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WO2024246814A1 - Macromères de diphénylsulfone fonctionnels comportant des chaînes latérales polymères greffées, et copolymères et articles préparés à partir de ceux-ci - Google Patents

Macromères de diphénylsulfone fonctionnels comportant des chaînes latérales polymères greffées, et copolymères et articles préparés à partir de ceux-ci Download PDF

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WO2024246814A1
WO2024246814A1 PCT/IB2024/055285 IB2024055285W WO2024246814A1 WO 2024246814 A1 WO2024246814 A1 WO 2024246814A1 IB 2024055285 W IB2024055285 W IB 2024055285W WO 2024246814 A1 WO2024246814 A1 WO 2024246814A1
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formula
repeat units
poly
membrane
group
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Austin G. KRUGER
Neelakandan Chandrasekaran
Gabriel GUERRA FAURA
David S. Hays
Jonathan F. Hester
Lucas D. MCINTOSH
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Solventum Intellectual Properties Co
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Solventum Intellectual Properties Co
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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
    • 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions 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; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/06—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

  • Separation devices having a porous polymeric substrate have been used in a wide range of different industrial, pharmaceutical, and medical applications. Some of these separation devices function by separating a mixture of materials based on the average size of the materials in the mixture. These separation devices typically retain materials of a certain size such as those having a diameter larger than the diameter of the pores in the polymeric substrate while allowing passage of other materials having a diameter smaller than the diameter of the pores in the polymeric substrate.
  • Membranes formed from poly ether sulfone (PES) have been used for separating biological materials such as proteins, viruses, and cells based on size.
  • the pore size of PES membranes can be tuned during membrane casting to suit a particular filtration need.
  • hydrophilic homopolymers such as, for example, poly(vinyl pyrrolidone) (PVP), poly(oxazoline) (POx), and polyethylene glycol) (PEG) can be added to the membrane casting solution to render the membrane hydrophilic and therefore somewhat resistant to biofouling.
  • PVP poly(vinyl pyrrolidone)
  • POx poly(oxazoline)
  • PEG polyethylene glycol
  • hydrophilic homopolymers are typically water soluble, a fraction of them can be extracted from the membrane during use. Therefore, users typically perform a pre-flush of the membrane to lower the extractable content to a suitable level before filtering the compositions of interest.
  • Functional diphenylsulfone macromers with grafted polymeric sidechains, copolymers having repeat units derived from the functional diphenylsulfone macromers with grafted polymeric sidechains, and porous polymeric articles containing these copolymers are provided.
  • the grafted polymeric sidechains contain repeat units derived from 2-oxazoline compounds and are usually polymeric.
  • the porous polymeric article is typically a membrane that can be either a flat sheet or a hollow fiber.
  • the porous polymeric articles can be used, for example, to separate mixtures of biomaterials having different average sizes based on the average pore size of the porous polymeric articles. For example, biomaterials such as proteins, viruses, and cells can be separated based on size.
  • Each R 1 is independently a leaving group or a nucleophilic group.
  • Group R 3 is an alkyl, alkenyl, aryl, or combination thereof.
  • the variables p and q are each an integer in a range of 0 to 4 with the sum of p + q being an integer equal to at least 1.
  • the compounds of Formula (I) can be referred to as macromers.
  • a copolymer in a second aspect, comprises a plurality of repeat units joined by -O- groups.
  • the plurality of repeat units includes (a) a first repeat unit of Formula (II) and (b) a second repeat unit of Formula (III).
  • the variables p and q are each equal to 0, 1 or 2 with the sum of p + q being an integer equal to at least 1.
  • Group R 3 is an alkyl, alkenyl, aryl, or combination thereof.
  • Each asterisk (*) is an attachment site to an -O- group that joins repeat units.
  • the first repeat unit of Formula (II) is of Formula (II-A) and/or Formula (II-B)
  • Each asterisk (*) is an attachment site to an -O- group that joins repeat units.
  • a porous polymeric article that comprises the copolymer described above in the second aspect.
  • the porous polymeric article is a membrane.
  • a method of separating biomaterials based on size includes providing a porous polymeric article as described above in the third aspect and passing an aqueous mixture of biomaterials through the porous polymeric article, wherein the mixture of biomaterials comprises a plurality of bio materials having different average sizes.
  • the method further includes separating the mixture of biomaterials based on their average sizes, wherein a first biomaterial that is smaller than a second biomaterial permeates through the porous polymeric article at a faster rate.
  • alkyl refers to a monovalent group that is a radical of an alkane.
  • the alkyl group can have 1 to 32 carbon atoms, 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • the alkyl can be linear, branched, cyclic, or a combination thereof.
  • a linear alkyl has at least one carbon atom while a cyclic or branched alkyl has at least 3 carbon atoms.
  • (hetero)alkyl refers to an alkyl, heteroalkyl, or both.
  • heteroalkyl refers to an alkyl having one or more of the catenated carbon atoms replaced by a heteroatom such as oxygen (-O-), sulfur (-S-), and nitrogen (e.g., -NR b - where R b is hydrogen or an alkyl). If there is more than one heteroatom, they are separated by at least one carbon atom.
  • alkylene refers to a divalent group that is a radical of an alkane.
  • the alkylene group can have 1 to 32 carbon atoms, 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • the alkylene can be linear, branched, cyclic, or a combination thereof.
  • a linear alkylene has at least one carbon atom while a cyclic or branched alkylene has at least 3 carbon atoms.
  • heteroalkylene refers to an alkylene or heteroalkylene.
  • heteroalkylene refers to an alkylene having one or more of the catenated carbon atoms replaced by a heteroatom such as oxygen (-O-), sulfur (-S-), and nitrogen (e.g., -NR b - where R b is hydrogen or an alkyl). If there is more than one heteroatom, they are separated by at least one carbon atom.
  • alkenyl refers to a monovalent group that is a radical of an alkene, which is a hydrocarbon compound having at least one carbon-carbon double bond. In some embodiments, the alkenyl has a single carbon-carbon double bond. In some more specific embodiments, the alkenyl has an ethylenically unsaturated group (the carbon-carbon double bond is between the last two carbon atoms in a chain).
  • the alkenyl can be linear, branched, cyclic or a combination thereof.
  • the alkenyl often has at least 2, at least 3, at least 4, or at least 5 carbon atoms and can have up to 32 carbon atoms, up to 24 carbon atoms, up to 20 carbon atoms, up to 12 carbon atoms, up to 10 carbon atoms, or up to 5 carbon atoms.
  • aryl refers to a monovalent group that is a radical of an aromatic carbocyclic compound.
  • the aryl group has at least one aromatic carbocyclic ring and can have 1 to 3 optional rings that are connected to or fused to the aromatic carbocyclic ring.
  • the additional rings can be aromatic, aliphatic, or a combination thereof.
  • the aryl group usually has 5 to 20 carbon atoms or 6 to 10 carbon atoms.
  • (hetero)aryl refers to an aryl, heteroaryl, or both.
  • heteroaryl refers to a monovalent group that is a radical of an aromatic heterocyclic compound.
  • the heteroaryl has at least one aromatic heterocyclic ring and can have optional rings that are connected or fused to the aromatic heterocyclic ring.
  • the additional rings can be aromatic, aliphatic, or a combination thereof.
  • the heteroaryl typically has 5 to 20, 5 to 12, or 5 to 10 ring atoms with at least one ring atom being a heteroatom such as oxygen, sulfur, or nitrogen.
  • leaving group refers to a group that can depart from a compound with a pair of electrons such as, for example, -F, -Cl, -Br, -I, CF3SO3-, and -SO2-C6H4-CH3.
  • nucleophilic group refers to a group that has an electron-rich atom that can donate a pair of electrons to form a covalent bond.
  • the nucleophilic group is often hydroxy (-OH) or -O-Si(R c )3 where R c is an alkyl or aryl.
  • macromer refers to a reactive compound having a polymeric group. More particularly, as used herein, the term macromer refers to a functional diphenylsulfone compound having (1) at least two functional groups that are leaving groups or nucleophilic groups and (2) a covalently attached (grafted) polymeric sidechain that is derived from ethylenically unsaturated monomers. The number of functional groups is typically two.
  • monomer is used herein to refer to a reactive compound that does not have a polymeric group. The monomer is typically a compound at least two functional groups that are leaving groups or nucleophilic groups. The number of functional groups is usually equal to two.
  • polymer and “polymeric material” are used interchangeably and refer to materials formed by reacting one or more monomers.
  • the terms include homopolymers, copolymers, terpolymers, or the like.
  • polymerize and “polymerizing” refer to the process of making a polymeric material that can be a homopolymer, copolymer, terpolymer, or the like.
  • copolymer is used herein to refer to a polymer and polymeric materials derived from more than one type of monomer and/or macromer.
  • casting solution and “polymer dope” are used interchangeably to refer to the composition used to form a porous membrane.
  • membrane refers to a porous article that is formed from a polymeric composition.
  • the membrane can be in the form of a flat sheet or a hollow fiber.
  • the membranes described herein are typically prepared using a phase separation process.
  • FIG.1 illustrates a perspective view of a partial cross-section of a portion of an exemplary hollow fiber membrane.
  • FIG. 2 illustrates a cross-section view of an exemplary hollow fiber membrane.
  • FIG. 3 is a scanning electron micrograph of a cross section of an exemplary hollow fiber membrane of Example HFM-1.
  • FIG. 4 is a scanning electron micrograph of a lumen wall of an exemplary hollow fiber membrane of Example HFM-1.
  • FIG. 5 is a scanning electron micrograph of an outside wall of an exemplary hollow fiber membrane of Example HFM-1.
