Non-fluorinated surface modifications for hydrophobic membranes

Abstract

A porous polymeric membrane having a surface treatment that includes a porous membrane having an average pore size between about 0.01 and 0.45 microns formed of a first polymer, said porous membrane having a surface which is modified on its surface with a solution of a second polymer; wherein the second polymer further comprises between 1.0-10% DMS or ALO cross-linked, and / or HDDA.

Description

Attorney Docket No. P24-188-SEC-WO01NON-FLUORINATED SURFACE MODIFICATIONS FOR HYDROPHOBIC MEMBRANESRELATED APPLICATIONS

[0001] The present application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 713,281, filing date October 29, 2024, the entire content of which is incorporated herein in its entirety.FIELD

[0002] This application relates to membranes for use in the biotechnology7or life science industry. In particular, embodiments of the technologies disclosed herein relate to surface treatments for hydrophobic membranes useful in venting, filtration, purification, or concentration applications.BACKGROUND

[0003] Technologies disclosed herein relate to membranes, for example, porous membranes further comprising a hydrophobic surface(s). Moreover, technologies relate to a microporous or ultrafiltration membrane modified to produce a hydrophobic surface(s) including the membrane pore surfaces and to processes for forming such a membrane.

[0004] Membranes and chemical surface treatments for membranes have commonly used fluorinated membranes and device formats. The chemical and biological inertness, thermal stability, and hydrophobicity7inherently associated with fluoroalkyl materials has led to significant rises in use. Fluorinated membranes have also found widespread use in the health and related industries. For example, the necessity of producing aseptic vent membranes for use in medical / biological devices has also naturally led to the selection of poly(tetrafluoroethylene) PTFE as the choice material in membrane applications. And, aseptic materials have been generated by chemical sterilization, notably by steam treatment, gamma irradiation, or treatment with ethylene oxide. The compatibility of PTFE with sterilizing chemicals and treatments, especially at elevated temperatures, is a known, desirable material property7characteristic of PTFE. One problem with the use of PTFE as a vent membrane material under steam treatment is pore blockage due to condensation of oil. from the machinery used to generate the steam, or water or both. The resulting loss of airAttorney Docket No. P24-188-SEC-WO01 permeability of the clogged membrane effectively reduces the membrane's utility as a gas vent. This condensation problem has led to the search and development of more hydrophobic and oleophobic membrane materials as substitutes for PTFE. A more acute problem concerns the chemical sterilization of membrane materials for use under aseptic conditions. Chemical sterilization, particularly with ethylene oxide, very often generates additional issues such as toxicity and waste disposal that raises serious health, environmental and economic concerns. These concerns have led to the w idespread use of ionizing radiation for sterilization of materials used in medical and biological devices. At least one major disadvantage of PTFE is its inherent instability towards ionizing irradiation. Ionizing irradiation of PTFE membranes results in the undesirable property of reduced mechanical strength. This loss of mechanical strength places severe restrictions in the use of PTFE membranes under moderate pressures. In addition, coatings adversely affect the permeability properties of porous substrates, e.g., flux.

[0005] Attempts to solve these drawbacks of irradiation have included the use of coatings disposed on membranes. Coating of materials allows the retention of the desirable bulk materials properties while only altering the surface and interfacial properties of the membrane substrate. Hydrophobic and oleophobic coatings have found use in the electronics industry as protective barriers for electronic components. However, coating membranes has not been a practical approach for modifying the surface properties of membranes since the tortuous morphologies associated with membranes rarely produce continuous, even, durable coatings. Furthermore, since coatings are not permanently anchored (bonded) to the underlying substrate, i.e., the membrane, the coated materials are susceptible to wear, e.g., delamination. Also, organic coatings can produce extractables, which can harm biological products. Importantly, polyfluoroalkyl and / or perfluoroalkyl substances (PF As), so called “forever chemicals,” are being highly regulated or eliminated for environmental reasons. Each of the foregoing drawbacks presents remediation challenges.

