (AA) to the at least one alicyclic diol (BB’) in the reaction medium is : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40.
Polar aprotic solvent
The at least one dihaloaryl sulfone monomer (CC), the at least one acyclic diol (AA), any optional co-diols (BB) and/or (BB’), and the base are dissolved and/or dispersed in a polar aprotic solvent.
The polar aprotic solvent employed is one generally known in the art and widely used for the manufacture of aromatic sulfone polymers. For example, sulfur containing solvents known and generically described in the art as dialkyl sulfoxides and dialkylsulfones wherein the alkyl groups may contain from 1 to 8 carbon atoms, including cyclic alkylidene analogs thereof, are disclosed in the art for use in the manufacture of PAES. Specifically, among the sulfur-containing solvents that may be suitable for the purposes of this invention are dimethylsulfoxide, dimethylsulfone, diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1, 1-dioxide (commonly called 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-methyl pyrrolidone (NMP) and the like have been disclosed in the art for use in these processes, and may also be found useful in the practice of this invention.
The polar aprotic solvent is preferably selected from the group consisting of l,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene- 1,1 -di oxi de (commonly called tetramethylene sulfone or sulfolane), N-Methyl-2-pyrrolidone (NMP , N- butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N-dimethylacetamide (DMAc), N,N'-dimethylpropyleneurea (DMPU), N,N’ -dimethylformamide (DMF), N-methylcaprolactame, N-ethylcaprolactame, tetrahydrothiophene-1 -monoxide, and any mixture of two or more thereof.
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-imidazolidinone (DMI), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), sulfolane, and any combination thereof.
The polymerization reaction to prepare the PAES is more advantageously carried out in the polar aprotic solvent being sulfolane, DMAc or NMP.
Optional co-solvent
For the purpose of the present invention, the term “additional solvent” or “cosolvent” is understood to denote a solvent different from the reactants and the products of the condensation reaction.
If desired, an additional solvent can be used together with the polar aprotic solvent which forms an azeotrope with water, whereby water that can originate from at least one raw material (for example the inorganic metal phosphate) and/or can be formed as a byproduct during the polymerization (for example when an alkali metal carbonate co-base is used) may be removed by azeotropic distillation continuously throughout the polymerization. In general, the reaction medium may be maintained in substantially anhydrous conditions during the polymerization by removing water continuously from the reaction mass. Water can be removed by distillation or with the azeotrope-forming solvent as an azeotrope, as described above.
The additional solvent that forms an azeotrope with water will generally be selected to be inert with respect to the monomer components and polar aprotic solvent. Suitable azeotrope-forming solvents for use in such polymerization processes include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like.
The azeotrope-forming solvent and polar aprotic solvent are typically employed in a weight ratio of from about 1 : 20 to about 1 : 1, preferably from about 1 : 10 to about 1 : 1, more preferably from about 1 : 5 to about 1 : 3.
The condensation reaction though is preferably carried out without an azeotrope-forming co-solvent.
Reaction medium
A reaction medium containing the following ingredients: the monomers, the base, and the polar aprotic solvent may be formed by :
1/ mixing all of these ingredients together, or
2/ pre-mixing some of the ingredients together to obtain a pre-mixture, and then adding the missing ingredient(s) to the pre-mixture.
The mixing or pre-mixing is preferably carried at a ‘mixing’ temperature not suitable for polycondensation reaction, such as a mixing temperature of at most 150 °C, or at most 130 °C, or at most 110 °C.
The adding step in 2/ may be done while at reaction temperature which is >110 °C, or > 130 °C, or >150 °C, or while at a ‘mixing’ temperature not suitable for polycondensation reaction, such as a mixing temperature of at most 150 °C, or at most 130 °C, or at most 110 °C.
The molar ratio of halogen groups (preferably chlorine) and the hydroxyl groups in the reaction medium can vary, depending on factors such as control of the end group types and contents or control of reaction speed and PAES molecular weight. It is generally preferred that the molar ratio of the hydroxyl groups of the acyclic diol (AA) and optional diols (BB) and/or (BB’) and the halogen groups of the dihaloaryl sulfone monomer (CC) which are reactive towards each other is controlled or adjusted.
The molar ratio between the overall amount of hydroxyl groups from the acyclic diol (AA) and optional other diols (BB) and/or (BB’) and the overall amount of halogen groups from the dihaloaryl sulfone monomer (CC) in the reaction medium is generally from 0.95 to 1.05, preferably from 0.98 to 1.02, more preferably from 0.985 to 1.015, yet more preferably from 0.99 to 1.01. Values of molar ratios of the overall amount of hydroxyl groups to the overall amount of halogen groups of from 0.995 and 1.008, or from 0.997 and 1.007, are particularly advantageous to achieve high Mw of greater than 40 kDa, preferably > 50 kDa.
While the molar ratio of the hydroxyl groups and halogen groups is preferably substantially equimolar with respect to obtaining higher molecular weights (Mw > 40 kDa, preferably > 50 kDa), alternatively the molar ratio of the halogen groups (preferably chlorine) can be higher than that of the hydroxyl groups or vice versa. For instance, to increase the number of phenolic OH end groups, the molar ratio of halogen (chlorine) end groups to phenolic OH end groups is adjusted by using a molar excess of the starting diol (AA) and optional diols (BB), (BB’) compared to the starting dihaloaryl sulfone mononer (CC). For example, the molar ratio of OH groups to halogen (chlorine) groups may be from 1.005 to 1.2, especially from 1.007 to 1.15, most preferably from 1.01 to 1.1.
When it is desired to have less reactive end groups in the PAES, it may be preferred to increase the number of halogen (chlorine) end groups, in particular phenyl chlorine, and the molar ratio of halogen (chlorine) end groups to phenolic OH end groups is adjusted by using a molar excess of the starting dihaloaryl sulfone mononer (CC) compared to the starting diol (AA) and optional diols (BB) and/or (BB’). whereby an excess of chlorine end groups is preferable. In such instance, the molar ratio of halogen (chlorine) groups to OH groups may be from 1.005 to 1.2, especially from 1.007 to 1.15, most preferably from 1.01 to 1.1.
The reaction medium in which the polycondensation reaction is carried out has a total weight % monomer concentration [hereinafter “total wt% monomers”] based on the total weight of the acyclic diol (AA), dihaloaryl sulfone mononer (CC), optional co-diols: aromatic diol (BB) and/or alicyclic diol (BB’) and the polar aprotic solvent, of:
- at least 30 wt%, preferably at least 35 wt%, more preferably at least 38 wt%, and/or
- at most 60 wt%, preferably at most 55 wt%, more preferably at most 50 wt%.
While the reaction medium comprises the base comprising an inorganic metal phosphate and optionally an alkali metal carbonate, the reaction medium is preferably free of any organic phosphorous base. For example, the strong hindered base disclosed in W02020/201522 (Roquette Freres) is not present in the reaction medium. Other than the base (comprising an inorganic metal phosphate and optionally an alkali metal carbonate) included in the reaction medium which participates in the polycondensation reaction, the reaction medium preferably does not comprise a catalyst. For example, the crown-ether catalyst disclosed in EP3653661 (Korea Research Institute of Chemical Technology) is not present in the reaction medium.
