# Patent

## Title
Functionalized nonwoven article

## Abstract

A grafted nonwoven substrate is disclosed having average fiber sizes of 0.7 to 15 microns, and a void volume of 50 to 95%, and a polymer comprising cationic aminoalkyl(meth)acryloyl monomer units grafted to the surface of the nonwoven substrate. The article may be used as a filter element to purify or separate target materials, such as oligonucleotides or monoclonal antibodies (MAb), from a fluid mixture.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application No. 61/140,168, filed Dec. 23, 2008, the disclosure of which is incorporated by reference herein in its entirety.


The present disclosure relates to functionalized nonwoven substrates, and methods for preparing the same. The present disclosure further relates to a filter using the functionalized nonwoven substrate and a method of filtering a fluid. The functionalized substrates are useful in selectively filtering and removing biological materials, such as biocontaminates, from biological samples.
BACKGROUND
Detection, quantification, isolation and purification of target biomaterials, such as viruses and biomacromolecules (including constituents or products of living cells, for example, proteins, carbohydrates, lipids, and nucleic acids) have long been objectives of investigators. Detection and quantification are important diagnostically, for example, as indicators of various physiological conditions such as diseases. Isolation and purification of biomacromolecules, such as monoclonal antibodies, produced from cell cultures or fermentation processes, are important for therapeutic and in biomedical research. Biomacromolecules such as enzymes have been isolated, purified, and then utilized for the production of sweeteners, antibiotics, and a variety of organic compounds such as ethanol, acetic acid, lysine, aspartic acid, and biologically useful products such as antibodies and steroids.
Chromatographic separation and purification operations can be performed on biological product mixtures, based on the interchange of a solute between a moving phase, which can be a gas or liquid, and a stationary phase. Separation of various solutes of the solution mixture is accomplished because of varying binding interactions of each solute with the stationary phase; stronger binding interactions generally result in longer retention times when subjected to the dissociation or displacement effects of a mobile phase compared to solutes which interact less strongly and, in this fashion, separation and purification can be effected.
Most current capture or purification chromatography is done via conventional column techniques. These techniques have severe bottlenecking issues in downstream purification, as the throughput using chromatography is low. Attempts to alleviate these issues include increasing the diameter of the chromatography column, but this in turn creates challenges due to difficulties of packing the columns effectively and reproducibly. Larger column diameters also increase the occurrence of problematic channeling. Also, in a conventional chromatographic column, the absorption operation is shut down when a breakthrough of the desired product above a specific level is detected. This causes the dynamic or effective capacity of the adsorption media to be significantly less than the overall or static capacity. Furthermore, a selective Protein A column must be protected from unwanted contamination that may plug the column making it difficult to clean or possibly ruining the column for reuse. This reduction in effectiveness has severe economic consequences, given the high cost of some chromatographic resins.
Polymeric resins are widely used for the separation and purification of various target compounds. For example, polymeric resins can be used to purify or separate a target compound based on the presence of an ionic group, based on the size of the target compound, based on a hydrophobic interaction, based on an affinity interaction, or based on the formation of a covalent bond. There is a need in the art for functionalized membranes that overcome limitations in diffusion and binding, and that may be operated at high throughput and at lower pressure drops. There is a need in the art for polymeric substrates having enhanced affinity for selective removal of biocontaminates, such host cell proteins, cell debris, DNA fragments, viruses and cell debris from biological feed-streams in the production of monoclonal antibodies.
SUMMARY
The present disclosure provides an article comprising a nonwoven substrate having average fiber sizes of 0.7 to 15 microns, and a void volume of 50 to 95%, and a polymer comprising cationic aminoalkyl(meth)acryloyl monomer units grafted to the surface of the nonwoven substrate. The article may be used as a filter element to purify or separate target materials, such as host cell proteins, DNA fragments, viruses, and cell debris, oligonucleotides or therapeutic proteins such as monoclonal antibodies (MAb), from a fluid mixture, such as those fluids produced by common cell product harvesting techniques. In particular, one of more layers of the article of this disclosure may be used in depth-type filtration applications, each of which layers may have the same, or different average fiber size, void volume, degree of polymer grafting, monomer composition of grafted polymer, porosity, loft, tensile strength and surface area. The functionalized substrate may further be used in combination with conventional filtration elements such as porous or microporous membranes.
This disclosure further provides a method of making the article comprising the steps of providing a nonwoven substrate, exposing the nonwoven substrate to ionizing radiation in an inert atmosphere, and subsequently imbibing the exposed substrate with a solution comprising grafting aminoalkyl(meth)acryloyl monomers to graft polymerize said monomers to the surface of the nonwoven substrate.



BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a plot of the filtration performance of the articles of Example 1 and Comparative Example 1.
FIG. 2 is a plot of the filtration performance of Example 4.
FIG. 3 is a plot of the filtration performance of Comparative Example 6
FIG. 4 is a plot of the filtration performance of Example 9.
FIG. 5 is a plot of the filtration performance of Examples 11a-d.
FIG. 6 is a perspective view of an exemplary embodiment of a filter media according to the present disclosure formed into a plurality of pleats;
FIG. 7 is a cross-sectional view of an exemplary filter device provided in lenticular form and comprising a filter media according to the present disclosure;
FIG. 8 is a perspective and partial cutaway view of an exemplary filter device provided in encapsulated form and comprising a filter media according to the present disclosure;
FIG. 9 is a cross-sectional view taken at 9-9 of FIG. 8 of an exemplary filter device provided in encapsulated form and comprising a first pleated media cylinder and a second pleated media cylinder according to the present disclosure; and
FIG. 10 is a cross-sectional view taken at 9-9 of FIG. 8 of an exemplary filter device provided in encapsulated form and comprising a core wherein a filter media according to the present disclosure is spirally wound about the core.



DETAILED DESCRIPTION
The present disclosure provides an article comprising a nonwoven substrate having average fiber sizes of 0.7 to 15 microns, and a void volume of 50 to 95%, and a polymer comprising cationic aminoalkyl(meth)acryloyl monomer units grafted to the surface of the nonwoven substrate. The polymer functionalized article may be described as a discontinuous, uncrosslinked hydrogel polymer, initiated from free radicals formed on a nonwoven substrate by ionizing radiation and the subsequent graft-polymerization of the monomers in an aqueous or aqueous/organic solvent solution. As used herein, a “hydrogel” is a water-containing gel; a polymer that is hydrophilic and will absorb water, yet is insoluble in water. The term hydrogel is used regardless of the state of hydration.
The nonwoven substrate is a nonwoven web which may include nonwoven webs manufactured by any of the commonly known processes for producing nonwoven webs. As used herein, the term “nonwoven web” refers to a fabric that has a structure of individual fibers or filaments which are randomly and/or unidirectionally interlaid in a mat-like fashion.
For example, the fibrous nonwoven web can be made by carded, air laid, wet laid, spunlaced, spunbonding, electrospinning or melt-blowing techniques, such as melt-spun or melt-blown, or combinations thereof. Spunbonded fibers are typically small diameter fibers that are formed by extruding molten thermoplastic polymer as filaments from a plurality of fine, usually circular capillaries of a spinneret with the diameter of the extruded fibers being rapidly reduced. Meltblown fibers are typically formed by extruding the molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into a high velocity, usually heated gas (e.g. air) stream which attenuates the filaments of molten thermoplastic material to reduce their diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to from a web of randomly disbursed meltblown fibers. Any of the non-woven webs may be made from a single type of fiber or two or more fibers that differ in the type of thermoplastic polymer and/or thickness.
Staple fibers may also be present in the web. The presence of staple fibers generally provides a loftier, less dense web than a web of only melt blown microfibers. Preferably, no more than about 20 weight percent staple fibers are present, more preferably no more than about 10 weight percent. Such webs containing staple fiber are disclosed in U.S. Pat. No. 4,118,531 (Hauser).
The nonwoven article may optionally further comprise one or more layers of scrim. For example, either or both major surfaces may each optionally further comprise a scrim layer. The scrim, which is typically a woven or nonwoven reinforcement made from fibers, is included to provide strength to the nonwoven article. Suitable scrim materials include, but are not limited to, nylon, polyester, fiberglass, and the like. The average thickness of the scrim can vary. Typically, the average thickness of the scrim ranges from about 25 to about 100 micrometers, preferably about 25 to about 50 micrometers. The layer of the scrim may optionally be bonded to the nonwoven article. A variety of adhesive materials can be used to bond the scrim to the polymeric material. Alternatively, the scrim may be heat-bonded to the nonwoven.
The microfibers of the nonwoven substrate typically have an effective fiber diameter of from about 0.5 to 15 micrometers preferably from about 1 to 6 micrometers, as calculated according to the method set forth in Davies, C. N., “The Separation of Airborne Dust and Particles,” Institution of Mechanical Engineers, London, Proceedings 1B, 1952. The nonwoven substrate preferably has a basis weight in the range of about 10 to 400 g/m2, more preferably about 10 to 100 g/m2. The average thickness of the nonwoven substrate is preferably about 0.1 to 10 mm, more preferably about 0.25 to 5 mm for the non-functionalized, uncalendared substrate. The minimum tensile strength of the nonwoven web is about 4.0 Newtons. It is generally recognized that the tensile strength of nonwovens is lower in the machine direction than in the cross-web direction due to better fiber bonding and entanglement in the latter.
Nonwoven web loft is measured by solidity, a parameter that defines the solids fraction in a volume of web. Lower solidity values are indicative of greater web loft. Useful nonwoven substrates have a solidity of less than 20%, preferably less than 15%. Solidity is a unitless fraction typically represented by α:

α=mf÷ρf×Lnonwoven 

where mf is the fiber mass per sample surface area, which ρf is the fiber density; and

Lnonwoven 

is the nonwoven thickness. Solidity is used herein to refer to the nonwoven substrate itself and not to the functionalized nonwoven. When a nonwoven substrate contains mixtures of two or more kinds of fibers, the individual solidifies are determined for each kind of fiber using the same Lnonwoven and these individual solidities are added together to obtain the web's solidity, α.

As an example, the nonwoven substrate before calendering or grafting preferably has an average pore size of 14 μm calculated from a thickness of 0.34 mm, effective fiber diameter of 4.2 um and solidity of 13%. After calendering the nonwoven web will have a thickness of 0.24 mm and solidity of 18% with an average pore size of 8 μm. The term “average pore size” (also known as average pore diameter) is related to the arithmetic median fiber diameter and web solidity and can be determined by the following formula: where D is the average pore size, df is arithmetic median fiber diameter, and α is the web solidity.




  D
  =
  
    
      d
      f
    
    ⁢
    
      {
      
        
          
            (
            
              
                2
                ⁢
                α
              
              π
            
            )
          
          
            
              -
              1
            
            /
            2
          
        
        -
        1
      
      }
    
  




The nonwoven substrate preferably has a mean pore size of 1-40 microns, preferably 2-20 microns. Mean pore size may be measured according to ASTM F 316-03 Standard Test Methods for Pore Size Characteristics of Membrane Filters by Bubble Point and Mean Flow Pore Test Method B using Freon TFTM as the test fluid.
The nonwoven substrate may be formed from any suitable thermoplastic polymeric material. Suitable polymeric materials include, but are not limited to, polyolefins, poly(isoprenes), poly(butadienes), fluorinated polymers, chlorinated polymers, polyamides, polyimides, polyethers, poly(ether sulfones), poly(sulfones), poly(vinyl acetates), copolymers of vinyl acetate, such as poly(ethylene)-co-poly(vinyl alcohol), poly(phosphazenes), poly(vinyl esters), poly(vinyl ethers), poly(vinyl alcohols), and poly(carbonates).
Suitable polyolefins include, but are not limited to, poly(ethylene), poly(propylene), poly(1-butene), copolymers of ethylene and propylene, alpha olefin copolymers (such as copolymers of ethylene or propylene with 1-butene, 1-hexene, 1-octene, and 1-decene), poly(ethylene-co-1-butene) and poly(ethylene-co-1-butene-co-1-hexene).
Suitable fluorinated polymers include, but are not limited to, poly(vinyl fluoride), poly(vinylidene fluoride), copolymers of vinylidene fluoride (such as poly(vinylidene fluoride-co-hexafluoropropylene), and copolymers of chlorotrifluoroethylene (such as poly(ethylene-co-chlorotrifluoroethylene).
Suitable polyamides include, but are not limited to, nylon 6, nylon 6,6, nylon 6,12 poly(iminoadipoyliminohexamethylene), poly(iminoadipoyliminodecamethylene), and polycaprolactam. Suitable polyimides include poly(pyromellitimide).
Suitable poly(ether sulfones) include, but are not limited to, poly(diphenylether sulfone) and poly(diphenylsulfone-co-diphenylene oxide sulfone).
Suitable copolymers of vinyl acetate include, but are not limited to, poly(ethylene-co-vinyl acetate) and such copolymers in which at least some of the acetate groups have been hydrolyzed to afford various poly(vinyl alcohols) including, poly(ethylene-co-vinyl alcohol).
Preferred polymers are inherently hydrophilic and are readily grafted by ionizing radiation, such as by exposure to e-beam or gamma radiation. Preferred polymers include of polyamides and ethylene vinyl alcohol polymers and copolymers. Nylon nonwoven substrates having 1 micron or smaller effective fiber diameters may be chosen from those described in U.S. Pat. No. 7,170,739 (Arora et al.), U.S. Pat. No. 7,112,389 (Arora et al.), U.S. Pat. No. 7,235,122, (Bryner et al.) and U.S. 20040116026 (=WO 04/02714). Useful nylon nonwoven substrate having 1 micron or smaller effective fiber diameters are also commercially available as HMTTM 16434 and HMTTM 16435 hybrid membrane technology membranes from DuPont, Wilmington, Del.