[0006] Past attempts for manufacturing hydrophobic membranes by surface modifications include the casting of hydrophobic PVDF (poly vinylidene fluoride) and hydrophobic poly ether sulfone (PES) membranes. PVDF membranes have been manufactured in a wide range of pore sizes (0.1 , 0.2, 0.45, 0.65. 1.0 microns). Pore sizes (0.2 microns) of PES membrane with hydrophobic chemistry have been commercially available for several years The hydrophobic modification is carried outAttorney Docket No. P24-188-SEC-WO01 by polymerizing and cross-linking molecules containing fluorocarbons on the membrane surface. These membranes are used in variety of devices across industrial applications, primarily for venting applications.

[0007] At least one monomer used for rendering a surface of a membrane phobic is called Perfluoroocty l ethyl acry late (POEA). This chemical falls under a list of chemicals, generally called PF As and was banned by the ECHA [European Chemicals Agency] under the REACH program [Registration, Evaluation, Authorization and Restriction of Chemicals], Attempts have been made to substitute POEA with PDA (1H, IH-Perfluoro-n-decyl acrylate). However, PDA also came under regulation. And, regulatory' bodies continue to focus on PF As, putting stringent threshold limits on impurity levels for degradation products as well as potential degradation products associated with these PF As, which is generally 25 parts per billion (PPB). Chemistries for hydrophobic membranes, and related products, include 2-Propenoic acid, 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl ester (DDA-19), a short-chain fluorocarbon monomer that was specifically developed to replace the previously used C8 fluorocarbon chemistry, which was restricted by REACH (European legislation) in 2020. Unfortunately, recent pronouncements from ECHA (European Chemicals Agency) on PF As and related materials has imperiled DDA-19 chemistries, i.e., restriction is likely. Accordingly, PFAs-free alternatives to replace the DDA-19 chemistry to ensure business continuity and compliance with regulations is now an important goal.

[0008] With the foregoing in view, alternatives to DDA-19 and other PF As for surface treatments, which are not currently subject to regulation for porous membranes, represent an advance in the art. A porous membrane having a surface treatment which is as hydrophobic, and / or more hydrophobic, than presently available membranes, and is not subject to regulation represents an advance in the art. In addition, a membrane having a surface treatment which retains its mechanical strength after being exposed to sterilizing ionizing radiation and which, upon environmental and other sources of degradation, does not break down into restricted or regulated components or molecules represents an advance in the art.Attorney Docket No. P24-188-SEC-WO01SUMMARY OF THE DISCLOSURE

[0009] Embodiments of the disclosure include surface treatments, wherein a surface chemistry fonnulation comprises a DMS monomer between 1% and 5.5% by weight DMS, and DMTS as a solvent for disposition on a PES membrane, which may be a symmetric or asymmetric membrane.

[0010] Embodiments of the disclosure include porous polymeric membranes which comprise a porous membrane having an average pore size between about 0.001 and 10 microns formed of a first polymer, said substrate having a surface which is modified on its surface with a cross-linked second polymer formed from a polymerizable nonfluorine containing monomer, substantially as shown in and / or described in connection with at least one of the figures or tables, as set forth more completely in the claims, are disclosed. Novel and inventive features of the present disclosure, as well as details of exemplary embodiments thereof, will be more fully understood from the following description and drawings. Novel approaches for both monomers and cross-linkers, avoiding the use of any perfluoroalkyl or polyfluoroalkyl (PFA) molecules in order to meet present, and possibly future, regulatory requirements. Approximately twenty-seven (27) monomers were sourced and screened in the lab using, primarily, PES membranes, the monomers belonging to at least one of 1) hydrocarbon-based or 2) silicon-based. Two performance characteristics were measured. 1) a measure of hydrophobicity using wettability7of the membrane by an isopropanol and water solution and 2) surface-water contact angle. Surface chemistry targets and methods according to some embodiments of the disclosure include a series of acrylates / allylic (called monomers), which are used alone or in conjunction with bi-functional acrylates (called cross-linkers), which were studied using the surface modification chemistry as described herein.