Reaction conditions
The reaction medium to prepare the PAES is kept at a temperature suitable for polycondensation to occur. Such a suitable temperature for the reaction medium may be:
- more than 110 °C, preferably at least 115°C, more preferably at least 120°C, yet more preferably at least 125°C, and
- less than 210 °C, preferably at most 205 °C, more preferably at most 200 °C, yet more preferably at most 195 °C.
Preferred temperature of the reaction medium may be from about 120°C to about 205°C, preferably from about 125°C to about 200°C, when NMP and/or sulfolane is used as solvent.
Preferred temperature of the reaction medium may be from about 110°C to about 175°C, preferably from about 115°C to about 175°C, when DMAc is used as solvent.
The process to manufacture the PAES is such that the reaction conversion is at least 90%, preferably at least 95%.
The time for reaction to prepare the PAES may be from about 3 hours to 24 hours, or from about 4 hours to 21 hours, or from 5 hours to 20 hours, or from 5 hours to 18 hours.
Alternatively, the reaction time period to prepare the PAES may vary from about 12 hours to 21 hours, or from 12 hours to 18 hours.
Typically, if the reaction is conducted at atmospheric pressure, the boiling temperature of the solvent selected usually limits the temperature of the reaction. The reaction may be conveniently carried out in an inert atmosphere, e. g., nitrogen, at atmospheric pressure, although higher or lower pressures may also be used.
Recovery of PAES in solid form
The PAES of the invention can be recovered by methods well known and widely employed in the art such as, for example, coagulation, solvent evaporation and the like. After polymerization the resulting PAES is in the form of a solution.
The resulting PAES may be isolated from the PAES solution by devolatilization of the reaction medium after separation of salts with or without first adding additional solvent(s) to fully dissolve any polymer and cause the precipitation of the metal halide (preferably KC1). The additional solvent may be different than the polar aprotic solvent used in the reaction, but preferably it is the same.
Alternatively, the PAES polymer may be isolated from the PAES solution by precipitation and/or coagulation by contacting the reaction medium, optionally after salt removal by filtration, with a non-solvent for the PAES polymer such as a Cl - C5 alcohol, water, or any mixture thereof. The precipitate/coagulate may be rinsed and/or washed with demineralized water or C1-C5 alcohol prior to drying at a temperature ranging from at least 70 °C to about 170 °C. While a vacuum may be applied during drying, drying is generally performed at ambient pressure.
Other than the inorganic metal phosphate used in the base during polymerisation, preferably no other phosphorous-containing material is used during the PAES recovery.
For example, preferably no phosphoric acid is used to acidify or neutralize the PAES solution after separation of salts and during rinsing and/or washing of the PAES solid.
Preferably no phosphorous-containing solvent (such as hexamethyltriamide phosphate) is used to quench or dilute the PAES solution after polymerization, after separation of salts and during rinsing and/or washing of the PAES solid. The resulting PAES solid may be further processed by extruding and pelletizing. The pelletized product may subsequently be subjected to further melt processing such as injection molding and/or sheet extrusion. The conditions for molding, extruding, and thermoforming the resulting PAES are well known in the art.
The PAES according to the present invention features all the benefits of the currently sold polyarylethersulfones while also unexpectedly featuring a reduced content in potential endocrine disruptors, potentially a higher renewable content especially when a bio-sourced diol is used in making such a PAES.
Use of PAES
The present invention also concerns polymer compositions that include at least one PAES of the present invention and at least one other ingredient.
The polymer composition comprise advantageously more than 1 wt%, preferably more than 10 wt%, still more preferably more than 50 wt%, and the most preferably more than 90 wt%, said wt% being relative to the total weight of the composition, of the PAES of the present invention.
Such other ingredient can be on or more PAES polymers, such as a commercially available PPSU, PSU and/or PES polymers. Such other ingredient can also be a polymer other than a PAES polymer such as polyvinylpyrrolidone or a polyethylene glycol.
Such other ingredient can also be a non polymeric ingredient such as a solvent, a filler, a lubricant, a mold release agent, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye and an optical brightener.
Dope solution
An example of such polymer composition is a dope polymer solution suitable for the preparation of membranes. A dope polymer solution is intended to denote a polymer solution that is used to prepare a membrane, i.e. by casting, spinning, etc.
The dope solution for preparing a membrane preferably comprises the PAES of the present invention in a polar organic solvent.
Suitable polar organic solvents for the dope solution may be any of the polar aprotic solvent described herein for the reaction’s solvent. The polar organic solvent in the dope solution may be selected from a group consisting of l,3-dimethyl-2- imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene- 1, 1 -dioxide (commonly called tetramethylene sulfone or sulfolane), N-Methyl-2-pyrrolidone (NMP), N-butylpyrrolidone (NBP), N- ethylpyrrolidone (NEP), N,N-dimethylacetamide (DMAc), N,N'- dimethylpropyleneurea (DMPU), N,N-dimethylformamide (DMF), N- methylcaprolactame, N-ethylcaprolactame, tetrahydrothiophene-1 -monoxide, and mixtures thereof. The polar organic solvent in the dope solution may preferably be DMAc or NMP.
The overall concentration of the polar organic solvent in the dope solution may be at least 20 wt%, preferably at least 30 wt%, based on the total weight of the polymer solution. Typically the concentration of the solvent in the dope solution does not exceed 85 wt%; preferably, it does not exceed 75 wt%; more preferably, it does not exceed 70 wt%, more preferably, it does not exceed 65 wt%, most preferably, it does not exceed 60 wt% based on the total weight of the dope solution.
The overall concentration of the PAES in the dope solution is preferably at least 8 wt%, more preferably at least 12 wt%, based on the total weight of the dope solution. Typically, the concentration of the PAES in the dope solution does not exceed 50 wt%; preferably, it does not exceed 40 wt%; more preferably, it does not exceed 30 wt%, based on the total weight of the dope solution. Concentrations of the PAES ranging from 15 wt% to 25 wt%, preferably from 16 wt% to 22 wt%, with respect to the total weight of dope solution have been found particularly advantageous.
The polymer solution (SP) may further comprise at least one additional polymer distinct form the PAES described herein, for example another sulfone polymer, e.g., poly sulfone (PSU), polyethersulfone (PES), poly(biphenylene ether sulfone) (PPSU), or a polyphenylene sulfide (PPS), a poly(aryl ether ketone) (PAEK), e.g., a poly(ether ether ketone) (PEEK), a poly(ether ketone ketone) (PEKK), a poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer), a poly etherimide (PEI), and/or a polycarbonate (PC). The other polymeric ingredient can also include or be a polyvinylpyrrolidone and/or a polyethyleneglycol (PEG) having a molecular weight of at least 200 g/mol.
In such instances, the concentration of the at least one additional polymer and the PAES in the dope solution does not exceed 50 wt%; preferably, it does not exceed 40 wt%; more preferably, it does not exceed 30 wt%, based on the total weight of the dope solution.
For porous membranes, the dope solution may further comprise a poreforming agent, such as polyvinylpyrrolidone or a polyethylene glycol.
The dope solution may contain additional components, such as nucleating agents, fillers and the like.
The Applicant has surprisingly found that the PAES of the present invention or the polymer composition of the present invention as detailed above, exhibiting excellent properties which are useful in providing high performance polymer membranes.
The dope solution of the present invention comprising the PAES of the present invention is preferably used for fabrication of membranes.