  • Functional diphenylsulfone macromers having grafted polymeric sidechains derived from a 2-oxazoline compound, copolymers having repeat units derived from the functional diphenylsulfone macromers with grafted polymeric sidechains, and porous polymeric articles containing the copolymers are provided.
  • the porous polymeric article which is typically a membrane that can be either a flat sheet or a hollow fiber, can be used to separate mixtures of materials such as biomaterials having different average sizes.
  • porous articles have chemical functionalities that can provide one or more desirable characteristics such as water wettability, resistance to fouling by proteins and other hydrophobic components of the fluids that are treated, ion exchange capabilities, absorption of certain fluid components, and/or the ability to adjust the effective pore size during use in response to changes in an environmental characteristic such as pH of the treated fluid.
  • the copolymers include macromeric units having covalently attached polymeric sidechains that are hydrophilic, the amount of pre-flushing that needs to be done to remove extractable hydrophilic polymers from a porous polymeric article prepared from these copolymers can be substantially reduced.
  • the grafted polymeric sidechains of the copolymer result in the formation of membranes with uniform hydrophilic surfaces. Consequently, these membranes tend to have greater resistance to fouling than those formed using hydrophilic homopolymers.
  • the copolymers with grafted polymeric sidechains are typically amphiphilic but not water soluble. Because these copolymers are typically not water soluble, they are typically less extractable than the previously used hydrophilic homopolymers.
  • Functional diphenylsulfone macromers are provided with grafted polymeric sidechains derived from a 2-oxazoline compound. These macromers with grafted polymeric sidechains typically have at least two functional groups that can react with other monomers to form a copolymer.
  • the functional groups can be either leaving groups or nucleophilic groups.
  • the functional diphenylsulfone macromers are of Formula (I).
  • Each R 1 is independently a functional group that is either a leaving group or a nucleophilic group.
  • Group R 3 is an alkyl, alkenyl, aryl, or combination thereof.
  • the variables p and q are each an integer in a range of 0 to 4 with the sum of p + q being an integer equal to at least 1. In most embodiments, p and q are each in a range of 0 to 2 or 0 to 1.
  • Each group R 1 is independently a leaving group or a nucleophilic group.
  • Suitable leaving groups include, for example, -F, -Cl, -Br, -I, -SO3-CF3-, and -SO2-C6H4-CH3.
  • Suitable nucleophilic groups include, for example, -OH or -O-Si(R 6 )3 where each R 6 group is an alkyl such as those having 1 to 4 carbon atoms. If R 1 is a hydroxy group, it is typically protected during the formation of the R 2 grafted polymeric sidechains. For example, the hydroxy group can be protected as a -O-Si(R 6 )3 group.
  • the nucleophilic group -O-Si(R 6 )3 can be converted to a -OH group after formation of the compound of Formula (I) having the grafted polymeric sidechains. It is the group R 1 that is reactive (i.e., functional) when a polymeric material (i.e., copolymer) is formed that includes repeat units derived from the macromer of Formula (I).
  • a first aromatic ring can have p groups of formula R 2 while a second aromatic ring can have q groups of formula R 2 .
  • the variable p and q are each an integer in a range of 0 to 2 with the sum of p + q being equal to at least 1.
  • the number of R 2 groups in the macromer of Formula (I) is equal to 1 , 2, 3 , or 4.
  • there is a single R 2 group per macromer (p + q is equal to 1) or a single R 2 group on each aromatic ring (p + q is equal to 2).
  • These first and second repeat groups can be arranged randomly or in blocks.
  • the grafted polymeric sidechains can be homopolymers or random copolymers.
  • the grafted sidechain optionally can include repeat units of formula -NH-CH 2 -CH 2 -.
  • n is in a range of 0 to 2 percent of the sum of m + n (i.e., m n + m) is in a range of 0 to 0.02).
  • the sum of n + m is in a range of 3 to 1000.
  • This sum can be at least 3, at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 100, at least 200, at least 300, at least 400, or at least 500 and up to 1000, up to 900, up to 800, up to 700, up to 600, up to 500, up to 400, up to 300, up to 200, up to 100, up to 90, up to 80, up to 70, up to 60, up to 50, up to 40, up to 30, or up to 20.
  • the sum can be in a range of 3 to 500, 3 to 100, 5 to 100, or 5 to 50.
  • Group R 3 is an alkyl, alkenyl, aryl, or combination thereof.
  • the alkyl often has 1 to 10 carbon atoms such as at least 1, at least 2, at least 3, or at least 4 and up to 10, up to 8, up to 6, or up to 4 carbon atoms.
  • Example alkenyl groups typically have 2 to 10 carbon atoms such as at least 2, at least 3, at least 4 and up to 10, up to 8, up to 6, or up to 4.
  • the aryl group is often phenyl.
  • Combination groups include, for example, an alkyl substituted with a phenyl group, an alkenyl substituted with a phenyl group, a phenyl substituted with an alkyl group, or a phenyl substituted with an alkenyl.
  • Oxazoline compounds that are commercially available include, for example, 2-ethyl oxazoline, 2- isopropyl oxazoline, 2-isopropenyl oxazoline, 2-phenyl oxazoline, and 2-butyl oxazoline where R 3 is respectively, ethyl, isopropyl, isopropenyl, phenyl, and butyl.
  • An alkylene group in R 4 can have any suitable number of carbon atoms but typically has 1 to 10 carbon atoms.
  • the number of carbon atoms can be at least 1, at least 2, at least 3, or at least 4 and up to 10, up to 8, up to 6, or up to 4 carbon atoms.
  • An arylene group in R 4 can have 6 to 10 carbon atoms but is often phenylene.
  • the polymeric sidechain R 2 can be terminated with any suitable end group Q.
  • the end group is typically a group resulting from a reaction of the growing polymeric chain with a quenching agent.
  • the monomer of Formula (I) is of Formulas (I-A) or (I-B).
  • p and q in Formula (I) is either 0 or 1 with the sum (p + q) being 1 or 2.
  • the groups R 1 and R 2 are the same as described above for Formula (I).
  • any suitable method can be used to form the macromers of Formula (I) such as those of Formula (I-A) and (I-B).
  • the suitable macromers and isomers thereof can be formed using a method such as that described in Reaction Scheme A. Reaction Scheme A
  • a pre-assembled diphenylsulfone with two leaving groups (L) (compound (1)) can be reacted sequentially in tetrahydrofuran with butyl lithium, dimethylformamide, and sodium borohydride to form a mixture of compounds (2) and (3).
  • Compound (2) and/or compound (3) can then be reacted with phosphorous bromide in the presence of a solvent such as dichloromethane.
  • a solvent such as dichloromethane.
  • compounds (2) and (3) are often separated from each other using column chromatography prior to treatment with phosphorous bromide. For ease of description of the reaction scheme, the reaction with phosphorous bromide is shown only for compound (2).
  • the brominated compound (4) can then be reacted to graft a sidechain to the diphenylsulfone compound.
  • Compound (4) is first reacted with the ethyl oxazoline compound having an R 3 group (compound (5)) and then with a quenching agent (compound (6)) as shown in the reaction above.
  • the terminal group Q is derived from the quenching agent.
  • Group R 3 as well as variables n and m are described above.
  • group R 4 is -CH 2 - but other R 4 groups can be used as described above.
  • the quenching agent (6) in Reaction Scheme A typically has a nucleophilic group that reacts with an end of the growing polymeric chain.
  • Any known quenching agent can be used. Suitable quenching agents include, but are not limited, to compounds such as water, alcohols (e.g., methanol, ethanol, or isopropanol), sodium phenoxide, pyridine, 4-dimethylaminopyridine, sodium thiophenolate, lithium 4-tert-butylphenoxide, and the like.
  • the resulting sidechains are shown in Table A below for these quenching agents.
  • Some quenching agents that can be used may result in a mixture of compound (7) materials with different Q groups or even result in attachment of multiple functionalized diphenylsulfone compounds together.
  • quenching agents include, for example, aminobenzoxazole and imidazole.
  • the products produced by the same quenching agent can depend on the composition of group R 3 as shown in Table A using tertbutanol as the quenching agent. If R 3 is ethyl and if tert-butanol is used as the quenching agent, a single product is obtained; however, if R 3 is phenyl and if tert-butanol is used as the quenching agent, a mixture of products is obtained. Typically, it is desirable to select a quenching agent that produces a single product.
  • the terminal group Q is of formula -X-R 5 where X is -O-, -S-, or -NH- and R 5 is hydrogen, an alkyl, an alkyl substituted with an acyl or hydroxy, an alkenyl, an aryl, or aryl substituted with an alkyl.
  • the terminal group Q is a cationic (hetero)aryl that is optionally substituted with an alkyl or amino group.
  • the functional diphenylsulfone macromers of Formula (I) typically have a weight average molecular weight (Mw) ranging from 380 to 50,000 Daltons.
  • Mw is often at least 380, at least 400, at least 500, at least 1000, at least 1500, at least 2000, at least 2500, at least 3000, at least 4000, at least 5000, at least 10,000, or at least 20,000 Daltons and up to 50,000, up to 45,000, up to 40,000, up to 30,000, up to 25,000, up to 20,000, up to 15,000, up to 10,000, or up to 5,000
  • the range can be from 380 to 20,000, 500 to 10,000, 1000 to 10,000, 2500 to 10,000, 2000 to 10,000, 2000 to 5000, or 2500 to 5000 Daltons.
  • the weight average molecular weight of the compounds of Formula (I) can be determined by Nuclear Magnetic Resonance (NMR) spectroscopy as described in the Examples below.
  • Copolymers having repeat units derived from functional diphenylsulfone macromers with grafted polymeric sidechains
  • POLY-1 is an amphiphilic graft copolymer.