Further details on the manufacturing method of non-woven webs of this invention may be found in Wente, Superfine Thermoplastic Fibers, 48 INDUS. ENG. CHEM. 1342 (1956), or in Wente et al., Manufacture Of Superfine Organic Fibers, (Naval Research Laboratories Report No. 4364, 1954). Useful methods of preparing the nonwoven substrates are described in U.S. RE39,399 (Allen), U.S. Pat. No. 3,849,241 (Butin et al.), U.S. Pat. No. 7,374,416 (Cook et al.), U.S. Pat. No. 4,936,934 (Buehning), and U.S. Pat. No. 6,230,776 (Choi).
In some embodiments the nonwoven substrate is calendared using a smooth roll that is nipped against another smooth roll. A calendared or compressed nonwoven web provides for a more uniform substrate and dimensional stability in later washing steps to remove unreacted monomers. Thus, in a preferred embodiment, the nonwoven substrate according to the present invention are thermally calendared with a smooth roll and a solid back-up roll (e.g., a metal, rubber, or cotton cloth covered metal) in addition to pattern embossing, described above. During calendering, it is important to closely control the temperature and the pressure of the smooth rolls. In general, the fibers are minimally thermally fused at the points of contact without imparting undesirable characteristics to the nonwoven substrate such as forming a film or skin on the surface thereof. For example, when using nylon nonwoven substrates, it is preferred to maintain the temperature of the smooth roll between about 40° C. and 100° C., more preferably between about 50° C. and 75° C. In addition, the smooth roll should contact the fibrous web at a pressure of from about 10 kilogram-force/cm to about 50 kilogram-force/cm, more preferably from about 15 kilogram-force/cm to about 30 kilogram-force/cm. The average thickness of the calendared nonwoven substrate is preferably about 2⁄3 the thickness of the starting nonwoven.
The functionalized article may be described as a discontinuous, uncrosslinked hydrogel polymer, initiated from free radicals formed on a non-woven substrate by ionizing radiation and the subsequent graft-polymerization of the monomers in an imbibing solution. As used herein, a hydrogel is a water-containing gel; a polymer that is hydrophilic and will absorb water, yet is insoluble in water. The term hydrogel is used regardless of the state of hydration.
The grafted polymer comprises polymer tendrils that are initiated from, and supported by, the nonwoven substrate, the polymer chains (tendrils) extending into the interstitial spaces of the nonwoven substrate. The grafted polymer chains have pendent quaternary ammonium groups, and optional pendent poly(alkylene oxide groups and other functional groups. In the presence of pure water the hydrogel reaches a state of maximum hydration and volume. As the polymer tendrils do not bridge and are free to move independently, the grafted nonwoven article may have a large flow response to very low quantities of stimulus.
In contrast to the instant uncrosslinked grafted hydrogel polymer, conventional hydrogels comprise individual polymer strands or tendrils that are crosslinked through multiple crosslinking sites. Due to the crosslinking the molecular weight of the polymer is infinite and the “gel” refers to the swollen polymer network, the properties of which are controlled through polymer concentration, polymer molecular weight and crosslinking density.
Depending on the degree of substitution of the nonwoven substrate and the weight of polymer grafted to the surface thereof, the hydrogel polymer can completely fill the interstitial spaces of the nonwoven substrate thereby providing a barrier which effectively blocks the flow of pure water through the functionalized nonwoven article resulting in the higher backpressure at a given flux rate (constant rate) or very low flux at a given pressure (constant pressure). It is believe that in pure water the positively charged quaternary ammonium groups electrostatically repulse one another causing maximum extension of the grafted polymer chains and consequently maximum hydration of the hydrogel.
When used in filtration, the hydrogel can reversibly expand in response to a very small amount of a “trigger” such as a salt, buffer, organic solvent, temperature, pH contaminate, or a biomolecule, consequently contracting allowing for higher flux at lower pressure through the hydrogel network. Surprisingly, the grafted hydrogel network doesn't lose it's filterability in a “triggered” state. In the absence of such a “trigger” the fully expanded hydrogel network can offer resistance to water flux.