Article
Another aspect of the present invention also concerns an article comprising the PAES of the present invention or the polymer composition as above described.
The PAES of the present invention may be used for the manufacture of membranes or a component thereof, coatings, films, sheets, and three-dimensional molded parts, in particular transparent or coloured parts.
Among applications of use wherein injection molded parts can be used, mention can be made of healthcare applications, in particular medical and dental applications, wherein shaped articles made from the PAES according to the present invention, can advantageously be used for replacing metal, glass and other traditional materials in single-use and reusable instruments and devices.
Particular shaped articles which comprise, or are made from, the PAES of the present invention may be selected from the group consisting of membranes, melt processed films, solution processed films, melt process monofilaments and fibers, solution processed monofilaments, hollow fibers and solid fibers, coatings, printed objects, injection molded objects and compression molded objects.
The article may also be a food contact article such as a plumbing article such as a fitting, a valve, a manifold or a faucet, a food tray, a water bottle or a baby bottle, a cookware.
The article may also be an electronic part.
The article may also be a housing or cover for a mobile electronic device.
The article may also be a medical tray or an animal cage.
The PAES of the invention or the polymer composition of the present invention as detailed above may be also useful in optical applications. The article may also be optical articles such as notably sunglass lenses, eyeglass lenses, optical lenses, optical discs.
The PAES of the invention or the polymer composition of the present invention as detailed above may be also useful used for manufacturing of sheets and films. These are particularly useful as specialized optical films or sheets, and/or suitable for packaging.
The PAES of the present invention and the polymer composition comprised in the article according to the present invention have the same characteristics respectively as the PAES of the present invention and the polymer composition according to the present invention, in all their embodiments, as above detailed. Membrane (as article)
The article is preferably a membrane.
Membranes suitable for the purpose of the invention include, without limitation, isotropic or anisotropic membranes, porous or non-porous membranes, composite membranes, or symmetric or non-symmetric membranes. Such membranes may be in the form of flat structures, corrugated structures, (such as corrugated sheets), tubular structures, or hollow fibers. The membranes according to the present invention can be manufactured using any of the conventionally known membrane preparation methods, for example, by a solution casting or solution spinning method.
Non limitative examples of membrane applications include water purification, wastewater treatment, pharmaceutical production, blood purification, in particular hemodialysis and a variety of industrial process separations, such as food and beverage processing, electropaint recovery and gas separation.
Particular preferred shaped articles which comprise, or are made from, the PAES of the present invention may be membranes being selected from membranes for bioprocessing and medical filtrations (such as hemodialysis membranes), membranes for food and beverage processing, membranes for water purification, membranes for waste water treatment, and/or membranes for industrial process separations involving aqueous media.
The membranes according to the present invention can be manufactured using any of the conventionally known membrane preparation methods, for example, by a solution casting or solution spinning method.
Preferably, the membranes according to the present invention are prepared by a phase inversion method occurring in the liquid phase, said method comprising the following steps:
(i) preparing a PAES dope solution comprising the PAES described herein and a polar solvent,
(ii) processing said dope solution into a film;
(iii) contacting said film with a non-solvent bath.
The membrane of the present invention may comprise the PAES described herein in an amount of 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%, based on the total weight of the membrane.
The membrane of the present invention may comprise the PAES described herein in an amount of more than 50 wt%, for example more than 55 wt%, more than 60 wt%, more than 65 wt%, more than 70 wt%, more than 75 wt%, more than 80 wt. %, more than 85 wt%, more than 90 wt%, more than 95 wt% or more than 99 wt%, said wt% being based on the total weight of the membrane.
According to an embodiment, the membrane of the present invention may comprise the PAES described herein in an amount ranging from 1 wt% to 99 wt%, for example from 3 wt% to 96 wt%, from 6 wt% to 92 wt% or from 12 wt% to 88 wt%, said wt% being based on the total weight of the membrane.
The membrane of the present invention may further comprise at least one polymer distinct form the PAES described herein, for example another sulfone polymer, e.g., polysulfone (PSU), polyethersulfone (PES), poly(biphenyl ether sulfone) (PPSU), or a polyphenylene sulfide (PPS), a poly(aryl ether ketone) (PAEK), e.g., a poly(ether ether ketone) (PEEK), a poly(ether ketone ketone) (PEKK), a poly(ether ketone) (PEK) or a copolymer of PEEK and poly(diphenyl ether ketone) (PEEK-PEDEK copolymer), poly etherimide (PEI), and/or polycarbonate (PC). The other polymeric ingredient can also be polyvinylpyrrolidone and/or polyethylene glycol.
The membrane may also further comprise at least one non-polymeric ingredient such as a solvent, a filler, a lubricant, a mold release, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye and/or an optical brightener.
A suitable example of a method for forming a membrane from a polyaryl ether sulfone polymer is described in US2019/054429A1 (Solvay Specialty Polymers USA), incorporated herein by reference.
Use of PAES in coatings
Another aspect of the present invention is a method for coating substrates comprising using the PAES of the present invention or the polymer composition of the present invention as detailed above.
The choice of substrates is not particularly limited. Such coatings may be useful for protecting substrates such as notably metals such as steel, in particular stainless steel, aluminum, copper, and other metals in applications such as food and beverage can coatings, marine-hull protection, aerospace, automotive, wire coating, electronics, optical and plastics.
The disclosure will now be illustrated with working examples, which are intended to illustrate the working of disclosure and not intended to take restrictively to imply any limitations on the scope of the present disclosure.
EXAMPLES
The invention will be now described in more details with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.
RAW MATERIALS
4,4 ’-di chlorodiphenylsulfone (DCDPS), 99.7%, was procured from Solvay Specialty Polymers USA, a member of the SYENSQO group.
2,2-dimethyl-l,3-propanediol [DMP], and polyethyleneglycol [PEG300] were procured from Sigma- Aldrich and used as received.
4,4 ’-biphenol, polymer grade, was procured from SI, USA and used as received.
Tribasic potassium phosphate (K3PO4), anhydrous, free-flowing, Redi-Dri™, reagent grade, >98% was procured from Sigma-Aldrich, and was dried at 120°C under vacuum for 12 h before use. The particle sizes measured on Microtrac S3500, in dry mode (20 psi, educator position set at zero) were Dso=62 pm and D9o=165 pm.
Potassium carbonate (K2CO3) with a D90 < 45 pm was procured from Armand products and was dried at 120°C under vacuum for 12 hours before use.
Sulfolane, N,N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) were procured from Sigma- Aldrich and used as received.
ANALYTICAL METHODS
Determination of Molecular Weights (Mn, Mw, M and ratios (Mw/Mn, Mz/Mw) by Gel Permeation Chromatography (GPC)
The molecular weights (Mn, Mw, Mz) were measured by GPC using as Waters Alliance E2695 with UV-Vis detector E2489 (detection at 270 nm) using two full size Agilent 5um MiniMixed-D columns (250 x 4.6mm) and one Guard column (50 x 4.6mm)(both have 5 pm particle sizes) using 0. IM LiBr solution in DMAc as mobile phase.
A sample (30 mg) of PAES polymer was weighed into a 20 ml vial and 5 ml of the mobile phase were added to dissolve the sample. The resulting solution was filtered using a 0.2 um PTFE syringe filter into a 4 ml vial. The sample volume injected was 10 pL.