[0011] In some embodiments, the PES membrane comprises pore sizes of any suitable size for a variety7of filtration applications as are known to those of skill in the art. In some embodiments, the membrane comprises pore sizes between 0. 1-10.0 microns. In some embodiments, the membrane comprises pore sizes between 0. 1-5.0 microns. In some embodiments, the membrane comprises pore sizes between 0.05-1 microns. In some embodiments, the membrane comprises pore sizes between 0.1-0.22 microns. In some embodiments, the membrane comprises pore sizes of approximately 0.2-0.45 microns. Also, in some embodiments, the substrate comprises a woven or non-wovenAttorney Docket No. P24-188-SEC-WO01 material. For example, suitable substrates comprise polyethylene, polypropylene, nylons, and other suitable polyolefins and / or polyamides.

[0012] These advances and others embodied herein will become clear from the description, claims, and figures below. Various benefits, aspects, novel and inventive features of the present disclosure, as well as details of exemplary embodiments of the coated membranes and venting filtration devices comprising the coated membranes thereof, will be more fully understood from the following description and drawings. Embodiments of the disclosure comprise a porous polymeric membrane that can be incorporated into a filter unit to facilitate venting of air or gas. So, the manner in which the features disclosed herein can be understood in detail, more particular descriptions of the embodiments of the disclosure, briefly summarized above, may be had by reference to the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the described embodiments may admit to other equally effective surface treatments, methods, and / or materials. It is also to be understood that elements and features of one embodiment may be found in other embodiments without further recitation and that, where possible, identical reference numerals have been used to indicate comparable elements that are common to the figures. As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary' skill in the art to which these embodiments pertain.

[0013] A surface is hydrophobic when its static water contact angle 0 is >90° and is generally considered hydrophilic when 0 is <90°. Superphobic and superhydrophobic are defined herein as having a static water contact angle 0 of approximately >150°. Membrane surface modification or treatment is defined as a chemical process to get surface properties, e.g., hydrophobicity7, a range of surface tension(s), etc., while retaining the bulk membrane properties such as mechanical and chemical resistance, morphology, pore sizeBRIEF DESCRIPTION OF THE DRAWING

[0014] The sole figure depicts a flowchart for a method for making a coated membrane, according to some embodiments of the disclosure.Attorney Docket No. P24-188-SEC-WO01DESCRIPTION OF SOME EMBODIMENTS

[0015] Embodiments of the disclosure include poly ethersulfone (PES) membranes having surface modifications using, e.g.. various hydrocarbons, e.g., ALO or ALO and HDDA or silicone-based molecules DMS or DMS and HDDA. The PES membranes having the surface treatments showed considerable increase in the hydrophobicity of the membrane surface. Embodiments of the membranes discussed herein are often used for various vent filter applications. The surface treatment step was achieved through the polymerization of acrylate molecules, and / or by cross-linking with multi-acrylate molecules under an energy source of E-beam or ultraviolet (UV) (in formulations having an initiator(s)). It is to be understood that in some embodiments, the PES membrane(s) comprises pore sizes of any suitable size for a variety of filtration applications as are known to those of skill in the art. In some embodiments, the membrane comprises pore sizes between 0.001-10.0 microns. In some embodiments, the membrane comprises pore sizes between 0.01-5.0 microns. In some embodiments, the membrane comprises pore sizes between 0.05-1 microns. In some embodiments, the membrane comprises pore sizes between 0.1-0.22 microns. In some embodiments, the membrane comprises pore sizes of approximately 0.2-0.45 microns. Also, in some embodiments, the substrate comprises a woven or non-woven material. For example, suitable substrates comprise polyethylene, polypropylene, nylons, and other suitable polyolefins and / or polyamides. Any of these membranes and substrates may be treated with the surface treatments discussed herein to produce porous polymeric membranes for filtration applications. The PES membranes described herein generally comprise asymmetric membranes, i.e., wherein the pore sizes get smaller starting from a first surface to a second surface opposite the first surface. The first side having the larger pore sizes is generally indicated as the open side or the dull side while the smaller pore sizes are the tighter side or shiny side.