  • POLY - 1 is typically formed by reacting a first macromer of Formula (I) having grafted polymeric sidechains of formula R 2 with a second monomer of Formula ( having two functional groups R 7 that are either nucleophilic groups or leaving groups.
  • R 1 , R 2 , plus the variables p and q are the same as defined above.
  • the reaction product is typically a copolymer (POLY-1) with repeat units connected via a -O- group.
  • the first macromer of Formula (I) is of Formula (I- A) and/or (I-B).
  • the repeat units of POLY-1 include first repeat units of Formula (II) derived from macromers of Formula (I) and second repeat units of Formula (III) derived from monomers of Formula (IV).
  • Copolymer POLY-1 contains a plurality of repeat units joined by -O- groups. Each asterisk (*) is an attachment site to an -O- group that joins repeat units. In many embodiments, POLY-1 has first repeat units of Formula (II- A) and/or (II-B).
  • R 1 in the first macromer of Formula (I) is a leaving group
  • at least some of the second monomer of Formula (IV) has two hydroxy nucleophilic groups as shown in Formula (IVA-1) or two group of formula -O-Si(R c )3 where each R c is an alkyl or aryl as shown in Formula (IV-A-2).
  • the second monomer with nucleophilic groups is of Formula (IV-A-1).
  • R 1 in the first macromer of Formula (I) is a nucleophilic group, however, then at least some of the second monomer of Formula (IV) has two leaving groups as shown in Formula (IV- B).
  • the two leaving groups are typically -F, -Cl, -Br, -I, CF3SO3-, and -SO2-C6H4-CH3
  • the molar ratio of the first macromer of Formula (I) to the second monomer of Formula (IV) is less than 1.
  • a mixture of second monomers of Formula (IV) are used with some of the second monomers having R 7 nucleophilic groups and other second monomers having R 7 leaving groups.
  • the second monomer is often a mixture of monomers of Formula (IV-A-1) and/or Formula (IV-A-2) plus monomers of Formula (IV-B).
  • the second monomer is a mixture of monomers of Formula (IV-A-1) and Formula (IV-B).
  • the first macromer and second monomers are combined such that the total moles of nucleophilic groups are equal to or approximately equal to the moles of leaving groups.
  • the second monomer is of Formula (IV-C), Formula (IV-D), or a mixture thereof.
  • the monomer of Formula (IV-C) is within the scope of Formula (IV-A-1) above while the monomer of Formula (IV-D) is within the scope of Formula (IV-B) above.
  • L is -Cl or -F.
  • the variables p and q are each equal to 0, 1 or 2 with the sum of p + q being an integer in a range of 1 to 4.
  • Group Q is derived from reaction of the growing polymeric chain with a quenching agent, which is typically a nucleophile.
  • the copolymer often has first repeat unit of Formula (II- A) and/or Formula (II-B)
  • Each asterisk (*) is an attachment site to an -O- group that joins repeat units.
  • Such a copolymer is formed from a macromer of Formula (I-A) and/or (I-B)
  • POLY-1 can include additional optional repeat units in addition to those of Formulas (II) and (III). These optional repeat units include the following third repeat units of Formula (V-A), Formula (V-B), Formula (V-C), Formula (V-D), Formula (V-E), or a combination thereof.
  • V-E wherein an asterisk (*) is the attachment site to an -0- group that joins repeat units.
  • these repeat units are derived from monomers such as, for example, those of Formula (VI-A) to (VI-E) respectively or isomers thereof.
  • the group R 8 is either a nucleophilic group or a leaving group as described above. In many embodiments, R 8 is hydroxy.
  • any amount of the first macromer of Formula (I) can be used to form POLY-1, the amount typically needs to be controlled if the resulting copolymer POLY-1 is used to prepare a membrane such as those described below. For example, if the membrane is prepared using a phase separation process, the amount of first macromer of Formula (I) needs to be controlled so that POLY-1 is amphiphilic but not water soluble. If the amount of the first macromer of Formula (I) is too low, a membrane formed from the copolymer tends not to have sufficient antifouling characteristics and biomaterials such as proteins can undesirably stick to its surface.
  • Increasing the amount of the first macromer of Formula (I) used to form the graft copolymer POLY-1 tends to increase the amount of POLY- 1 on the membrane surface during solvent induced phase separation (SIPS) casting and tends to provide the desired membrane surface properties (e.g., water wettability and fouling resistance) at lower concentrations of POLY-1 in the casting solution. If the content of the first macromer of Formula (I) is too great, however, POLY-1 may be water soluble. Water solubility of POLY-1 is generally undesirable because this can lead to loss of the copolymer into the precipitation bath during membrane casting and/or to higher water extractability of the graft copolymer from the finished membrane.
  • SIPS solvent induced phase separation
  • the amphiphilic grafted copolymer POLY-1 is often prepared from a polymerizable composition that contains 10 to 60 weight percent of a first macromer of Formula (I) based on a total weight of the polymerizable material (i.e., macromers and monomers).
  • the amount of the first macromer is often at least 10, at least 15, at least 20, at least 25, or at least 30 weight percent and up to 60, up to 55, up to 50, up to 45, up to 40, up to 35, or up to 30 weight percent based on the total weight of polymerizable composition.
  • the amount of the first macromer of Formula (I) ranges from 10 to 55, 10 to 50, 10 to 45, 10 to 40, 10 to 30, 15 to 60, 15 to 55, 15 to 50, 15 to 45, 15 to 40, 20 to 60, 20 to 55, 20 to 50, 20 to 45, 20 to 40, 20 to 35, or 20 to 30 weight percent based on the total weight of polymerizable composition.
  • the polymerizable composition used to form POLY-1 can contain 40 to 90 weight percent of a second monomer of Formula (IV).
  • the amount of the monomer of Formula (IV) can be at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, or at least 70 and up to 90, up to 85, up to 80, up to 75, up to 70, up to 65, or up to 60 weight percent based on a total weight of polymerizable composition.
  • the amount of the second monomer of Formula (IV) ranges from 45 to 90, 50 to 90, 55 to 90, 60 to 90, 70 to 90, 40 to 85, 45 to 85, 50 to 85, 55 to 85, 60 to 85, 40 to 80, 45 to 80, 50 to 80, 55 to 80, 60 to 80, 65 to 80, or 70 to 80 weight percent based on the total weight of polymerizable composition.
  • the polymerizable composition used to form POLY-1 can optionally contain 0 to 50 weight percent of a third monomer of Formula (V-A), (V-B), (V-C), (V-D), (V-E), or a mixture thereof.
  • the amount of this third monomer, if present, can be at least 1, at least 2, at least at least 5, at least 10, or at least 15 and up to 50, up to 40, up to 30, up to 25, up to 20, up to 15, up to 10, or up to 5 weight percent based on the total weight of polymerizable composition.
  • POLY-1 typically has a weight average molecular weight (Mw) ranging from 10,000 to 250,000 Daltons.
  • the weight average molecular weight is typically at least 10,000, at least 15,000, at least 20,000 at least 25,000, at least 30,000, at least 35,000, at least 40,000, at least 45,000, at least 50,000, at least 75,000, or at least 100,000 Daltons and up to 250,000, up to 225,000, up to 200,000, up to 175,000, up to 150,000, up to 125,000, up to 100,000, up to 80,000, up to 60,000, up to 50,000, up to 40,000, up to 35,000, or up to 30,000 Daltons.
  • Mw weight average molecular weight
  • the range is from 20,000 to 200,000, 25,000 to 100,000, from 25,000 to 80,000, from 25,000 to 60,000, from 25,000 to 50,000, or from 25,000 to 40,000 Daltons.
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) as described in the Examples below.
  • Porous polymeric articles are provided that contain an amphiphilic grafted copolymer POLY-1 having repeat units derived from the functional diphenylsulfone macromers with grafted polymeric sidechains as described above.
  • the porous polymeric article can be in any form, it typically is a membrane.
  • the membrane can be, for example, in the form of a flat sheet or a hollow fiber.
  • the membranes are typically formed by a phase separation process.
  • the phase separation process used to form the membrane is a solvent induced phase separation (SIPS) process and the resulting membrane can be referred to as a “SIPS membrane”.
  • SIPS membranes are sometime referred to by other names such as, for example, “DIPS membranes” formed by diffusion induced phase separation, “NIPS membranes” formed by non-solvent induced phase separation, or as “phase inversion membranes”. These processes are all referred to herein as SIPS processes and the products as SIPS membranes.
  • the polymeric material is combined with other solution components such as a suitable solvent for the polymeric material to prepare a substantially homogeneous solution that is referred to interchangeably as a “casting solution” or as a “polymer dope”.
  • the casting solution is formed into either a flat sheet using a coating process or a hollow tube using a spinning process.
  • the flat sheet or hollow fiber is then immersed in a “quench solution” containing a non-solvent for the polymeric material. Exchange of the solvent in the casting solution with the non-solvent in the quench solution results in phase separation of the polymer solution yielding a solid, porous flat sheet or hollow fiber.
  • the flat sheet or hollow fiber can be exposed to a humid atmosphere or steam prior to immersion into the quench solution to begin the phase separation process.
  • the casting solution used to form the SIPS membrane typically includes a mixture of polymeric materials and a water-miscible organic solvent.
  • the mixture of polymeric materials includes POLY-1 as described above having grafted polymeric sidechains, a second polymer POLY-2 that is typically an aromatic polyether sulfone lacking grafted polymeric sidechains, and an optional third polymer POLY-3 that is typically a hydrophilic pore former.
  • the casting solution also contains a water-miscible solvent that can dissolve POLY-1, POLY-2, and optional POLY-3. Still further, the casting solution can optionally contain water.