In the state of maximum hydration, the hydrogel is constrained only by the nonwoven substrate, most significantly in the x and y axes (coplanar with the nonwoven substrate) and less so on the z axis, normal to the plane of the nonwoven substrate. The gel is less constrained on the z axis. The gel may swell up to 800 percent or more on the z axis, but the x and y axes desirably swell less than 100%, more preferably less than 50%, constrained by the nonwoven substrate.
In the art of melt-blown non-woven webs conditions can be adjusted to maximize the resiliency in the z direction (normal to the plane of the nonwoven by (a) adjusting the die and collector for proper fiber lay-down (b) adjusting melt temp and air temp to prevent fibers from over-fusing and forming fiber-fiber bonds, (c) minimize asymmetry caused by the collector being too close in proximity to the die. It is preferred that nonwoven fibers are below the polymer melt temperature before impinging on the collector to reduce the degree of fiber-fiber links. Desirably, the nonwoven may expand maximally in “z” direction (normal to the plane of the nonwoven) to allow for expansion of the hydrogel.
The hydrogel reversibly contracts and allows water to flow (flux) through the resulting interstices in the presence of dissolved species, such as neutral compounds, salts, buffers and negatively charged ions. It is believed the dissolved species such as dissolved ions more effectively charge-couple to the positively charged quaternary ammonium groups in the graft polymer so that the electrostatic repulsion between the quaternary ammonium groups are reduced and the hydrogel constricts or collapses. Alternatively the dissolved species may displace the hydration sphere of the water (and possible solvent) molecules with the result that the hydrogel collapses around the non-woven substrate. Therefore the article exhibits a stimulus-response hydrogel (“responsive hydrogel”) that is discontinuous in nature—able to reversibly open and close the pores or interstices of the hydrogel.
The nonwoven substrate has a polymer comprising aminoalkyl(meth)acryloyl monomer units grafted to the surface of the nonwoven substrate. The polymer is grafted to the surface(s) of the nonwoven substrate by e-beam initiated polymerization of grafting monomers, which include aminoalkyl (meth)acryloyl monomers, optionally poly(alkylene oxide) monomers and optionally other hydrophilic monomers. In general, the grafted (co)polymer comprises:
a) 70 to 100 wt. % of grafting aminoalkyl (meth)acryloyl monomers, preferably at least 80 wt. %, more preferable 80 to 98 wt. %;
b) 0 to 20 wt. %, preferably 2 to 20 wt. %, more preferably 5 to 10 wt. % of grafting poly(alkylene oxide) monomers; and
c) 0 to 10 wt. % of second hydrophilic monomers, each weight percentage relative to the weight of total monomer content.
Generally the total grafted monomer content may be from 0.5 to 5 times the weight of the nonwoven substrate. It is desirable to fill the interstitial spaces of the nonwoven substrate but not have the polymer chains bridge to link separate fibers of the nonwoven with grafted polymer strands, as this will restrict expansion of the nonwoven substrate and impede flux. One way to reduce this fiber-fiber bridging by the grafted polymer is to lower the monomer concentration for a given fiber size. It has been determined that the amount of grafted polymer may be maximized by adding a water miscible organic solvent to the grafting imbibing solution to maximize the molecular weight of the grafted hydrogel polymer tendrils and reduce bridging of the tendrils.
The flux pressure buildup having packed hydrogel tendrils in the interstitial spaces of the nonwoven is simply relieved by the ionic trigger or the biological contamination itself. The benefit from packing the interstitial spaces with hydrogel strands is effectively extending the surface area of the nonwoven to include polymer strands in the void volume where the contamination can displace the water of the hydrogel. The unexpected net effect of nonwovens with grafted hydrogel polymer tendrils in the packed configuration is the ability to hold significantly greater amounts of soluble and insoluble biological contaminants without fouling and the multiple long flexible hydrogel tendrils are capable of multiple bond or hydrogen bonding sites allowing for affinity absorption with greatly improved salt tolerance. In contrast to other microporous substrates, the nonwoven substrate may be considered a scaffold for the grafted polymer, rather than a surface coated substrate.
The grafting aminoalkyl (meth)acryloyl monomers are amino (meth)acrylates or amino (meth)acrylamides of Formula I or quaternary ammonium salts thereof