[0016] Novel approaches for both monomers and cross-linkers and avoided use of any PFA molecules in order to meet regulatory' requirements. Surface chemistry' targets and methods according to some embodiments of the disclosure include a series of nonfluorinated functional acrylates / allylic (called monomers), such as hydrocarbons and silicon or siloxanes and bi-functional acrylates (called cross-linkers), which were studied using the surface modification chemistry described herein. It is to be furtherAttorney Docket No. P24-188-SEC-WO01 understood that some molecules have multiple reactive functionalities, which can sen e as either or both of a monomer and a cross-linker, e.g., ALO and DMS.Attorney Docket No. P24-188-SEC-WO01Attorney Docket No. P24-188-SEC-WO01Attorney Docket No. P24-188-SEC-WO01Attorney Docket No. P24-188-SEC-WO01

[0017] Table 1 depicts the results of a wettability on the dull side of a membrane having a surface treatment as in Process 1, using the twenty-seven monomers. Wettability is rate on a scale using a mixture of isopropanol-water mixture. Also shown are the water contact angles that the water makes with the surface-treated membrane.

[0018] Tables 2-5 list formulations for various surface chemistries comprising monomers and solvents, and some further comprising initiators and cross-linkers (and energy sources for promoting reactions), for disposition on various membranes. TableAttorney Docket No. P24-188-SEC-WO012 depicts the results of a wettability on the dull side of a membrane having a surface treatment as in Process 1 and water contact angle data for four differing formulations for DMS as the monomer. It is noted that the excellent results of 35% non-wettability are evident where DMS is cross-linked with HDDA and where DMS is cross-linked with DMS. Also shown are the water contact angles that the water makes with the surface-treated membrane.

[0019] Table 3 depicts wettability data for four formulations of ALO. 1) ALO cross-linked with HDDA in the presence of an initiator, using UV light to create the initiator free radicals, 2) ALO cross-linked with HDDA wherein E-beam creates the free-radicals, initiating polymerization and cross-linking 3) is ALO without using HDDA as a cross-linker, i.e.. ALO cross-linked with itself using DMPA as an initiator in the presence of UV light; and 4) wherein ALO is cross-linked with itself in the presence of an E-beam. Also shown are the water contact angles that the water makes with the surface-treated membrane. In some embodiments, a surface chemistry formulation comprising DMS as a monomer 1% and 5.5% by weight DMS, and DMTS as a solvent for disposition on a PES membrane, which may be a symmetric or asymmetric membrane. In some embodiments, a surface chemistry formulation comprising DMS as a monomer 2% and 5.5% by w eight DMS, and DMTS as a solvent for disposition on a PES membrane, which may be a symmetric or asymmetric membrane. In some embodiments, a surface chemistry formulation comprising DMS as a monomer 3% and 5.5% by weight DMS, and DMTS as a solvent for disposition on a PES membrane, which may be a symmetric or asymmetric membrane.

[0020] Table 4 depicts data using process 4 and DMS as a monomer. Process 4 is considered the simplest of the formulation solutions because there is only one monomer and no separate chemical initiator. In other words, the DMS is both a monomer and a cross-linker, cross-linking to other DMS molecules. It is noted that the wettability7seems largely independent of the amount of DMS in the formulation. Also shown are the water contact angles that the water makes with the surface-treated membrane.

[0021] Table 5 depicts wettability of the DMS chemistry on various membranes having 0.2 micron or 0.45 micron pore sizes. It is to be noted that PVDF and UPE membranes are symmetric, not asymmetric, as the PES membrane is. Also shown are the water contact angles that the water makes with the surface-treated membrane.Attorney Docket No. P24-188-SEC-WO01

[0022] The sole figure depicts a flowchart for a method 100 for making a coated membrane, according to some embodiments of the disclosure. At step 102 of the method 100, a solution is made. For example, the polymeric solution comprises making the chemi stry solution / mix with a monomer, e.g., one of the twenty-seven monomers shown in Graph 1A and Graph IB, and for some embodiments, a cross-linker and, optionally including an initiator, within a solvent. In some embodiments, the solvent is DMTS. However, the solvent is not limited to DMTS, e.g.. the solvent may also be monomer / polymer soluble alcohols such as butanol, hexanol, isopropyl alcohol, or hydrocarbon solvents such as decane, dodecane, etc.