  • the casting solution contains POLY-1, which is the copolymer described above that comprises (1) repeat units of Formula (II) that is a diphenylsulfone with at least one grafted polymeric sidechain R 2 as well as (2) repeat units of Formula (III) that is a diphenylsulfone without grafted polymeric sidechains.
  • the casting solution typically contains 1 to 20 weight percent of POLY-1 based on a total weight of the casting solution. The amount can be at least 1, at least 1.5, at least 2, at least 2.5, at least 3, at least 4, or at least 5 weight percent and up to 20, up to 18, up to 15, up to 12, up to 10, up to 8, or up to 5 weight percent based on the total weight of the casting solution.
  • the amount of POLY-1 can be in a range of 1.5 to 20, 1.5 to 15, 2 to 20, 2 to 15, 2 to 10, or 2 to 5 weight percent based on the total weight of the casting solution.
  • the various repeat units are connected to each other by -O- linkages.
  • the casting solution includes a second polymer that can be referred to as POLY-2.
  • POLY-2 is an aromatic polyether sulfone having repeat units of Formula (III) wherein an asterisk (*) is the attachment site to an -O- group that joins two repeat units.
  • This second polymer can be a homopolymer or copolymer. If POLY-2 is a copolymer, it is free of repeat units of Formula (II) and is made from a polymerizable mixture that is free of the macromer of Formula (I). POLY-2 lacks the grafted polymeric sidechains that are included in POLY-1.
  • the repeat units of Formula (III) are combined with one or more optional repeat units of Formula (V-A), Formula (V-B), Formula (V-C), Formula (V-D), Formula (V-E), or a combination thereof as described above as optional repeat units that can be included in POLY-1.
  • These optional repeat units typically are no greater than 50 mole percent of all the repeat units in POLY-2. That is, they can be present in an amount of 0 to 50 mole percent based on all the repeat units included in POLY-2.
  • these optional repeat units can be up to 50, up to 45, up to 40, up to 35, up to 30, up to 25, up to 20, up to 15, up to 10, or up to 5 mole percent of all the repeat units in POLY-2.
  • POLY-2 typically has a weight average molecular weight (Mw) in a range of 30,000 to 150,000 Daltons (30 to 150 kDa).
  • Mw is often at least 30, at least 40, at least 50, at least 60, or at least 70 and up to 150, up to 140, up to 130, up to 120, up to 100, up to 90, up to 80, up to 70, up to 60, or up to 50 kDa.
  • the range can be, for example, from 30 to 120, 50 to 120, or 60 to 100 kDa.
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) as described in the Examples below.
  • the amount of POLY-2 in the casting solution is typically in a range of 10 to 40 weight percent based on the total weight of the casting solution.
  • the amount can be at least 10, at least 12, at least 15, or at least 20 weight percent and up to 40, up to 35, up to 30, up to 25, up to 20, or up to 15 weight percent based on the total weight of the casting solution.
  • the amount of POLY-2 can be in a range of 10 to 35, 10 to 30, 10 to 25, 12 to 40, 12 to 35, 12 to 30, 12 to 25, 15 to 40, 15 to 35, 15 to 30, 15 to 25, 20 to 40, 20 to 35, or 20 to 30 weight percent based on the total weight of the casting solution.
  • the amount of POLY-2 in the casting solution can impact the pore size of the resulting membrane formed from the casting solution. For example, an increase in the amount of POLY-2 tends to decrease the average pore size of the membrane. Varying the amount of POLY -2 can be used to alter the size of materials that can permeate though the membrane and/or the speed of permeation through the membrane.
  • An optional third polymeric material which is referred to as POLY-3, is often included in the casting solution in addition to POLY-1 and POLY-2.
  • This third polymer is typically selected to be a hydrophilic polymer that has greater water solubility than either POLY-1 or POLY-2.
  • the third polymer typically does not undergo phase separation. That is, POLY-3 remains in solution unlike both POLY-1 and POLY-2.
  • Suitable POLY-3 hydrophilic polymers include, for example, poly(2- vinylpyrrolidone), polyethylene glycol, polyvinyl alcohol, polyglycol monoester, carboxylmethylcellulose, a polysorbitate such as polyoxyethylene sorbitan monooleate, carboxymethylcellulose polyacrylic acid, polyacrylamide, poly(oxazoline) a copolymer thereof, or a blend thereof.
  • POLY-3 is a polyethylene glycol or a polymeric mixture that includes polyethylene glycol.
  • POLY-3 can have any desired molecular weight and may comprise a mixture of polymers of multiple molecular weights.
  • the amount of one or more components of POLY-3 in the membrane is desired to be low to reduce its extractability.
  • the weight average molecular weight of that component of POLY-3 is often less than 1000 Daltons.
  • the weight average molecular weight may be up to 750 Daltons such as in a range of 100 to 750, 100 to 500, 100 to 400, 200 to 750, 200 to 500, or 200 to 400 Daltons.
  • the amount of one or more components of POLY-3 in the membrane is desired to be high to impart greater fouling resistance or to tune the porosity of the membrane.
  • the weight average molecular weight of that component of POLY-3 is often greater than 1000 Daltons.
  • the weight average molecular weight of that component of POLY-3 can be up to 750,000 Daltons such as in a range of 1,100 to 750,000 Daltons, 1,100 to 500,000 Daltons, 1,100 to 400,000 Daltons, 2,000 to 500,000 Daltons, or 20,000 to 50,000 Daltons.
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) as described in the Examples below.
  • the amount of POLY-3 in the casting solution is typically in a range of 0 to 65 weight percent based on a total weight of the casting solution.
  • the amount can be at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, or at least 40 weight percent and up to 65, up to 60, up to 55, up to 50, up to 45, up to 40, or up to 35 weight percent based on the total weight of the casting solution.
  • the amount can be in a range of 1 to 65, 1 to 60, 5 to 60, 10 to 60, 10 to 50, 10 to 40, 10 to 30, 20 to 60, 20 to 50, 20 to 40, 30 to 30 to 60, 30 to 50, or 30 to 40 weight percent based on the total weight of the casting solution.
  • the casting solution can include a water- miscible organic solvent.
  • Water-miscible organic solvents that can be used include, for example, glycol, glycerol, butyrolactone, s-caprolactam, ⁇ -mcth Ipy rrolidone, dimethyl sulfoxide, dimethyl acetoamide, dimethyl formamide, and combinations thereof.
  • the water- miscible organic solvent includes ⁇ -mcth Ipy rrolidone because it usually is a good solvent for both POLY-1 and POLY-2.
  • any suitable amount of the water-miscible organic solvent can be included in the casting solution.
  • the amount can be, for example, in a range of 20 to 70 weight percent based on a total weight of the casting solution.
  • the amount can be at least 20, at least 25, at least 30, at least 35, at least 40, or at least 45 weight percent and up to 70, up to 65, up to 60, up to 55, up to 50, up to 45, or up to 40 weight percent based on the total weight of the casting solution.
  • the amount can be in a range of 20 to 65, 20 to 60, 20 to 55, 20 to 50, 20 to 45, 20 to 40, 25 to 65, 25 to 60, 25 to 55, 25 to 50, 25 to 45, 25 to 40, 30 to 60, 30 to 55, 30 to 50, 30 to 45, or 30 to 40 weight percent based on the total weight of the casting solution.
  • the casting solution can optionally include water.
  • the casting solution can contain 0 to 10 weight percent water. If present, the amount can be at least 1, at least 2, at least 3, at least 4, or at least 5 and up to 10, up to 8, up to 6, up to 5, or up to 4 weight percent based on the total weight of the casting solution. The amount can be, for example, in a range of 1 to 8, 1 to 6, 1 to 5, 2 to 10, 2 to 8, 2 to 6, 2 to 5, 3 to 10, 3 to 8, 3 to 6, or 3 to 5 weight percent based on the total weight of the casting solution.
  • the casting solution contains 1 to 20 weight percent POLY-1, 10 to 40 weight percent POLY-2, 0 to 65 weight percent POLY-3, 20 to 70 weight percent water- miscible organic solvent, and 0 to 10 weight percent water based on a total weight of the casting solution.
  • the casting solution contains 1.5 to 15 weight percent POLY-1, 12 to 30 weight percent POLY-2, 20 to 50 weight percent POLY-3, 25 to 55 weight percent water- miscible organic solvent, and 2 to 6 weight percent water.
  • the casting solution contains 2 to 10 weight percent POLY-1, 15 to 25 weight percent POLY-2, 30 to 40 weight percent POLY-3, 30 to 40 weight percent water-miscible organic solvent, and 3 to 5 weight percent water.
  • the casting solution is transparent and macroscopically homogeneous.
  • the membrane that is formed from the casting solution can be either in the form of a sheet or a hollow fiber membrane. Both types of membranes can be formed from the casting solution. After casting either a sheet or hollow fiber, the sheet or the hollow fiber is immersed in a quenching bath that results in the precipitation of the membrane. If desired, the membrane can optionally be transferred to a second bath such as a water bath to extract additional materials from the membrane.
  • the precipitation bath includes water and optionally can further include water-miscible organic solvents such as those listed above for use in the casting solution.
  • the precipitation bath often contains 50 to 100 weight percent water and 0 to 50 weight percent of a water-miscible organic solvent.
  • the precipitation bath includes 55 to 100 weight percent water and 0 to 45 weight percent water-miscible organic solvent or 60 to 100 weight percent water and 0 to 40 weight percent water-miscible organic solvent.
  • the water-miscible solvent is often selected to be ⁇ -mcth lpyrrolidonc.
