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US-12616941-B2 - Surface-modified polyethersulfone membranes and method of making thereof

US12616941B2US 12616941 B2US12616941 B2US 12616941B2US-12616941-B2

Abstract

The present disclosure is related to a polymeric membrane, comprising a modified surface obtained from coating with hydrophilic monomers and curing the hydrophilic monomers with actinic irradiation, preferably UV light, wherein the hydrophilic monomers comprise at least one amino moiety; at least one polyoxyalkylene unit; and at least one (meth)acrylate moiety.

Inventors

  • Sven Frost
  • Frans A. Audenaert
  • Pierre-Alexandre Bourgeois
  • Tim Wolf

Assignees

  • SOLVENTUM INTELLECTUAL PROPERTIES COMPANY

Dates

Publication Date
20260505
Application Date
20201104
Priority Date
20191108

Claims (13)

  1. 1 . A polymeric membrane, comprising a modified surface obtained from coating with hydrophilic monomers and curing the hydrophilic monomers with actinic irradiation, wherein the hydrophilic monomers comprise (i) at least one amino moiety; (ii) at least one polyoxyalkylene unit; and (iii) at least one (meth)acrylate moiety; wherein the hydrophilic monomer is a hydrophilic monomer according to any one of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), or (XIV): wherein R is a linear or branched alkyl or alkoxy, wherein m and n may be different or the same, wherein m and n may each be in a range of from 1 to 100; wherein x, y, z may be different or the same, wherein x, y, z may be each in a range of from 1 to 100.
  2. 2 . The polymeric membrane according to claim 1 , wherein the polymeric membrane is selected from polymeric sulfone membranes, polyethylene membranes, polypropylene membranes, polyvinylidene difluoride membranes and polyacrylonitrile membranes.
  3. 3 . The polymeric membrane according to claim 2 , wherein the polymeric membrane is a polymeric sulfone membrane selected from polysulfone, polyethersulfone, and polyarylsulfone.
  4. 4 . The polymeric membrane according to claim 1 , wherein the at least one polyoxyalkylene unit of the hydrophilic monomers is selected from polyethers.
  5. 5 . The polymeric membrane according to claim 1 , wherein the hydrophilic monomers comprise acrylate moieties in an amount of from 1 to 10.
  6. 6 . The polymeric membrane according to claim 1 , wherein the hydrophilic monomers are obtained from reacting at least one polyoxyalkylamine with at least one (meth)acrylate compound.
  7. 7 . The polymeric membrane according to claim 1 , wherein that the amount of surface-bound IgG to the membrane is lower than 16 μg/cm 2 .
  8. 8 . A process for producing a surface-modified polymeric membrane, comprising the following steps: (I) Providing a polymeric membrane; (II) Applying a solution comprising hydrophilic monomers to the polymeric membrane; and (III) Irradiating the polymeric membrane with actinic radiation, wherein the hydrophilic monomers comprise (i) at least one amino moiety; at least one polyoxyalkylene unit; and at least one (meth)acrylate moiety; wherein the hydrophilic monomer is a hydrophilic monomer according to any one of formulae (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), or (XIV): wherein R is a linear or branched alkyl or alkoxy, wherein m and n may be different or the same, wherein m and n may each be in a range of from 1 to 100; wherein x, y, z may be different or the same, wherein x, y, z may be each in a range of from 1 to 100.
  9. 9 . The process according to claim 8 , wherein the actinic radiation in step (III) is UV light.
  10. 10 . The process according to claim 8 , wherein irradiating with actinic radiation is carried out an irradiation dose of a mean value in the range of from 1 to 25 J/cm 2 .
  11. 11 . The process according to claim 8 , wherein irradiating with actinic irradiation is carried out at wavelengths greater than 300 nm.
  12. 12 . The process according to claim 8 , wherein the polymeric membrane is selected from polymeric sulfone membranes, polyethylene membranes, polypropylene membranes, polyvinylidene difluoride membranes and polyacrylonitrile membranes.