[0023] At step 104, a membrane, which may be an asymmetric membrane or a symmetric membrane, is provided prepared. For example, the membrane may be a PES membrane. Other membranes may also be considered, i.e., UHMWPE. One way of preparing the membranes is to prepare a membrane sheet(s) for coating with the chemistry solution / mix from step 102. For example, cutting a desired size (e.g., 5” x 3"’) of base membranes for PES.

[0024] At step 106, the chemistry solution / mix is applied on a membrane surface. The application of the chemistry solution / mix can be done either by immersing the membrane sheet in the chemistry mix solution in a tray, e.g., a glass tray or by disposing the chemistry solution / mix directly on the membrane surface (in some embodiments, a wetted membrane surface) using, e.g., a pipette or other delivery means. Exemplary examples include having a monomer in an amount equal to approximately 1-10% of a solution. In some embodiments, the monomer may be crosslinked with itself, e.g., DMS. In some embodiments, the monomer DMS may be crosslinked using another monomer, e g., HDD A. Also. ALO may be cross-linked with itself or using HDDA as a cross-linker.

[0025] At step 108, the membrane sheets having the chemistry solution / mix is exposed to an energy source, e.g., UV / e-beam source for polymerization reaction, creating a polymeric coating on the membrane surface. For example, the application of approximately 75-100 kilograys (kGy).

[0026] At step 110, a w ashing step is employed to remove unreacted chemistry solution / mix using solvents (e.g., methanol and water or isopropyl alcohol and water).

[0027] At step 112, a drying step is employed to dry' the washed membrane (e.g., 60-100°C for 10-20 minutes). The method 100 ends following step 112.Attorney Docket No. P24-188-SEC-WO01

[0028] When polymerizing polymerizable monomers having more than one degree of unsaturation, an additional cross-linker in the coating of this disclosure need not be added. The three reactants, e.g., a polymerizable monomer, polymerization initiator and cross-linking agents are contacted with the porous membrane as a mixture in a solvent which is compatible with the three reactants and the porous membrane so that the desired free radical polymerization and cross-linking is achieved without the formation of a significant amount of slowly extractable by-products. If readily extractable by-products are formed, these can be removed by conducting a washing step with a suitable solvent subsequent to the coating step.

[0029] Generally, the polymerizable monomer is present in the reactant solution or formulation at a concentration between approximately 1% and approximately 10%. In some embodiments, there is between approximately 2.5% and 7.5% based upon the weight of the polymerizable monomer. The cross-linking agent, in some formulations, is present in an amount of between approximately 0.5% and approximately 5% byweight, based upon the weight of the polymerizable monomer. The polymerization initiator, which is optional, is present in an amount of between about 0.1% and about 1% by weight, based upon the weight of the polymerizable monomer. A polymerization initiator is generally chosen when ultra-violet rays are used to create free-radical(s) of the initiator(s). It is to be understood that, in some embodiments, the cross-linking agent can be utilized without the monomer and thereby functions as the polymerizable monomer.

[0030] Polymerization and cross-linking may be created by exposing the monomer reaction system to ultraviolet (UV) light, thermal sources, and / or ionizing radiation. Embodiments of the disclosure comprise using UV light because it is quick. The process comprises dipping the membrane substrate in the reactant solution or formulation, i.e., a solution containing the monomer, cross-linking agent, and the optional initiator, placing the membrane between two ultraviolet light transparent sheets such as polyethylene and exposing the sandwich to UV light. This process can be conducted continuously and the desired cross-linking coating is formed within minutes after UV exposure is initiated. By controlling the reactant concentrations and UV exposure, as set forth above, a composite is produced which is unplugged and has the same porous configuration as the membrane substrate. Furthermore, the composite membrane produced is wettable only by solvents that have a surface tension of less than about 25 dynes / cm. That is, the composites and / or coated membranes of this disclosureAttorney Docket No. P24-188-SEC-WO01 have a highly hydrophobic surface. And, composites and / or coated membranes of this disclosure retain their hydrophobicity even after being exposed to sterilizing ionizing radiation.