  • the casting solution is often heated to an elevated temperature such as, for example, in a range of 40 to 80 degrees Celsius.
  • the casting solution can be coated onto a support that is also heated in a range of 40 to 80 degrees Celsius.
  • the film can be prepared as a coating using, for example, a notch bar with a suitable gap height, such as in a range of 25.4 to 508 micrometers.
  • the notch bar is often heated in a range of 40 to 80 degrees Celsius before spreading the casting solution out on the surface of the support.
  • the coated support is typically immersed into the precipitation bath that is often heated in a range of 40 to 80 degrees Celsius.
  • the membrane optionally can be further extracted in a second bath that contains water.
  • the membrane can be dried in an oven after formation. The temperature of the oven can be, for example, in a range of 40 to 80 degrees Celsius.
  • the membrane is in the form of a sheet.
  • the sheet typically has a thickness in a range of 30 to 250 micrometers.
  • the thickness can be at least 30, at least 40, at least 50, at least 60, at least 80, or at least 100 and up to 250, up to 225, up to 200, up to 175, up to 150, up to 125, up to 120, up to 110, or up to 100 micrometers.
  • the range can be, for example, from 30 to 200, 30 to 150, 50 to 150, 50 to 125, 50 to 1110, or 50 to 100 micrometers.
  • the membrane is in the form of a hollow fiber.
  • the hollow fiber can be formed by extruding the casting solution through a coaxial spinneret die.
  • This coaxial spinneret die typically has an annular gap as well as a central inner channel that is arranged coaxially to the annular gap.
  • the annular gap is separated from the central inner channel by a needle.
  • the casting solution is introduced into the annular gap while a bore liquid is introduced into the inner chamber.
  • the bore liquid stabilizes the lumen of the hollow fiber membrane as it is formed.
  • the spinneret die is selected depending on the desired dimensions of the hollow fiber membranes. While any suitable spinneret die can be used, the outer diameter of the annulus is often in a range of 300 to 1000 micrometers.
  • the annulus outer diameter can be, for example, at least 300, at least 400, at least 500 and up to 1000, up to 800, or up to 600 micrometers.
  • the inner diameter of the annulus which is also the outer diameter of the needle, is often in a range of 190 to 980 micrometers.
  • the annulus inner diameter can be, for example, at least 190, at least 200, at least 300, or at least 500 and up to 980, up to 900, up to 800, up to 600, or up to 500 micrometers.
  • the inner diameter of the needle is often in a range of 40 to 830 micrometers.
  • the needle inner diameter can be, for example, at least 40, at least 50, at least 75, at least 100, at least 150, at last 200 at least 250, at least 300, at least 350, at least 400 and up to 830, up to 800, up to 750, up to 700, up to 650, up to 600, up to 550, or up to 500 micrometers.
  • One exemplary spinneret die has an annulus outer diameter of 1000 micrometers, a needle outer diameter of 980 micrometers, an annular gap of 10 micrometers, a needle inner diameter of 830 micrometers, and a needle thickness of 75 micrometers.
  • Another exemplary spinneret die has an annulus outer diameter of 500 micrometers, a needle outer diameter of 300 micrometers, an annular gap of 100 micrometers, a needle inner diameter of 150 micrometers, and a needle thickness of 75 micrometers.
  • Yet another exemplary spinneret die has an annulus outer diameter of 410 micrometers, a needle outer diameter of 300 micrometers, an annular gap of 55 micrometers, a needle inner diameter of 150 micrometers, and a needle thickness of 75 micrometers. Still another exemplary spinneret die has an annulus outer diameter of 300 micrometers, a needle outer diameter of 190 micrometers, an annular gap of 55 micrometers, a needle inner diameter of 40 micrometers, and a needle thickness of 75 micrometers.
  • the bore liquid composition typically includes a water-miscible organic solvent, water, and optionally a hydrophilic polymer such as those listed above for POLY-3. Any suitable water- miscible organic solvent can be used such as those described above for use in the casting solution.
  • the water-miscible organic solvent used in the bore liquid includes N- methylpyrrolidone and any optional hydrophilic polymer used in the bore liquid includes polyethylene glycol.
  • the amount of the water-miscible organic solvent in the bore liquid composition is often in a range of 30 to 95 weight percent based on a total weight of the bore liquid.
  • the amount can be at least 30, at least 35, at least 40, at least 45, or at least 50 weight percent and up to 95, up to 90, up to 85, up to 80, up to 75, up to 70, up to 65, up to 60, up to 55, or up to 50 weight percent.
  • the amount can be in a range of 30 to 90, 30 to 80, 30 to 75, 30 to 70, 30 to 60, 30 to 50, 40 to 90, 40 to 80, 40 to 75, 40 to 70, 40 to 60, or 40 to 50 weight percent.
  • the amount of water in the bore liquid composition is often in a range of 1 to 55 weight percent based on a total weight of the bore liquid.
  • the amount can be at least 1.5, at least 2, at least 2.5, at least 3, at least 4, at least 5, at least 10 weight percent and up to 55, up to 50, up to 45, up to 40, up to 35, up to 30, up to 25, up to 20, up to 15, or up to 10 weight percent.
  • the amount can be in a range of 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 15, 1 to 10, 2 to 50, 2 to 40, 2 to 30, 2 to 20, 2 to 15, 2 to 10, 5 to 50, 5 to 40, 5 to 30, 5 to 20, or 5 to 15 weight percent.
  • the amount of the optional hydrophilic polymer in the bore liquid composition is often in a range of 0 to 60 weight percent based on the total weight of the bore liquid.
  • the amount can be 0, at least 1, at least 5, at 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40 weight percent and up to 60, up to 55, up to 50, up to 45, up to 40, up to 35, or up to 30 weight percent.
  • the amount can be in a range of 0 to 50, 10 to 60, 10 to 55, 10 to 50, 10 to 45, 10 to 40, 20 to 60, 20 to 55, 20 to 50, 20 to 45, 20 to 40, 30 to 60, 30 to 55, 30 to 50, 30 to 45, 40 to 60, or 40 to 50 weight percent.
  • the bore liquid composition contains 30 to 95 weight percent water-miscible organic solvent, 1 to 55 weight percent water, and 0 to 60 weight percent of the optional hydrophilic polymer. In some examples, the bore liquid composition contains 35 to 80 weight percent water-miscible organic solvent, 2 to 40 weight percent water, and 20 to 55 weight percent hydrophilic polymer. In other examples, the bore liquid composition contains 35 to 75 weight percent water-miscible organic solvent, 2 to 20 weight percent water, and 30 to 55 weight percent hydrophilic polymer. In still other examples, the bore liquid composition contains 40 to 50 weight percent water-miscible organic solvent, 5 to 15 weight percent water, and 40 to 50 weight percent hydrophilic polymer. Typically, the bore liquid is transparent and macroscopically homogenous.
  • the bore liquid is introduced into the inner chamber while the casting solution is introduced into the annular gap of the coaxial spinneret die.
  • the casting solution is passed through a fdter to remove any particulate materials prior to introduction into the annular gap.
  • Both fluid streams are often heated prior to introduction into the die.
  • both fluid streams can be heated in a range of 30 to 80 degrees Celsius.
  • the flow rate of the bore liquid and the flow rate of the casting solution each usually can be independently controlled.
  • the extruded product After leaving the coaxial spinneret die and before entering the precipitation bath, the extruded product optionally passes through a climate-controlled zone with defined climatic conditions.
  • the climate-controlled zone is often in the form of an encapsulated chamber.
  • the extruded product often has a retention time no greater than 10 seconds within the climate- controlled zone having a relative humidity of 20 to 95 percent and a temperature of 25 to 75 degrees C.
  • the relative humidity is often at least 40, at least 50, at least 55, at least 60, at least 65, at least 70, or at least 75 percent and up to 90, up to 85, up to 80, up to 75, or up to 70 percent.
  • the temperature is often at least 25, at least 30, at least 35, at least 40, at least 45, or at least 50 degrees Celsius and up to 90, up to 85, up to 80, or up to 75 degrees Celsius.
  • the climate-controlled zone contains air with a relative humidity of 75 to 90% and a temperature of 30 to 50 °C, a relative humidity of 60 to 75% and a temperature of 50 to 70°C, or a relative humidity of 75 to 90% and a temperature of 50 to 70°C.
  • the retention time within the climate-controlled zone is often at least 0.5, at least 1, at least 2, or at least 3 and up to 10, up to 8, up to 6, or up to 5 seconds.
  • the air often flows through the climate-controlled zone with a velocity of less than 0.5 m/s and preferably with a velocity in the range from 0.15 to 0.35 m/s.
  • pre-coagulation may occur on the outside of the extruded product by absorption of water vapor acting as the non-solvent, before entering the precipitation bath.
  • the extruded product After passing through the climate-controlled zone, the extruded product is directed into the precipitation bath that is in a range of 50 to 80 degrees Celsius to complete the formation of the hollow fiber membrane structure.
  • the composition of the precipitation bath can be the same as described above for prepare membranes in the form of sheets.
  • the membrane structure is formed by precipitation (e.g., coagulation) and then stabilized. Extraction of the water-miscible solvents and the hydrophilic polymer occurs at the same time. That is, water, the water-miscible organic solvent, and the optional hydrophilic POLY-3 can be extracted. The pores of the membrane are formed within the precipitation bath due to the phase separation and extraction processes that occur.
  • the hollow fiber membrane can be processed using conventional methods.
  • the hollow fiber membrane optionally can be further treated by pouring deionized water through the lumen and extracted in water at an elevated temperature such as, for example, 70 to 100 degrees Celsius for several hours.