A flow rate of 0.3 ml/min was selected. Calibration was performed using 10 narrow calibration standards of Polystyrene obtained from Agilent Technologies (Peak molecular weight range: 371000 to 580).
The GPC Distribution Values for the PAES Sample: Mw, Mn, Mz, PDI (Mw/Mn), and ratio Mz/Mw were calculated by Agilent OpenLab CDS using the calibration curve for the polystyrene standards that was generated.
Measurement of inherent viscosity IV
Inherent viscosity IV of the PAES samples was measured in a solvent mixture dichloromethane/trifluoroacetic acid (9/1 v/v), at a concentration of 0.2g PAES/lOOmL at 20 °C using a Cannon-Fenske viscometer tube (N°50) according to the procedure as described by Kricheldorf and Chatti in High Performance Polymers, 2009, vol. 21, pages 105-118.
Determination of the glass transition temperature (Tg) of the PAES
The glass transition temperature (Tg) of PAES samples was determined using the mid-point method on the 2nd heat scan in Differential Scanning Calorimeter (DSC) according to ASTM D3418-03, E1356-03, E793-06, E794-06. Details of the procedure as used in this invention were as follows: a TA Instruments DSC Q20 was used with nitrogen as carrier gas (99.998% purity, 50 mL/min). Temperature and heat flow calibrations were done using indium. Sample size was 5 to 7 mg. The weight was recorded ±0.01 mg. The heat cycles were:
- 1st heat cycle: 30.00°C to 350.00°C at 20.00°C/min, isothermal at 350.00°C for 1 min;
- 1st cool cycle: 350.00°C to 30.00°C at 20.00°C/min, isothermal for 1 min;
- 2nd heat cycle: 30.00°C to 350.00°C at 20.00°C/min, isothermal at 350.00°C for 1 min.
Determination of Chlorine Content in PAES by Chlorine analyzer
Using forceps, a clean, dry combustion boat was placed onto a microbalance, and the balance was zeroed. One to five mg of PAES sample was weighed into a combustion boat and the weight was recorded to 0.001 mg. The combustion boat and sample were placed in the introduction port of a ThermoGLAS 1200 Total Organic Halogen Analyzer, and the port was capped. The sample weight was entered into the sample weight field on the instrument computer. The sample analysis cycle was then started. The sample was burned in a mixture of argon and oxygen and the combustion products were passed through concentrated sulfuric acid scrubber to remove moisture and byproduct. Hydrogen chloride and oxychlorides from the combustion process were absorbed into the cell acetic acid solution from the gas stream. Chloride entered the cell was titrated with silver ions generated coulometrically. Percent chlorine in the sample was calculated from the integrated current and the sample weight.
Determination of phosphorus content in PAES by ICP-OES
A clean, dry platinum crucible is placed onto an analytical balance, and the balance was zeroed. One half to 3 grams of PAES sample was weighed into a boat and its weight was recorded to 0.0001 g. The crucible with PAES sample was placed in a muffle furnace (Thermo Scientific Thermolyne F6000 Programmable Furnace). The furnace was gradually heated to 525°C and held at that temperature for 10 hours to dry ash the sample. Following ashing, the furnace was cooled down to room temperature, and the crucible was taken out of the furnace and placed in a fume hood. The ash was dissolved in diluted hydrochloric acid. The solution was transferred to a 25 mL volumetric flask, using a polyethylene pipette. The crucible was rinsed twice with approximately 5 mL of ultrapure water (R<18 MQcm) and the washes were added to a volumetric flask to effect a quantitative transfer. Ultrapure water was added to total 25 mL in the flask. A stopper was put on the top of the flask and the contents are shaken well to mix.
Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) analysis was performed using an inductively-coupled plasma emission spectrometer Perkin-Elmer Optima 8300 dual view. The spectrometer was calibrated using a set of NIST traceable multi-element mixed standards with analyte concentrations between 0.0 and 10.0 mg/L. A linear calibration curve was obtained in a range of concentrations with a correlation coefficient better than 0.9999 for each of 48 analytes. The standards were run before and after every ten samples to ensure instrument stability. The ICP-OES results were reported as an average of three replicates. The concentration of elemental impurities in the sample was calculated with the following equation: A = (B * C) / (D), where:
A = concentration of element in the sample in mg/kg (=wt.ppm);
B = element in the solution analyzed by ICP-OES in mg/L;
C = volume of the solution analyzed by ICP-OES in mL; and D = sample weight in grams used in the procedure.
Determination of content of residual polar aprotic solvent in the PAES
A 0.25 g sample of PAES is dissolved into 5 mL DMF and the solution is filtered through a 0.22 um syringe filter and analyzed by Gas Chromatography (GC) using a Restek RTX-200ms (30m X 250pm X 0.25pm) column, a constant Flow of hydrogen as carrier gas of 1.6 mL/min. The GC conditions are :
• Injector: injection vol: 1.5 pL
• Inlet:
Mode: Split
Temp: 270 °C
Pressure: 8.5744 psi
Split Ratio: 10:1
Split Flow 16 mL/min
• Detector: FID
Makeup: N2 Temp: 310 °C H2 Flow: 40 mL/min Air Flow: 400 mL/min Makeup Flow: 15 mL/min Constant Makeup and Fuel Flow
• Oven:
Initial Temp: 30 °C
• Ramp: 30 °C, Hold 4 min
Ramp @ 40 °C/min to 105C, Hold 1 min Ramp @ 40 °C/min to 175C, Hold 0 min
Ramp @ 30 °C/min to 300C, Hold 0 min
The residual level of solvent is determined using external standards of DMAc, sulfolane, NMP in DMF.
Determination of content of residual BPS in the PAES
A 0.5-g sample of PAES is dissolved in 10 mL DMF. After dissolution, 10 mL of acetonitrile are added under agitation to precipitate the polymer. The solution is filtered through a 0.22-pm syringe filter and analyzed (20pL injection volume) by Liquid Chromatography using a Supelco Discovery® C18 HPLC column (4.6 mm x 25 mm, 5 pm particle size).
The mobile phase has the following gradient composition:
The detector is a UV detector set at 254 nm. The concentration of BPS is determined using external standards of BPS.
Determination of content of residual BPA in the PAES
A 0.25-g sample of PAES is dissolved into 5 mL trichloromethane. The solution is filtered through a 0.22 -micron syringe filter and analyzed by Gas Chromatography using a Restek™ RTX™-5MS capillary column (30m length, 0.25mm ID, 0.25 pm film thickness), a constant pressure of 14.5 psi of helium. The GC conditions are :
• Injector:
Injection vol: 2 pL
• Inlet:
Mode: Split
Temp: 290 °C split Ratio: 3:1
• Detector: FID
Makeup: helium
Temp: 300 °C
H2 Flow: 30 mL/min
Air Flow: 400 mL/min
Makeup Flow: 35 mL/min Constant Makeup and Fuel Flow
• Oven:
Initial Temp: 35 °C
• Ramp: 35 °C, Hold 1 min
Ramp @ 20 °C/min to 325 °C, Hold 10 min
The concentration of BP A is determined using external standards of BP A.