[0031] The composites of this disclosure, after being sterilized by exposure to gamma radiation, usually between about 2 and 5 MegaRads are capable of withstanding a forward or reverse pressure of at least 10 PSI. In addition, the sterilized membrane composite of this disclosure retains a desirable degree of hydrophobicity such that it is not wet by aqueous solutions including solutions containing surfactants. The composites are useful as gas vents to selectively pass gas through while preventing passage of organic and aqueous liquids through such as in the apparatus described in U.S. Pat. No. 3.854,907 which is incorporated herein by reference. Embodiments of the disclosure include membranes suitable for use in filtering devices. The membrane is a hydrophobic membrane incorporated into a filtering device that allows gas to be selectively vented, i.e., impervious to aqueous solutions, as, for example, when an aqueous solution is filtered through a hydrophilic filter prior to intravenous administration. As an integral part of the filtering device, the membrane remains hydrophobic, i.e., not wet by aqueous solutions, in its functional use(s) as a gas vent membrane and incorporation into a vent filter device.

[0032] The porous polymeric membrane, according to some embodiments, comprise nylons, polyamides, polyimides, polyethersulfones, polysulfones, polyarylsulfones, cellulose, regenerated cellulose, cellulose esters, acrylic polymers, methacrylic polymers, copolymers acry lic methacrylic polymers, and combinations thereof.

[0033] All ranges for formulations recited herein include ranges therebetween and can be inclusive or exclusive of the endpoints. Optional included ranges are from integer values therebetween (or inclusive of one original endpoint), at the order of magnitude recited or the next smaller order of magnitude. For example, if the lower range value is 0.2, optional included endpoints can be 0.3, 0.4, . . . 1.1, 1.2, and the like, as well as 1, 2, 3 and the like; if the higher range is 8, optional included endpoints can be 7, 6. and the like, as well as 7.9, 7.8. and the like. One-sided boundaries, such as 3 or more, similarly include consistent boundaries (or ranges) starting at integer values at the recited order of magnitude or one lower. For example, 3 or more includes 4, or 3.1 or more.

[0034] Reference throughout this specification to "one embodiment,” "‘certain embodiments,” ‘‘one or more embodiments,” “some embodiments,” or “anAttorney Docket No. P24-188-SEC-WO01 embodiment” indicates that a feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Therefore, the appearances of the phrases such as “in one or more embodiments,” “in certain embodiments,” “in one embodiment,” “some embodiments,” or “in an embodiment” throughout this specification are not necessarily referring to the same embodiment.

[0035] Although some embodiments have been discussed above, other implementations and applications are also within the scope of the following claims. Although the specification describes, with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It is therefore to be further understood that numerous modifications may be made to the illustrative embodiments and that other arrangements and patterns may be devised without departing from the spirit and scope of the embodiments according to the disclosure. Furthermore, particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more of the embodiments.

[0036] Publications of patent applications and patents and non-patent references cited in this specification are herein incorporated by reference in their entirety in the entire portion cited as if each individual publication or reference were specifically and individually indicated to be incorporated by reference herein as being fully set forth. Any patent application to which this application claims priority is also incorporated by reference herein in the manner described above for publications and references.

Claims

Attorney Docket No. P24-188-SEC-WO01CLAIMS1. A porous polymeric membrane which comprises a porous membrane having an average pore size between:0.01-10.0 microns, or0.01-5.0 microns, or between 0.05-1 microns, or between 0.1-0.22 microns, or between 0.2-0.45 microns, formed of a first polymer, said porous polymeric membrane having at least one surface modified with a solution of a second polymer, wherein the second polymer is non-fluorinated, and said second polymer being polymerized and crosslinked on said porous membrane.