  • the hollow fiber membrane After drying either at room temperature or elevated temperatures, the hollow fiber membrane can be wound onto a coil or formed directly into bundles with a suitable fiber count and length. Before production of the bundles, supplementary threads in the form of multifilament yams can be added to the hollow fiber membranes to ensure a spacing of the hollow fiber membranes relative to one another for better flow around the individual hollow fiber membranes in the bundle.
  • the membrane typically contains 1 to 50 weight percent POLY-1 based on a total weight of the membrane.
  • the membrane can contain at least 1, at least 2, at least 3, at least 5, at least 10, at least 15, at least 20, or at least 25 and up to 50, up to 45, up to 40, up to 35, up to 30, up to 25, or up to 20 weight percent POLY-1.
  • the amount can be in a range of 2 to 50, 2 to 40, 3 to 30, 5 to 30, 5 to 25 or 5 to 20 weight percent based on a total weight of the membrane.
  • the membrane typically contains 50 to 99 weight percent POLY-2 based on a total weight of the membrane.
  • the amount of POLY-2 can be at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, or at least 80 and up to 99, up to 98, up to 97, up to 95, up to 90, up to 85, up to 80, up to 75 based on a total weight of the membrane.
  • the amount of POLY-2 can be in a range of 50 to 98, 60 to 98, 70 to 97, 70 to 95, 75 to 95, or 80 to 95 based on a total weight of the membrane.
  • the membrane may optionally contain POLY-3, the water-miscible organic solvent, and/or water.
  • the amount of POLY-3 is typically in a range of 0 to 20 weight percent based on the total weight of the membrane.
  • the amount of POLY-3 can be at least 0.1, at least 0.5, or at least 1, at least 2, at least 3, or at least 5 and up to 20, up to 15, up to 10, up to 8, or up to 5 weight percent.
  • the amount of water-miscible organic solvent is typically in a range of 0 to 1 weight percent based on the total weight of the membrane.
  • the amount of the water- miscible organic solvent can be at least 0.05, at least 0.1, at least 0.2, at least 0.3, or at least 0.5 and up to 1, up to 0.8, up to 0.6, up to 0.5, up to 0.3, or up to 0.1 weight percent.
  • FIG. 1 illustrates a perspective view of a partial cross-section of a portion of an exemplary hollow fiber membrane 12.
  • Hollow fiber membrane 12 may have a continuous hollow lumen 16 that extends from one end to the other end of the fiber.
  • An outer surface 18 facing outwards forms an outer side of the fiber and an inner surface 20 facing towards the hollow lumen 16 define a fiber portion 26 having a wall thickness 28.
  • the fiber portion 26 is typically porous and contains a polymeric blend comprising a mixture of POLY- 1 and POLY-2.
  • the hollow fiber membranes formed are typically an integrally asymmetric, permeable hollow fiber membrane.
  • asymmetric means that the average pore size varies throughout the wall thickness 28.
  • integralally means that the pore size changes gradually in size over the wall thickness 28 of the fiber portion 26.
  • the wall thickness 28 of the fiber portion 26, measured between the outer surface 18 and the inner surface 20 of the fiber 26 portion of the hollow fiber membrane 12, can be in the range of from 10 to 400 micrometers or 20 to 300 micrometers.
  • the fiber portion 26 is formed from the casting solution.
  • the wall thickness can be at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 80, or at least 100 micrometers and up to 400, up to 350, up to 300, up to 275, up to 250, up to 225, up to 200, up to 175, up to 150, up to 125, up to 100, up to 80, or up to 60, or up to 50 micrometers.
  • the wall thickness is in a range of 30 to 200, 30 to 100, 40 to 150, 40 to 100, 40 to 80, or 40 to 60 micrometers.
  • the inside diameter of the hollow fiber membranes which corresponds to the diameter of the inner wall 20 in FIG. 1, is often in the range of from 50 to 800 micrometers.
  • This diameter can be at least 50, at least 60, at least 80, at least 100, at least 150, at least 200, at least 250, or at least 300 micrometers and up to 800, up to 700, up to 600, up to 500, up to 400, up to 300, or up to 200 micrometers.
  • the inside diameter is in a range of 50 to 700, 50 to 600, 100 to 500, 100 to 400, 100 to 300, or 100 to 200 micrometers.
  • Wall thicknesses and diameters (i.e., inner or lumen diameter, and outer diameter) of the membranes can be determined using scanning or transmission electron micrographs (SEM or TEM, respectively), for example with a magnification up to 20,000 times.
  • the hollow fiber membrane can have tortuous structures extending from the inner surface toward to the outer surface.
  • FIG. 2 illustrates a cross-section view of an exemplary hollow fiber membrane 112.
  • Hollow fiber membrane 112 may have a continuous hollow lumen 116, which extends from one end to the other end of the fiber; an outer surface 118 facing outwards, which forms an outer side of the fiber; an inner surface 120 facing towards the hollow lumen 116, which defines the limits of the continuous hollow lumen 116.
  • the fiber portion 126 of the membrane has a cross sectional thickness 128 that begins at the inner surface 120 and extends to the outer surface 118.
  • the pore size progressively changes across the cross-sectional thickness 128. Although the pore size can either progressively increase or decrease across the cross-section zone 128, the pore size often progressively decreases.
  • the pore size often varies in a range from 10 to 100 nanometers but there can be pores having a larger diameter such as up to 500, up to 1000, up to 5000, or even up to 10,000 nanometers.
  • FIG. 3, FIG. 4, and FIG. 5 are scanning electron micrographs of an exemplary the hollow fiber membrane that was formed in Example HFM-1 as described below.
  • FIG. 3 shows a cross section of the hollow fiber membrane
  • FIG. 4 shows the lumen wall of the hollow fiber membrane
  • FIG. 5 shows the outside wall of the hollow fiber membrane.
  • the hollow fiber membrane is porous across its width, but the size and shape of the pores vary across the diameter of the membrane.
  • POLY-1 is a copolymer that is often prepared by reacting a first macromer of Formula (I) having grafted polymeric sidechains of formula R 2 . with a second monomer of Formula (IV) having two functional groups R 7 that are either nucleophilic groups or leaving groups.
  • the reaction product is typically a copolymer with repeat units connected via an -O- group.
  • the copolymer has a plurality of groups R 2 , which are grafted poly(oxazoline) sidechains.
  • the structural features of POLY- 1 can be modified and controlled. For example, both the molecular weight and graft density of the poly(oxazoline) sidechains can be controlled via stoichiometry during synthesis. Thus, the polymeric structure of POLY- 1 can be systematically refined to impart desirable characteristics to the membrane such as a particular porosity, pore size, and/or surface hydrophilicity.
  • POLY-1 is purified by conventional synthetic techniques and provided as a solid for direct incorporation into the membrane casting formulations along with POLY-2 and optionally POLY-3.
  • WO 2021/1011987 describes randomly crosslinking the poly(oxazoline) at multiple locations to a matrix of poly(ether sulfone) in an uncontrolled manner. Further, the crosslinked networks described in WO 2021/1011987 present a cumbersome manufacturing pathway in that a mixture of poly(oxazoline) and poly(ether sulfone) must be coated or cast. Then the coating is irradiated to induce crosslinking of the polymers. Finally, the crosslinked network must be taken up in a suitable solvent for casting into a membrane format. Without the crosslinking, the poly(oxazoline) can be undesirably extracted from the membrane after its formation. A separate crosslinking step in not needed when the membranes are formed from POLY-1 and POLY -2 as described herein.
  • the porous articles can be used for separating various composition based on the size of components in the composition.
  • the porous articles are membranes suitable for separating components of a mixture based on the size of the components.
  • a mixture of biomaterials can be separated based on the size of the various biomaterials in the mixture.
  • the larger biomaterials are typically retained upstream of the membranes and/or pass through (i.e., permeate) the membrane at a slower speed than smaller biomaterials.
  • the composition exiting the membrane tends to have an enriched concentration of the smaller biomaterials compared to the original mixture of biomaterials.
  • a method of separating components based on size includes providing a porous separation article as described above, which is typically a membrane.
  • the method further includes passing a first composition through the membrane, wherein the first composition of biomaterials comprises a plurality of different biomaterials with different average sizes.
  • the method further includes separating the plurality of different biomaterials based on their different average sizes.
  • a first biomaterial that has a smaller average size than a second biomaterial can typically permeate through the membrane more rapidly than the second biomaterial.
  • the second biomaterial that has a larger average size than the first biomaterial will be retained by the membrane and/or will permeate through the membrane more slowly than the first biomaterial.
  • a second composition exiting the membrane will have a higher concentration of the first biomaterial and a lower concentration of the second component compared to the original first composition of biomaterials.
  • biomaterials that can be separated include, for example, bacteria, viruses, viral particles, proteins, protein fragments, fusion proteins, cells, and the like. Different size biomaterials within the same general category as well as biomaterials within different general categories can be separated based on their different average sizes.
  • the second composition exiting the membrane will have a higher concentration of the smaller biomaterials.
  • the membrane can selectively retain viruses or viral particles having a larger average size than other biomaterials in the first composition of biomaterials. Further different size viruses and/or viral particles can be separated from each other with the smaller vimses and/or viral particles permeating though the membrane more quickly.
  • an adeno- associated virus or a portion of an adeno-associated virus can be separated from larger viruses.
  • bacteria can be separated based on their average sizes with the smaller bacteria permeating through the membrane more quickly or bacteria can be separated from different types of biomaterials based on average size differences.
  • proteins or protein fragments can be separated from other biomaterials.
  • the proteins or protein fragments are smaller than the other biomaterials can permeate faster though the membrane.
  • the protein or protein fragment can be, for example, a monoclonal antibody, a monoclonal antibody fragment, or a fusion protein.