Examples
General procedure for the preparation of PAES homopolymers and copolymers made from acyclic diol (AA), optionally co-diol (BB) or (BB’), and DCDPS
For making a PAES copolymer, to a 1-L four-neck round bottom flask (reactor vessel) fitted with a mechanical stirrer, Dean-Stark or Barrett trap, condenser, and nitrogen inlet, were loaded 2,2-dimethylpropane-l,3-diol (DMP) or PEG300 as acyclic diol (AA), 4,4’-biphenol (BP) as aromatic diol (BB), 4,4 ’-di chlorodiphenyl sulfone (DCDPS) as dihaloaryl sulfone monomer (CC), and potassium carbonate (K2CO3) and/or tribasic potassium phosphate (K3PO4) as the base, followed by the polar aprotic solvent (DMAc) to form a reaction medium.
The total wt% monomers loaded in the reaction medium was from 44 wt% to 51 wt%, such wt% being based on the total weight of monomers + solvent.
The amounts of the monomers were selected so as to achieve a total wt% polymer of from 40 to 45 wt% in the reaction medium at the end of polymerization, said wt% being based on the total weight of PAES + solvent.
The amount of potassium phosphate, when used as the sole base in the reaction medium, was expressed by the molar ratio of K3PO4 to diol(s) of 2.5 or 3.
The amount of potassium carbonate, when used as the sole base in the reaction medium, was expressed by the molar ratio of K2CO3 to diol(s) of 3.
The molar ratio of the overall amount of the overall amount of halogen groups from DCDPS [as monomer (CC)] to the hydroxyl groups from the acyclic diol (AA) and any optional co-diols (BB) is from 0.995 to 1.000.
The reactor vessel was purged with nitrogen for 15 minutes before initiating the reaction. The reaction medium comprising the monomers was stirred with the overhead mechanical agitator and heated up to initiate reaction up to a suitable reaction temperature (110 °C to 200 °C) using an heating mantle controlled at the target internal reaction temperature. The reaction medium temperature was increased from room temperature (e.g., 20-21 °C) to the appropriate reaction temperature over about 30-60 minutes. In the case of reactions with K2CO3, water, a byproduct of the polymerization reaction, was continuously stripped out of the reactor vessel and collected in the dean-stark trap, and the reaction medium is stirred with an overhead mechanical agitator and heated up to the suitable reaction temperature). Upon reaching the target reaction temperature, the reaction medium was held at that temperature for a period of reaction time suitable until a desired Mw was achieved, generally measured by viscosity. The reaction time period may vary from 5 to 24 hours, and was generally from about 14.5 hours to 21.5 hours.
Once the desired molecular weight was achieved, the polymerization was terminated by bubbling 50 g of gaseous methyl chloride through the reaction medium over 30 minutes. Because the reaction medium became viscous and difficult to stir at the end of the reaction, the reaction medium was diluted with DMAc to obtain 20 wt% PAES polymer and was cooled to a temperature which was less than the reaction temperature, preferably less than 130 °C, more preferably less than 120 °C, yet more preferably less than 110 °C.
The cooled medium was filtered through a 2.7-pm glass fiber filter pad under pressure to remove salts. The polymer was then coagulated from the filtered solution by pouring it into a Waring blender containing 2.5-L of non-solvent (methanol, water or a blend of water/methanol) using a weight ratio of 1 :5 PAES solution to non-solvent to precipitate the PAES and obtain a white solid. The resulting solid was then isolated by filtration, and washed five times with 2.5 L of methanol at room temperature. The resulting solid was dried in a vacuum oven overnight at 120 °C.
Each PAES sample was analysed to measure its inherent viscosity IV, its Mw, Mn, Mz by GPC, its Tg by DSC (2nd heat), its phosphorous content by ICP-OES, and its chlorine content by Chlorine analyser. The ratios: Mw/Mn (PDI) and Mz/Mw for each PAES sample were also calculated.
The polymerisaion conditions and polymer characterisation are summarized in Table 1.
The data in Table 1 shows that under similar polymerisation conditions, high Mw (84.5 kDa, 52.8 kDa) for the PAES copolymers E2, E3 made from DMP and biphenol (with DMP/BP molar ratio of 60/40 and 80/20) with DCDPS were achieved using K3PO4 alone (sole base). In contrast, the PAES copolymer CE1 made from DMP and biphenol (with DMP/BP molar ratio of 60/40) with DCDPS using K2CO3 alone (sole base) had a low Mw of 11.3 kDa. Table 1
* wt ppm = ppm based on weight Additionally, the data in Table 1 shows that under similar polymerisation conditions, high Mw (79.6 kDa, 82.3 kDa) for the PAES copolymers E5, E6 made from polycondensation of PEG300 and biphenol (with PEG300/BP molar ratio of 60/40 and 80/20) with DCDPS were achieved using K3PO4 alone (sole base). In contrast, the PAES copolymer CE4 made from polycondensation of PEG300 and biphenol (with PEG300/BP molar ratio of 60/40) with DCDPS using K2CO3 alone (sole base) had a low Mw of 18.9 kDa.
While preferred embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of systems and methods are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention.
What is claimed is:

Claims

C L A I M S
1. A polyarylethersulfone (PAES) being made by condensation of :
- at least one acyclic diol (AA) of formula (D): HO-Q-OH, said Q being an acyclic moiety, and
- at least one dihaloaryl sulfone monomer (CC) comprising at least one -S(=O)2- group, said PAES having a phosphorous content of at least 3 ppm P, or at least 4 ppm P, or at least 5 ppm P, or at least 6 ppm, said ppm being based on the total weight of the PAES.
2. The PAES of claim 1, wherein the PAES comprises a recurring unit (Ra) of following formula (I):
-[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m-O-Q-O- (I), wherein the group -O-Q-O- is derived from the at least one acyclic diol (AA); wherein the group -[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m- is derived from the at least one dihaloaryl sulfone monomer (CC); wherein n and m are independently 0, 1, 2, 3 or 4; wherein Ar3, Ar4 are equal or different from each other and are aromatic moieties of the formula: wherein Ar5 is selected from the group consisting of:
wherein each of R in any of Ar3, Ar4, Ar5 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.
3. The PAES of claim 1 or 2, wherein the PAES comprises a recurring unit
(Ra) represented by following formula (la):
(la), preferably represented by following formula (lb): wherein the group -O-Q-O- is derived from the at least one acyclic diol (AA) of formula HO-Q-OH; and wherein in formula (la):
- each Ri 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
- i for each Ri is 0, 1, 2, 3 or 4.
4. The PAES of any one of claims 1 to 3, wherein the at least one acyclic diol (AA) is selected from alkylene oxides and/or poly(alkylene oxide)s, 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-l,3-propanediol; 2,2-dimethylpropane- 1,3-diol; 2,2,4-trimethyl-l,3-pentanediol; 2-ethyl-2-butyl-l,3-propanediol; polyethylene glycol); polypropylene glycol); poly(tetramethylene oxide); and any combination of two or more thereof.
5. The PAES of any one of claims 1 to 4, wherein Q is represented by formula (V):
-[Rk-O-]z-Rk- (V), in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, more preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [042-04(043 )], tetramethylene [CH2- CH2-CH2-CH2], 2,2-dimethylpropylene [O42-C(O43)2-O42], 2-ethyl-2 -butyl- 1,3- propylene [CH2-C(C2H5)(C4H9)-CH2], 2,2,4-trimethyl-l,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, yet more preferably an integer from 2 to 50; preferably, represented by any one of formulae (V’), (V”), (V’”) and (V””): -[CH2-CH2-O]Z-CH2-CH2- (V’), -[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (V”),
-[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (V’”),
-[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (V””), in which 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, yet more preferably an integer from 2 to 50.