2. The porous polymeric membrane of claim 1, wherein the second polymer is DMS or ALO and cross-linked after it is exposed to gamma radiation of up to 100 kGy.

3. The porous polymeric membrane of claims 1-2, wherein the first polymer comprises nylons, polyamides, polyimides, polyethersulfones, polysulfones, polyarylsulfones, PVDF, PES, cellulose, regenerated cellulose, cellulose esters, acrylic polymers methacrylic polymers, copolymers acry lic methacrylic polymers, and combinations thereof.

4. The porous polymeric membrane of claims 1-3, wherein the porous polymeric membrane is an asymmetric membrane or a symmetric membrane.

5. The porous polymeric membrane of claims 1-4, wherein the solution comprises a cross-linker.

6. The porous polymeric membrane of claims 1-5, can be incorporated into a filter unit to facilitate venting of air or gas.

7. A porous polymeric membrane having a surface treatment, comprising:Attorney Docket No. P24-188-SEC-WO01 a porous membrane having an average pore size between about 0.01 and 0.22 microns formed of a first polymer, said porous membrane having a surface which is modified on its surface with a solution of a second polymer; wherein the second polymer further comprises between 1.0-10% DMS or ALO cross-linked.

8. The porous polymeric membrane having a surface treatment of claim 7. wherein the solution of the second polymer further comprises between 0.5- 1.0% initiator.

9. The porous polymeric membrane having a surface treatment of claims 7-8, wherein the cross-linked second polymer further comprises 1.0-10.0% HDDA.

10. The porous polymeric membrane having a surface treatment of claims 7-9, wherein the first poly mer comprising of polyvinylidene fluoride, nylons, polyamides, polyimides, poly ethersulfones, polysulfones, polyarylsulfones, cellulose, regenerated cellulose, cellulose esters, acrylic polymers methacrylic polymers, copolymers acrylic methacrylic polymers, and combinations thereof.

11. The porous polymeric membrane having a surface treatment of claims 7-10, wherein the membrane is an asymmetric membrane or a symmetric membrane.

12. The porous polymeric membrane having a surface treatment of claims 7-11, wherein the membrane comprises a poly ethersulfone membrane.

13. The porous polymeric membrane having a surface treatment of claims 7-12, can be incorporated into a filter unit to facilitate venting of air or gas.

14. The porous polymeric membrane having a surface treatment of claims 7-13 further comprising decamethyltetrasiloxane as a solvent.

15. A porous polymeric membrane having a surface treatment, wherein a surface chemistry formulation comprises a DMS monomer between 1% and 5.5% by weight DMS, and DMTS as a solvent for disposition on a PES membrane, which may be a symmetric or asymmetric membrane.Attorney Docket No. P24-188-SEC-WO0116. The porous polymeric membrane of claim 15, wherein the surface chemistry formulation comprises a DMS monomer between 2% and 5.5% by weight DMS. and DMTS as a solvent for disposition on a PES membrane, which may be a symmetric or asymmetric membrane.

17. The porous polymeric membrane of claim 15, wherein the surface chemistry formulation comprises a DMS monomer between 3% and 5.5% by weight DMS, and DMTS as a solvent for disposition on a PES membrane, which may be a symmetric or asymmetric membrane.

18. A method for preparing a polymeric surface treatment for membranes, comprising: preparing a polymeric solution comprising a DMS monomer within a solvent; applying the polymeric solution to a PES, PVDF, or UPE membrane, wherein the membrane is symmetric or asymmetric; exposing the membrane having the polymeric solution applied thereto to an energy source; and drying the polymeric solution.

19. The method of claim 18, wherein the applying step is a coating step by immersing the membrane in a polymeric solution or directly disposing the polymeric solution on the membrane using a pipette.

20. The method of claim 18, wherein the polymeric solution further comprises a cross-linker.

21. The method of claims 18-20, wherein the cross-linker is a multi-acrylate.

22. The method of claims 18-21 , wherein the polymeric solution further comprises an initiator.

23. The method of claims 18-22. wherein the energy source is an E-beam or ultraviolet light.

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