  • the hollow fiber membrane of the present discourse can be used for multiple extracorporeal blood purification procedures including dialysis, blood oxygenation, and plasmapheresis. Examples
  • Gel permeation chromatography data was obtained using an Agilent 1260 Infinity GPC equipped with isocratic pump, standard degasser, standard autosampler, thermostatted column compartment set to 55 °C, and a refractive index detector using two Agilent PLGel 5 pm Mixed-D 300 x 7.5 mm gel permeation chromatography columns.
  • Gel permeation chromatography samples were prepared at 5 mg/mL in a solution of 20 mM lithium bromide in N-methylpyrrolidone and then passed over a Pall 0.2 micrometer polypropylene syringe filter. The columns were held at 55 °C and the flow rate was 0.8 mL/min. All molecular weight data are reported against Agilent polystyrene standards (Polystyrene calibration kit S-M-10 part # PL2010-0100).
  • Hollow fiber membranes were extracted in water to determine the concentration of nitrogen (“total nitrogen”, or TN) in the aqueous extract.
  • Ten dry fibers approximately 30 inches in length were weighed, then placed in a 40 mL glass vial, to which 25 mL of ultrapure water (obtained from a Milli-Q Gradient A10 lab water purification system, available as catalog number ZMQS6V0T1 from MilliporeSigma, St. Louis, MO) was added.
  • the vial opening was covered with aluminum foil, and the vial was placed in an oven (Thelco Laboratory Oven) set to a temperature of 50 °C.
  • the vial was removed from the oven.
  • the aqueous extract was filtered with a 0.45 micrometers polypropylene syringe fdter (available as Target2 from Fisher Scientific) into a separate 20 mL glass vial. Prior to being used, the syringe filter was flushed with 20 mL of ultrapure water.
  • the concentration of total nitrogen (TN) in aqueous extracts was measured on a commercially available Total Organic Carbon Analyzer (available as TOC-L from Shimadzu Scientific Instruments) with a Total Nitrogen Module (available as TNM-L).
  • the TN curve was calibrated over the range from 0 to 20 ppm TN using potassium nitrate, with check standards (6.8 ppm TN by ⁇ -vinvlpy rrolidonc) run before and after the aqueous extract samples tested.
  • TN data are reported as milligrams of TN per gram of fiber (mg/g).
  • Nuclear magnetic resonance spectra were obtained using a Bruker Avance III 300 MHz instrument or a Bruker Avance III 500 MHz equipped with a broadband cryoprobe.
  • Proton ( 1 H) spectra were obtained at a 15° pulse angle and a relaxation delay of 4 seconds.
  • aqueous extract 4 mL of aqueous extract were transferred to a dried, weighed glass vial. The extract was rehydrated with 600 pL (microliters) of D2O solution. Samples were then transferred to an NMR sample tube using a glass Pasteur pipette. H NMR spectra were collected using a 15° pulse and 0.1s relaxation delay over 128 scans using a Bruker Avance 600 MHz spectrometer equipped with an inverse cryoprobe.
  • Scanning electron microscopy images were obtained using secondary electron imaging (SEI), which is used to image surface morphology of a sample. Analysis was performed on the Hitachi SU8230 field emission scanning electron microscope (HITACHI, Schaumburg, IL). A low accelerating voltage of 2.0 keV, 10 pA current, and working distance of 3.5-4.5 mm were used. To reduce the likelihood of sample charging and allow for improved imaging, samples were sputter coated with a thin gold/palladium conductive coating prior to analysis.
  • SEI secondary electron imaging
  • the reactant solution was frozen in liquid nitrogen, the entire apparatus pumped down to > 0.4 mTorr, and the toluene was statically distilled into the receiving flask which was cooled in liquid nitrogen. After the distillation was complete, the apparatus was back-filled with argon, the stopcocks sealed, and the reaction vessel was transferred to a glovebox for storage.
  • the product obtained was 60.24 g sodium phenoxide as a white solid in 98% yield.
  • the reaction mixture was cooled to 43 °C and 12.88 g DEP (93.26 mmol, 0.50 equivalents) and 4.93 g DIPEA (38.1 mmol, 0.20 equivalents) were added to the reaction and the temperature was maintained at 50 °C for 2 hours before cooling to room temperature. The solids were filtered and the reaction mixture concentrated under reduced pressure. The product was isolated by recrystallization from isopropanol to give 50.0 g of 2-(bromomethyl)-4-fluoro-l-(4- fluorophenyl) sulfonyl benzene as an off-white solid in 77% yield.
  • reaction was warmed to room temperature and diluted with 200 mL each H2O and MeOH and transferred to a 3 L round bottom flask and cooled to 0 °C in an ice bath. 21.73 g NaBH 4 (574.4 mmol, 2.4 equivalents) was then added portionwise and the reaction allowed to warm to room temperature over 1 hour before cooling once more to 0 °C.
  • the reaction mixture was acidified to pH 5-6 with 2 M HO and extracted with 3 x 350 mL portions EtOAc. The combined extracts were washed with saturated aqueous NaHCO, and brine. The washed extract was dried over MgSOj. filtered over celite, and concentrated under reduced pressure.
  • the monomer and solvent were stirred with the 2-phenyl-2- oxazolinium tetrafluoroborate for 1 hour and the vessel was equipped with a distillation bridge connected to the 250 mL Schlenk flask containing the 2-(chloromethyl)-4-fluoro-l-(4- fluorophenyl) sulfonyl benzene and potassium iodide.
  • the monomer and solvent solution was freeze-pump-thawed for 3 cycles before evacuating the entire apparatus and statically distilling the monomer and solvent into the receiving/reaction vessel. After the static distillation had completed, the reactant solution was heated to 70 °C until NMR analysis indicated about 90% conversion.
  • the polymerization was terminated by addition of 1.63 mL methanol (40.4 mmol, 10 equivalents) until the living chain-end signal at 4.90 ppm in CD 3 CN had disappeared by X H NMR. After the chain end had been consumed, the reactant solution was filtered over a plug of cotton and concentrated. The crude was refluxed overnight with methyl tert-butyl ether and decanted. The polymer was dried in a vacuum oven at 60 °C overnight 19.41 g of poly(ethyl oxazoline)-a-2-N-benzyl-4,4'- difluorodiphenylsulfone as a white resinous solid in 92% yield.
  • the monomer and solvent were stirred with the 2-phenyl-2- oxazolinium tetrafluoroborate for 1 hour and the vessel was equipped with a distillation bridge connected to the 250 mL Schlenk flask containing the 2-(chloromethyl)-4-fluoro-l-(4- fluorophenyl) sulfonyl benzene and potassium iodide.
  • the monomer and solvent solution was freeze-pump-thawed for 3 cycles before evacuating the entire apparatus and statically distilling the monomer and solvent into the receiving/reaction vessel. After the static distillation had completed, the reactant solution was heated to 70 °C until NMR analysis indicated about 90% conversion.
  • the polymerization was terminated by addition of 817 pL (microliters) methanol (20.2 mmol, 10 equivalents) until the living chain-end signal at 4.90 ppm in CD 3 CN had disappeared by NMR.
  • Graft Copolymer Example 1 (GCE1): Polyfether sulfone)-graft-polv(ethyl oxazoline) 30 wt.%. 1.9 mol% polyfethyl oxazoline) 50mer sidechains
  • the resin kettle was equipped with a heating mantle connected to a J-KEM temperature controller affixed with a ! inch stainless-steel thermocouple inserted into the reaction vessel.
  • the resin kettle was also equipped with a stainless-steel mechanical stir shaft equipped with a stainless-steel backed Teflon stir blade and a 4-prong propeller.
  • the resin kettle was also equipped with a ! inch stainless-steel dip tube inserted into the reactant solution to deliver a steady N2 stream.
  • the resin kettle was equipped with a short path distillation head equipped with a thermocouple and a 500 mL pear shaped flask immersed in a dry ice isopropanol bath.
  • Graft Copolymer Example 2 (GCE2): Polytether sulfone)-graft-poly(ethyl oxazoline) 15 wt.%. 0,85 mol% polvtethyl oxazoline) 50mer sidechains
  • the resin kettle was equipped with a heating mantle connected to a J-KEM temperature controller affixed with a ‘A inch stainless-steel thermocouple inserted into the reaction vessel.
  • the resin kettle was also equipped with a stainless-steel mechanical stir shaft equipped with a stainless-steel backed Teflon stir blade and a 4-prong propeller.
  • the resin kettle was also equipped with a 0.25 inch stainless-steel dip tube inserted into the reactant solution to deliver a steady N 2 stream.
  • the resin kettle was equipped with a short path distillation head equipped with a thermocouple and a 500 mL pear shaped flask immersed in a dry ice isopropanol bath.
  • Graft Copolymer Example 3 Polylether sulfone)-graft-polv(ethyl oxazoline) 5 wt.%, 0.24 mol% polvtethyl oxazoline) 50mer sidechains
  • the resin kettle was equipped with a heating mantle connected to a J-KEM temperature controller affixed with a 0.25 inch stainless-steel thermocouple inserted into the reaction vessel.
  • the resin kettle was also equipped with a stainless-steel mechanical stir shaft equipped with a stainless-steel backed Teflon stir blade and a 4-prong propeller.
  • the resin kettle was also equipped with a 0.25 inch stainless-steel dip tube inserted into the reactant solution to deliver a steady N2 stream.
  • the resin kettle was equipped with a short path distillation head equipped with a thermocouple and a 500 mL pear shaped flask immersed in a dry ice isopropanol bath.