6. The PAES of any one of claims 1 to 5, which is a copolymer made by condensation of :
- the at least one acyclic diol (AA),
- the at least one dihaloaryl sulfone monomer (CC), and at least one co-diol selected from aromatic diols (BB) and/or alicyclic diols (BB’); wherein the molar ratio r of the at least one acyclic diol (AA) to the at least one codiol is : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40.
7. The PAES of claim 6, wherein the at least one aromatic diol (BB) is selected from the group consisting of bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4’ -biphenol, diallyl biphenol, bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, hydroquinone, resorcinol, an aromatic triol such as l,l,l-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 ’-biphenol, diallyl biphenol, bisphenol F, tetramethyl bisphenol F, and any combination of two or more thereof; yet more preferably selected from the group consisting of 4,4 ’-bi phenol, diallyl biphenol, tetramethyl bisphenol F, and any combination of two or more thereof, most preferably being 4,4’ -biphenol; and/or the at least one alicyclic diol (BB’) is selected from the group consisting of l,4:3,6-dianhydrohexitols such as isosorbide, isomannide, isoidide; 1,4:3, 6- dianhydrohexitols with acyclic aliphatic end groups such as isosorbide with acyclic aliphatic end groups; 2,3-di-O-alkylene-l-threitols such as 2,3-O-isopropylidene-l- threitol and/or 2,3-di-O-methylene-l-threitol; tetrahydrofurandimethanol; tetramethylcyclobutanediol; cis-l,5-cyclooctanediol; cyclohexanedimethanol; hydrogenated bisphenols such as hydrogenated Bisphenol A (“H-BPA”); decalindiols such as 2,6-decalindiol; and any combination of two or more thereof; preferably selected from the group consisting of isosorbide and isosorbide with acyclic aliphatic end groups.
8. The PAES of claim 6, wherein the at least one alicyclic diol (BB’) is represented by formula (D”): HO - E - OH, wherein E comprises the at least one cyclic aliphatic moiety (M) and is a group comprising from 4 to 30 carbon atoms, preferably from 4 to 15 carbon atoms;
(Ell) , and any combination thereof, more preferably, E being selected from the group consisting of those of the formulae (El), (E2), (E3), (E4), (E5) and (El l), yet more preferably, E being selected from the group consisting of those of the formula (El) and/or formula (El 1); wherein each sign * in the formulae (El) to (El 1) denotes where E is bonded to an oxygen atom of the -O-E-O- formula; and wherein each Q’, being the same or different in the formula (Ell), is an acyclic moiety.
9. The PAES of any one of claims 1 to 8, wherein the PAES has a weight average molecular weight (Mw) of > 40 000 g/mol, and preferably at most 120 000 g/mol.
10. The PAES of any one of claims 1 to 9, wherein the PAES has at least one of the following characteristics: an inherent viscosity (IV) of at least 0.25 dL/g, and preferably at most 1.5 dL/g;
- a number average molecular weight (Mn) of at least 15 000 g/mol, and preferably at most 80 000 g/mol; a molecular weight distribution characterized by a Mz/Mw of at least 1.5 and at most 1.8; a chlorine content of : at least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm, yet more preferably at least 300 ppm, and/or at most 3000 ppm, preferably at most 2900 ppm, more preferably at most 2800 ppm; an amount of less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm, of Bisphenol A; an amount of less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm, of Bisphenol S; an amount of no more than 2 wt% of an oligomer fraction having a number molecular weight of less than 3000 g/mol; and/or a residual polar aprotic solvent content of less than 3000 ppm, preferably less than 2500 ppm, more preferably less than 2000 ppm; said ppm and wt% being based on total weight of the PAES, wherein Mn is the number molecular weight of the PAES, Mz is the size average molecular weight of the PAES, and Mw is the weight average molecular weight of the PAES, and said Mn, Mw and Mz of the PAES being determined by gelpermeation chromatography (GPC) calibrated with polystyrene standards and performed using DMAc as mobile phase.
11. A process for manufacturing a poly arylethersulfone polymer [hereinafter “PAES”] comprising: reacting in a reaction medium comprising a polar aprotic solvent and a base containing an inorganic metal phosphate,
- at least one acyclic diol (AA), and
- at least one dihaloaryl sulfone monomer (CC) comprising at least one -S(=O)2- group, wherein the inorganic metal phosphate comprises a metal being selected from Groups 1, 2 or 3 of the IUPAC periodic table.
12. The process according to claim 11, wherein the inorganic metal phosphate is an alkali metal phosphate characterized by a pKa of its conjugated acid greater than 10.5 and less than 15; preferably is atribasic alkali metal phosphate in which the alkali metal is K, Na, Cs and/or Li; more preferably is tripotassium phosphate (K3PO4) and/or trisodium phosphate (NasPCL); yet more preferably is K3PO4.
13. The process according to claim 11 or 12, wherein the inorganic metal phosphate is tripotassium phosphate (K3PO4) which has a mean average particle size (D50) of from 10 microns to 400 microns, said D50 being measured by light scattering in dry mode.
14. The process according to any one of claims 11 to 13, wherein the base 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, more preferably being potassium carbonate.
15. The process according to any one of claims 11 to 14, wherein the at least one acyclic diol (AA) is of formula (D): HO - Q - OH, and wherein Q is represented by formula (V):
-[Rk-O-]z-Rk- (V), in which Rk is selected from alkylenes, preferably alkylenes having from 1 to 10 carbon atoms, preferably selected from the group consisting of methylene [CH2], ethylene [CH2-CH2], isopropylene [CH2-CH(CH3)], tetramethylene [CH2-CH2- CH2-CH2], 2,2-dimethylpropylene [CH2-C(CH3)2-CH2], 2-ethyl-2-butyl-l,3- propylene [CH2-C(C2Hs)(C4H9)-CH2], 2,2,4-trimethyl-l,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, yet more preferably an integer from 2 to 50; preferably, represented by any one of following formula (V’), (V”), (V’”) or (V””):
-[CH2-CH2-O]Z-CH2-CH2- (V’),
-[CH2-CH(CH3)-O]Z-CH2-CH(CH3)- (V”),
-[CH2-CH2-CH2-CH2-O]Z-CH2-CH2-CH2-CH2- (V’”),
-[CH2-C(CH3)2-CH2-O]Z-CH2-C(CH3)2-CH2- (V””), in which 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, yet more preferably an integer from 2 to 50.
16. The process according to any one of claims 11 to 15, wherein the at least one dihaloaryl sulfone monomer (CC) is of formula (Cl):
(Cl), wherein : each of Ri, equal to or different from each other, is 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, alkali metal phosphonate, alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- each i, equal to or different from each other, is independently zero or an integer from 1 to 4, preferably is independently zero or 1, more preferably is zero; and
- X and X’, equal to or different from each other, are independently a halogen atom, preferably Cl or F, more preferably Cl.