  13. 13 . A method for microfiltration, nanofiltration, or ultrafiltration, said method comprising contacting a solution or mixture to be filtered with the polymeric membranes according to claim 1 , wherein said method is for water purification, filtration in the production of food, filtration in the production of beverages, filtration in the electronics industry, medical filtration or filtration in the biopharmaceutical industry.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a national stage filing under 35 U.S.C. 371 of PCT/IB2020/060395, filed Nov. 4, 2020, which claims the benefit of European Application No. 19208127.1, filed Nov. 8, 2019, the disclosure of which is incorporated by reference in its/their entirety herein. FIELD The present disclosure relates to hydrophilic microporous membranes comprising a modified surface. In addition, the present disclosure relates to a process for producing such hydrophilic membranes by modification of microporous membranes with certain hydrophilic monomers and actinic irradiation such as UV light. The present disclosure further relates to use of the modified membranes for filtration purposes of aqueous media. BACKGROUND Polymeric membranes such as aromatic polysulfones are widely used in industry as base material for micro- and ultrafiltration materials. In certain applications, it is desirable that the surface of the membranes is hydrophilic. For example, it may be desirable to obtain a low protein binding tendency. This may be the case in pharmaceutical applications such as filtration of media in biopharmaceutical processes where protein-containing solutions are processed. In exemplary processes known in the art, the hydrophobic polyethersulfone (PES) is blended with hydrophilic polymers like polyvinylpyrrolidone (PVP), polyethyleneglycol (PEG) and sulfonated polyethersulfone (SPES) to render the membrane surface hydrophilic. However, leaching of the hydrophilic polymers out of the polymer matrix may lead to a decrease of the membrane hydrophilicity over time as well as to a contamination of the permeate stream. Accordingly, the scope and duration of the application of a certain membrane may be limited. On the one hand, this is relevant for applications where contamination of the filtrate with polymer compounds is generally undesired, which is particularly true for pharmaceutical processes. On the other hand, long-term hydrophilicity and thus high protein resistance is required to minimize the loss of target proteins (such as monoclonal antibodies), e.g. during the purification of biopharmaceuticals (e.g. sterile filtration). Various efforts to fix hydrophilic polymers into a hydrophobic polymer matrix (such as a PES matrix) have been published. Similarly, it has been also tried to modify the PES membrane surface to obtain a certain hydrophilicity. For example, U.S. Pat. No. 9,045,602 B2 discloses a method for producing a microporous membrane wherein a polymer is fixed by means of irradiation with an E-beam onto the surface of the membrane. This membrane is described as intended to be used in hemodialysis, virus filtration and sterile filtration. U.S. Pat. No. 5,468,390 describes the modification of an aryl polysulfone membrane using a photo-grafting process without the use of a photoinitiator. The membrane is UV-irradiated for a certain time at wavelengths of about 254 nm in the presence of hydrophilic vinyl monomers. Similarly, U.S. Pat. No. 6,852,769 B2 discloses a method to modify a polymeric photoactive sulfone membrane in an attempt to reduce protein fouling. The method comprises dipping the sulfone membrane into a solution containing hydrophilic monomers and a chain transfer agent and exposing the membrane to UV radiation in the presence of a filter. Without wanting to diminish the efforts known from the prior art, there still exists a need in the art for hydrophilic membranes exhibiting long-term hydrophilicity, show low protein adsorption even after exposition to extraction conditions, and which are therefore useful for various applications in micro- and nanofiltrations. Particularly desirable are hydrophilic membranes for biopharmaceutical applications. There also exists a need for an efficient process for producing such membranes. SUMMARY The present disclosure provides a polymeric membrane, comprising a modified surface obtained from coating with hydrophilic monomers and curing the hydrophilic monomers with actinic irradiation, preferably UV light, wherein the hydrophilic monomers comprise (i) at least one amino moiety;(ii) at least one polyoxyalkylene unit; and(iii) at least one (meth)acrylate moiety. The present disclosure further provides a process for producing a surface-modified polymeric membrane, comprising the following steps: (I) Providing a polymeric membrane;(II) Applying a solution comprising hydrophilic monomers to the polymeric membrane; and(III) Irradiating the polymeric membrane with actinic radiation, preferably UV light,wherein the hydrophilic monomers comprise(i) at least one amino moiety;(ii) at least one polyoxyalkylene unit; and(iii) at least one (meth)acrylate moiety. Furthermore, the present disclosure relates to certain uses in applications in filtration applications of liquid media. These applications comprise the purification of biopharmaceuticals and chemical pharmaceuticals, water, blood and beverages. DETAILED DESCRIPTION Before any em