  • Graft Copolymer Example 4 (GCE4): Polvtether sulfone)-graft-polv(ethyl oxazoline) 30 wt.%, 3,7 mol% polvtethyl oxazoline) 25mer sidechains
  • the resin kettle was equipped with a heating mantle connected to a J-KEM temperature controller affixed with a 0.25 inch stainless-steel thermocouple inserted into the reaction vessel.
  • the resin kettle was also equipped with a stainless-steel mechanical stir shaft equipped with a stainless-steel backed Teflon stir blade and a 4-prong propeller.
  • the resin kettle was also equipped with a 0.25inch stainless-steel dip tube inserted into the reactant solution to deliver a steady N2 stream.
  • the resin kettle was equipped with a short path distillation head equipped with a thermocouple and a 500 mL pear shaped flask immersed in a dry ice isopropanol bath.
  • a polymer dope (i.e., casting solution) was prepared with PES, PEG400, NMP, and GCE1 according to the amounts in Table 2.
  • the polymer dope was mixed using a centrifugal mixer (available as SpeedMixerTM from FlackTek) for 15 seconds at 800 rpm, followed by 9.75 minutes at 1200 rpm, then heated in an oven set to 50 °C for 30 minutes to 1 horn, then mixed again at the same settings.
  • the resulting polymer dope was a macroscopically homogenous, viscous liquid.
  • the polymer dope was kept in an oven set to 50 °C until right before casting.
  • a glass plate and notch bar were both pre-heated in the same oven and removed immediately prior to each casting.
  • a bead of polymer dope was poured onto the glass plate and was spread into a thin film using a notch bar coater with a gap height of 10 mil (254 micrometers).
  • the film was immersed in a precipitation bath comprising 1500 mL of NMP and 2000 mL of water at a temperature of 50 °C.
  • the thin film precipitated within a few seconds, to form a white, opaque membrane, at which point the membrane was transferred to a second water bath for extraction. After sitting in the second water bath overnight, the membrane was placed in an oven set to 50 °C to dry.
  • the membrane was tested using the Water and Isopropanol Drop Wicking Test to determine porosity and hydrophobicity /hydrophilicity.
  • a polymer dope was prepared with the following composition: 21.7 wt% PES, 2.4 wt% GCE1, 36.5 wt% PEG400, 36.5 wt% NMP, and 3 wt% deionized water.
  • the polymer dope was mixed using a centrifugal mixer (available as SpeedMixerTM from FlackTek) for 15 seconds at 800 rpm, followed by 9.75 minutes at 1200 rpm.
  • the polymer dope was transferred to a hopper, heated to 50 °C, and allowed to degas overnight.
  • the resulting polymer dope was transparent and macroscopically homogeneous.
  • a gear pump (Model H-9000, available from Zenith Pumps, 1710 Airport Road, P.O. Box 5020, Monroe, NC 28111-5020) was used to pump the polymer dope from the hopper to a spinneret die with an inner channel for a bore liquid and an annular gap for the polymer dope, separated by a needle.
  • the flow path was heated to 50 °C and included a 15 micrometer in-line filter.
  • the spinneret die had an annular gap of 410 micrometers, a needle outer diameter of 300 micrometers, and a needle inner diameter of 150 micrometers.
  • the spinneret die was fixed at a height of 26.5 cm above an aqueous precipitation bath and was heated to 50 °C.
  • the bore liquid consisted of 45 wt% PEG400, 45 wt% NMP, and 10 wt% deionized water.
  • the extruded polymer dope fell through a climate-controlled zone with an air temperature of 54 °C and a relative humidity of 89%. Air was blown through the climate-controlled zone to achieve a steam mass flow rate of 1.5 kg/h. The extruded polymer dope then entered an aqueous precipitation bath heated to 50 °C, thereby vitrifying the pore structure of the hollow fiber membrane. The hollow fiber membrane was collected at a line speed of 135 ft/min and wound on a drum.
  • the resulting hollow fiber membrane bundle was flushed down the lumen volume with approximately 4 L of deionized water, then extracted in water heated to 90 °C for 1 horn, and finally dried at room temperature overnight.
  • the hollow fiber membrane had an inner diameter of 200 micrometers and an average wall thickness of 63 micrometers.
  • the hollow fiber membrane was analyzed using NMR spectroscopy and the membrane comprised 91.01 wt% PES, 7.83 wt% GCE1, 1.04 wt% PEG400, and 0.126 wt% NMP.
  • the hollow fiber membrane was extracted and the total nitrogen (TN) in the aqueous extract was 0.1358 mg/g.
  • the aqueous extract was analyzed with NMR spectroscopy and no poly(ethyl oxazoline) was detected.
  • FIG. 3 Scanning electron micrographs of the hollow fiber membrane are shown in FIG. 3, FIG. 4, and FIG. 5.
  • PES 9 wt% poly(2-ethyl-2 -oxazoline) (available under the trade name Aquazol® 50 from Polymer Chemistry Innovations, 4231 S. Fremont Ave., Arlington, AZ 85714-1628), 30.3 wt% polyethylene glycol) with a molecular weight of 200 g/mol (PEG200, available from J.T. Baker, 100 Matsonford Road, Suite 200 Radnor, PA 19087), 33.2 wt% NMP, and 2 wt% deionized water.
  • the polymer dope was transferred to a hopper, heated to 50 °C, and allowed to degas overnight. The resulting polymer dope was transparent and macroscopically homogeneous.
  • a gear pump was used to was pump the polymer dope from the hopper to a spinneret die with an inner channel for a bore liquid and an annular gap for the polymer dope, separated by a needle.
  • the flow path was heated to 50 °C and included a 15 micrometers in-line filter.
  • the spinneret die had an annular gap of 410 micrometers, a needle outer diameter of 300 micrometers, and a needle inner diameter of 150 micrometers.
  • the spinneret die was fixed at a height of 27 cm above an aqueous precipitation bath and was heated to 50 °C.
  • the bore liquid consisted of 50 wt% PEG200, 45 wt% NMP, and 5 wt% deionized water.
  • the extruded polymer dope fell through a climate-controlled zone with an air temperature of 52 °C and a relative humidity of 90%.
  • the extruded polymer dope then entered an aqueous precipitation bath heated to 50 °C, thereby vitrifying the pore structure of the hollow fiber membrane.
  • the hollow fiber membrane was collected at a line speed of 146 ft/min and wound on a drum.
  • the resulting hollow fiber membrane bundle was extracted in water heated to 90 °C for 1 hour, then dried at room temperature overnight.
  • the hollow fiber membrane had an inner diameter of 202 micrometers and an average wall thickness of 64 micrometers.
  • the hollow fiber membranes were extracted and the total nitrogen (TN) in the aqueous extract was 0.3699 mg/g.
  • Table 3 Total Nitrogen in Aqueous Extract

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Abstract

L'invention concerne des macromères de diphénylsulfone fonctionnels comportant des chaînes latérales polymères greffées, des copolymères comportant des motifs de répétition dérivés des macromères de diphénylsulfone fonctionnels à chaînes latérales polymères greffées et des articles polymères poreux contenant ces copolymères. Les chaînes latérales polymères greffées contiennent des motifs de répétition dérivés de composés de 2-oxazoline. L'article polymère poreux est généralement une membrane qui peut être une feuille plate ou une fibre creuse. Les articles polymères poreux peuvent être utilisés pour séparer des mélanges de biomatériaux présentant différentes tailles moyennes sur la base de la taille moyenne des pores des articles polymères poreux. Par exemple, des biomatériaux tels que des bactéries, des protéines, des virus et des cellules peuvent être séparés sur la base de leur taille.
PCT/IB2024/055285 2023-05-31 2024-05-30 Macromères de diphénylsulfone fonctionnels comportant des chaînes latérales polymères greffées, et copolymères et articles préparés à partir de ceux-ci Pending WO2024246814A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070231652A1 (en) * 2006-03-31 2007-10-04 Fujifilm Corporation Polymer Electrolyte, Membrane/Electrode Assembly, and Fuel Cell
JP2007269718A (ja) * 2006-03-31 2007-10-18 Fujifilm Corp 新規芳香族化合物、その製造方法、及びそれにより得られる重縮合ポリマー
JP2008120956A (ja) * 2006-11-15 2008-05-29 Toyobo Co Ltd スルホン酸基含有ポリマー、その製造方法及びその用途
WO2017052226A1 (fr) * 2015-09-22 2017-03-30 주식회사 엘지화학 Polymère séquencé et membrane électrolytique polymère le comprenant
WO2017171290A1 (fr) * 2016-03-29 2017-10-05 주식회사 엘지화학 Polymère séquencé et membrane électrolytique polymère le comprenant
WO2021101987A1 (fr) 2019-11-21 2021-05-27 Emd Millipore Corporation Membranes hydrophiles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070231652A1 (en) * 2006-03-31 2007-10-04 Fujifilm Corporation Polymer Electrolyte, Membrane/Electrode Assembly, and Fuel Cell
JP2007269718A (ja) * 2006-03-31 2007-10-18 Fujifilm Corp 新規芳香族化合物、その製造方法、及びそれにより得られる重縮合ポリマー
JP2008120956A (ja) * 2006-11-15 2008-05-29 Toyobo Co Ltd スルホン酸基含有ポリマー、その製造方法及びその用途
WO2017052226A1 (fr) * 2015-09-22 2017-03-30 주식회사 엘지화학 Polymère séquencé et membrane électrolytique polymère le comprenant
WO2017171290A1 (fr) * 2016-03-29 2017-10-05 주식회사 엘지화학 Polymère séquencé et membrane électrolytique polymère le comprenant
WO2021101987A1 (fr) 2019-11-21 2021-05-27 Emd Millipore Corporation Membranes hydrophiles

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