17. The process according to any one of claims 11 to 16, wherein the at least one dihaloaryl sulfone monomer (CC) is selected from the group consisting of dichlorodiphenylsulfone (DCDPS), difluorodiphenylsulfone (DFDPS), monosulfonated dichlorodiphenylsulfone (msDCDPS), disulfonated dichlorodiphenylsulfone (dsDCDPS), and any combination of two or more thereof; preferably selected from the group consisting of DCDPS, msDCDPS, dsDCDPS and any combination thereof.
18. The process according to any one of claims 11 to 17, wherein the reaction medium further comprises at least one co-diol selected from aromatic diols (BB) and/or alicyclic diols (BB’), and wherein the molar ratio r of the at least one alicyclic diol (AA) to the at least one co-diol is : at most 95:5, preferably at most 90: 10, more preferably at most 85: 15, yet more preferably at most 80:20, and/or at least 10:90, preferably at least 20:80, preferably at least 30:70, more preferably at least 40:60, yet more preferably at least 50:50, even more preferably at least 60:40.
19. The process according to claim 18, wherein the co-diol is :
- an aromatic diol (BB) selected from the group consisting of bisphenol A, diallyl bisphenol A, bisphenol S, diallyl bisphenol S, 4,4 ’-biphenol, diallyl biphenol, bisphenol F, tetramethyl bisphenol F, diallyl bisphenol F, hydroquinone, resorcinol, an aromatic triol such as l,l,l-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 ’-biphenol, diallyl biphenol, bisphenol F, tetramethyl bisphenol F, and any combination of two or more thereof; more preferably selected from the group consisting of 4,4’ -biphenol, diallyl biphenol, tetramethyl bisphenol F, and any combination of two or more thereof; most preferably being 4,4’-biphenol; and/or
- an alicyclic diol (BB’) selected from the group consisting of 1,4:3, 6- dianhydrohexitols such as isosorbide, isomannide or isoidide; 2,3-di-O-alkylene-l- threitols such as 2,3-O-isopropylidene-l-threitol and/or 2,3-di-O-methylene-l- threitol; tetrahydrofurandimethanol; tetramethylcyclobutanediol; cis-1,5- cyclooctanediol; cyclohexanedimethanol; hydrogenated bisphenols such as hydrogenated Bisphenol A (“H-BPA”); decalindiols such as 2,6-decalindiol; and l,4:3,6-dianhydrohexitols with acyclic aliphatic end groups, such as isosorbide with acyclic aliphatic end groups; preferably selected from the group consisting of isosorbide; 2,3-O-isopropylidene-l- threitol; tetrahydrofurandimethanol; tetramethylcyclobutanediol; cis-1,5- cyclooctanediol; cyclohexanedimethanol; hydrogenated Bisphenol A; 2,6- decalindiol; and isosorbide with acyclic aliphatic end groups; more preferably selected from the group consisting of isosorbide; 2,3-0- isopropylidene-l-threitol; tetramethylcyclobutanediol; cis-l,5-cyclooctanediol; cyclohexanedimethanol; and isosorbide with acyclic aliphatic end groups; yet more preferably selected from the group consisting of isosorbide and isosorbide with acyclic aliphatic end groups.
20. The process according to any one of claims 11 to 19, wherein the molar amount in the reaction medium of the inorganic metal phosphate, relative to the molar amount in the reaction medium of the at least one acyclic diol (AA) and any optional co-diols, is:
- 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
- at most 3.0, or at most 2.8, or at most 2.75, or at most 2.5, or at most 2.4.
21. The process according to any one of claims 11 to 20, wherein the reaction is carried out with a total weight % monomer concentration [hereinafter “total wt% monomers”] based on the total weight of the acyclic diol (AA), any optional codiols, dihalo monomer (CC), and the polar aprotic solvent, of:
- at least 30 wt%, preferably at least 35 wt%, more preferably at least 38 wt%, and/or
- at most 60 wt%, preferably at most 55 wt%, more preferably at most 50 wt%.
22. The process according to any one of claims 11 to 21, wherein reacting is carried out at a reaction temperature of :
- more than 110 °C, preferably at least 115°C, preferably at least 120°C, and
- less than 210 °C, preferably at most 200 °C, more preferably at most 190 °C, yet more preferably at most 180 °C, even more preferably at most 175 °C.
23. The process according to any one of claims 11 to 22, wherein the molar ratio of the overall amount of hydroxyl groups from the at least one acyclic diol (AA) and any optional co-diols to the overall amount of halogen groups from the dihaloaryl sulfone monomer (CC) in the reaction medium is from 0.95 to 1.05, preferably from 0.98 to 1.02, more preferably from 0.985 to 1.015, yet more preferably from 0.99 to 1.01, even yet more preferably from 0.995 to 1.007.
24. The process according to any one of claims 11 to 23, wherein the polar aprotic solvent is selected from the group consisting of l,3-dimethyl-2- imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethyl sulfone (DMSO2), diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene- 1,1 -di oxi de (sulfolane), N-Methyl-2-pyrrolidone (NMP), N- butylpyrrolidone (NBP), N-ethylpyrrolidone (NEP), N,N-dimethylacetamide (DMAc), N,N'-dimethylpropyleneurea (DMPU), N,N-dimethylformamide (DMF), N-methylcaprolactame, N-ethylcaprolactame, tetrahydrothiophene- 1 -monoxide, and any mixture of two or more of these solvents; preferably selected from the group consisting of DMI, NMP, NBP, NEP, DMAc, DMF, 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.
25. A PAES obtained by the process of any one of claims 11 to 24, comprising a phosphorous content of at least 6 ppm, and preferably at most 150 ppm, preferably said PAES further having at least one of the following characteristics:
- a weight average molecular weight (Mw) of > 40 000 g/mol, and preferably at most 120 000 g/mol;
- a number average molecular weight (Mn) in of at least 15 000 g/mol, and preferably at most 80 000 g/mol;
- a molecular weight distribution characterized by a ratio Mz/Mw of at least 1.5 and at most 1.8;
- an inherent viscosity (IV) of at least 0.25 dL/g, and preferably at most 1.5 dL/g;
- a chlorine content of : at least 50 ppm, preferably at least 100 ppm, more preferably at least 200 ppm, yet more preferably at least 300 ppm, and/or at most 3000 ppm, preferably at most 2900 ppm, more preferably at most 2800 ppm;
- an amount of less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm, of Bisphenol A;
- an amount of less than 10 ppm, preferably less than 5 ppm, more preferably less than 1 ppm, of Bisphenol S;
- an amount of no more than 10 wt%, preferably no more than 8 wt%, more preferably no more than 5 wt%, most preferably no more than 2 wt%, of an oligomer fraction having a number molecular weight (Mn) of less than 3000 g/mol; and/or
- 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 and wt% being based on total weight of the PAES, wherein Mn is the number molecular weight of the PAES, Mz is the size average molecular weight of the PAES, and Mw is the weight average molecular weight of the PAES, and said Mn, Mw and Mz of the PAES being determined by gelpermeation chromatography (GPC) calibrated with polystyrene standards and performed using DMAc as mobile phase.
26. Use of the PAES of any one of claims 1 to 10 or 25 for the manufacture of membranes, coatings, films and sheets, and/or three-dimensional molded parts.
27. A dope polymer solution for preparing a membrane, which comprises the PAES of any one of claims 1 to 10 or 25 in a polar organic solvent.
28. Shaped articles manufactured from the PAES of any one of claims 1 to 10 or 25, being selected from the group consisting of membranes, melt processed films, solution processed films, melt process monofilaments and fibers, solution processed monofilaments, hollow fibers and solid fibers, coatings, printed objects, and injection and compression molded objects, preferably membranes being selected from membranes for bioprocessing and medical flitrations (such as hemodialysis membranes), membranes for food and beverage processing, membranes for water purification, membranes for waste water treatment and membranes for industrial process separations involving aqueous media.
PCT/EP2025/059167 2024-04-05 2025-04-03 Polyarylethersulfone containing phosphorous and made from dihaloarylsulfone and acyclic diol Pending WO2025210173A1 (en)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0739925A2 (en) 1995-04-28 1996-10-30 Bayer Ag Polysulfone-polyether block copolycondensates
EP0781795A2 (en) * 1995-12-26 1997-07-02 Teijin Limited Application of sulfone, ketone and ester containing polyalkyl ethers to medical materials
JP2000239385A (en) * 1999-02-23 2000-09-05 Bayer Ag Production of polyether block copolysulfone
WO2006012453A1 (en) * 2004-07-22 2006-02-02 Solvay Advanced Polymers, L.L.C. Polysulfone - polyether blockcopolymers, process to synthesize it, membranes made therefrom
US20140113093A1 (en) 2011-05-25 2014-04-24 Solvay Speciality Polymers Usa, Llc Polymers with reduced estrogenic activity
WO2014072473A2 (en) 2012-11-09 2014-05-15 Solvay Specialty Polymers Usa, Llc Polyarylene ether sulfones
WO2014177640A1 (en) * 2013-05-02 2014-11-06 Basf Se Polyaryl ether sulphone copolymers
US20150011446A1 (en) 2012-02-17 2015-01-08 Solvay Specialty Polymers Italy S.P.A. (PER)FLUOROPOLYETHERS WITH bi- OR ter-PHENYL END GROUPS
US20150129487A1 (en) 2012-05-15 2015-05-14 Solvay Specialty Polymers Usa, Llc. High performance polysulfones made from cycloaliphatic diols
WO2017157933A1 (en) * 2016-03-15 2017-09-21 Solvay Specialty Polymers Italy S.P.A. Composition and method for manufacturing sulfone polymer membrane
WO2019013529A1 (en) * 2017-07-12 2019-01-17 한국화학연구원 Method for preparing polyarylene ether copolymer comprising isohexide units and polyarylene ether copolymer prepared thereby
WO2020201522A1 (en) 2019-04-05 2020-10-08 Safran Aircraft Engines Method and system for monitoring a system for actuating a component of a turbomachine
CN113388111A (en) * 2021-07-05 2021-09-14 天津师范大学 Preparation method of low-chroma polyaromatic ether

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08302018A (en) * 1995-04-28 1996-11-19 Bayer Ag Polysulfone / polyether block copolycondensate
EP0739925B1 (en) * 1995-04-28 1999-07-07 Bayer Ag Polysulfone-polyether block copolycondensates
EP0739925A2 (en) 1995-04-28 1996-10-30 Bayer Ag Polysulfone-polyether block copolycondensates
EP0781795A2 (en) * 1995-12-26 1997-07-02 Teijin Limited Application of sulfone, ketone and ester containing polyalkyl ethers to medical materials
JP2000239385A (en) * 1999-02-23 2000-09-05 Bayer Ag Production of polyether block copolysulfone
US6365678B1 (en) 1999-02-23 2002-04-02 Bayer Aktiengesellschaft Process for the production of polyether block copolysulfones
WO2006012453A1 (en) * 2004-07-22 2006-02-02 Solvay Advanced Polymers, L.L.C. Polysulfone - polyether blockcopolymers, process to synthesize it, membranes made therefrom
US20140113093A1 (en) 2011-05-25 2014-04-24 Solvay Speciality Polymers Usa, Llc Polymers with reduced estrogenic activity
US20150011446A1 (en) 2012-02-17 2015-01-08 Solvay Specialty Polymers Italy S.P.A. (PER)FLUOROPOLYETHERS WITH bi- OR ter-PHENYL END GROUPS
US20150129487A1 (en) 2012-05-15 2015-05-14 Solvay Specialty Polymers Usa, Llc. High performance polysulfones made from cycloaliphatic diols
WO2014072473A2 (en) 2012-11-09 2014-05-15 Solvay Specialty Polymers Usa, Llc Polyarylene ether sulfones
WO2014177640A1 (en) * 2013-05-02 2014-11-06 Basf Se Polyaryl ether sulphone copolymers
WO2017157933A1 (en) * 2016-03-15 2017-09-21 Solvay Specialty Polymers Italy S.P.A. Composition and method for manufacturing sulfone polymer membrane
US20190054429A1 (en) 2016-03-15 2019-02-21 Solvay Specialty Polymers Italy S.P.A. Composition and method for manufacturing sulfone polymer membrane
WO2019013529A1 (en) * 2017-07-12 2019-01-17 한국화학연구원 Method for preparing polyarylene ether copolymer comprising isohexide units and polyarylene ether copolymer prepared thereby
EP3653661A1 (en) 2017-07-12 2020-05-20 Korea Research Institute of Chemical Technology Method for preparing polyarylene ether copolymer comprising isohexide units and polyarylene ether copolymer prepared thereby
WO2020201522A1 (en) 2019-04-05 2020-10-08 Safran Aircraft Engines Method and system for monitoring a system for actuating a component of a turbomachine
CN113388111A (en) * 2021-07-05 2021-09-14 天津师范大学 Preparation method of low-chroma polyaromatic ether

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A. G. FARNHAM, J. POLYM. SCI. A-1 POLYM. CHEM., vol. 5, no. 9, 1967, pages 2415 - 2427
H. KRICHELDORFM. AL MASRI, J. POLYMER SCI., PT A: POLYMER CHEMISTRY, vol. 33, 1995, pages 2667 - 2671
KRICHELDORF H C ET AL: "New Polymer Syntheses LXXXII", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, JOHN WILEY & SONS, INC, US, vol. 33, 1 January 1995 (1995-01-01), pages 2667 - 2671, XP002674685, ISSN: 0887-624X, DOI: 10.1002/POLA.1995.080331513 *
KRICHELDORFCHATTI, HIGH PERFORMANCE POLYMERS, vol. 21, 2009, pages 105 - 118
POLYMER, vol. 55, no. 22, 2014, pages 5623 - 5634
SABER CHATTI ET AL: "Poly(ether sulfone) of Isosorbide, Isomannide and Isoidide", HIGH PERFORMANCE POLYMERS, INSTITUTE OF PHYSICS PUBLISHING, BRISTOL, GB, vol. 21, no. 1, 1 February 2009 (2009-02-01), pages 105 - 118, XP008151327, ISSN: 0954-0083, DOI: 10.1177/0954008308088296 *
TING Y ET AL: "Preparation of Polysulfone/Poly(ethylene oxide) Block Copolymers", MACROMOLECULES, vol. 29, no. 23, 1 January 1996 (1996-01-01), pages 7619 - 7621, XP093239445, DOI: https://doi.org/10.1021/ma9600421 *

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