In Formula II, R1 is hydrogen or methyl, preferably methyl; L is —O— or —NH—; and Y is an alkylene (e.g., an alkylene having 1 to 10 carbon atoms, 1 to 6, or 1 to 4 carbon atoms). Each R2 is independently hydrogen or alkyl, preferably C1-C4 alkyl. Alternatively, the two R2 groups taken together with the nitrogen atom to which they are attached can form a heterocyclic group that is aromatic, partially unsaturated (i.e., unsaturated but not aromatic), or saturated, wherein the heterocyclic group can optionally be fused to a second ring that is aromatic (e.g., benzene), partially unsaturated (e.g., cyclohexene), or saturated (e.g., cyclohexane). The counter ions of the quaternary ammonium salts are often halides, sulfates, phosphates, nitrates, and the like. Such grafting monomers may be quaternary ammonium monomers, i.e. having a —N(R2)3+X− group, wherein each R2 is as defined, an X− is the counter anion. Such monomers having a quaternary ammonium group may be directly grafted to the surface of the nonwoven substrate or a grafting aminoalkyl (meth)acryloyl monomer, having a primary, secondary or tertiary amine group, may be grafted and subsequently converted to a quaternary ammonium group by alkylation.

In some embodiments of Formula I, both R2 groups are hydrogen. In other embodiments, one R2 group is hydrogen and the other is an alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms. In yet other embodiments, the R2 groups combine with the nitrogen atom to which they are attached to form a heterocyclic group. The heterocyclic group includes at least one nitrogen atom and can contain other heteroatoms such as oxygen or sulfur. Exemplary heterocyclic groups include, but are not limited to imidazolyl. The heterocyclic group can be fused to an additional ring such as a benzene, cyclohexene, or cyclohexane. Exemplary heterocyclic groups fused to an additional ring include, but are not limited to, benzoimidazolyl.
Exemplary aminoalkyl (meth)acrylates (i.e., L in Formula I is oxy) include N,N-dialkylaminoalkyl(meth)acrylates such as, for example, N,N-dimethylaminoethylmethacrylate, N,N-dimethylaminoethylacrylate, N,N-diethylaminoethylmethacylate, N,N-diethylaminoethylacrylate, N,N-dimethylaminopropylmethacrylate, N,N-dimethylaminopropylacrylate, N-tert-butylaminopropylmethacrylate, N-tert-butylaminopropylacrylate and the like.
Exemplary amino (meth)acrylamides (i.e., L in Formula I is —NH—) include, for example, N-(3-aminopropyl)methacrylamide, N-(3-aminopropyl)acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-(3-imidazolylpropyl)methacrylamide, N-(3-imidazolylpropyl)acrylamide, N-(2-imidazolylethyl)methacrylamide, N-(1,1-dimethyl-3-imidazoylpropyl)methacrylamide, N-(1,1-dimethyl-3-imidazoylpropyl)acrylamide, N-(3-benzoimidazolylpropyl)acrylamide, and N-(3-benzoimidazolylpropyl)methacrylamide.
Exemplary quaternary salts of the aminoalkyl (meth)acryloyl monomers of Formula I include, but are not limited to, (meth)acrylamidoalkyltrimethylammonium salts (e.g., 3-methacrylamidopropyltrimethylammonium chloride and 3-acrylamidopropyltrimethylammonium chloride) and (meth)acryloxyalkyltrimethylammonium salts (e.g., 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 3-methacryloxy-2-hydroxypropyltrimethylammonium chloride, 3-acryloxy-2-hydroxypropyltrimethylammonium chloride, and 2-acryloxyethyltrimethylammonium methyl sulfate).
The grafted polymer optionally contains monofunctional ethylenically-unsaturated grafting monomer units having a poly(alkylene oxide) group. These monomers copolymerize with the grafting aminoalkyl (meth)acryloyl monomers to form a grafted copolymer chain on the surface of the nonwoven substrate. When present, these monomers are used in amounts of 2 to 20 wt. %, more preferably 5 to 10 wt. %, relative to the total monomer weight.
The monomer units having a poly(alkylene oxide) group is of the formula:

Z-Q-(CH(R3)—CH2-Q)m-R4,  II

wherein Z is a polymerizable ethylenically unsaturated moiety, R3 is a H or a C1 to C4 alkyl group, R4 is a H, a C1 to C4 alkyl group, aryl group, or combinations thereof and m is from 2 to 100, preferably 5 to 20, and Q is a divalent linking group selected from —O—, —NR1—, —CO2— and —CONR1.

In one embodiment, the poly(alkylene oxide) group is a poly(ethylene oxide) (co)polymer. In another embodiment, the pendent poly(alkylene oxide) group is a poly(ethylene oxide-co-propylene oxide) copolymer. Such copolymers may be block copolymers, random copolymers, or gradient copolymers.
Useful ethylenically unsaturated moiety, Z, of the monomer may include:




wherein R3 is H or Me and r=1-10.

The monomer having a poly(alkylene oxide) group can be prepared, for example, by reacting mono- or di-functional alkylene oxide (co)polymers (which are typically commercially available) with reactive ethylenically unsaturated compounds (e.g., acrylates). The functional groups terminating the poly(alkylene oxide) may include hydroxy groups, amine groups and carboxy groups. A variety of reactive ethylenically unsaturated compounds such as acrylate derivatives can be used including, but not limited to, (meth)acrylic acid, (meth)acryloyl chloride, (meth)acrylic anhydride, and 2-isocyanatoethyl (meth)acrylate. Preferably, the monomer is prepared by reacting the mono- or di-functional alkylene oxide (co)polymer with (meth)acrylic anhydride. Typically, if a stoichiometric amount of the ethylenically unsaturated reactant is combined with the monofunctional alkylene oxide (co)polymer (such as a monohydroxy terminated alkylene oxide (co)polymer), 100% conversion to the monosubstituted product is obtained.
Examples of suitable monofunctional poly(alkylene oxide) monomers include poly(ethylene oxide) (meth)acrylate, poly(propylene oxide) (meth)acrylate, poly(ethylene oxide-propylene oxide) (meth)acrylate, and combinations thereof. Such monomers preferably include one nonreactive end group such as (C1-C4)alkoxy, aryloxy (e.g., phenoxy), and (C1-C4)alkaryloxy. These groups can be linear or branched. These monomers can be of a wide range of molecular weights and are commercially available from sources such as Sartomer Company, Exton, Pa.; Shinnakamura Chemical Co., Ltd., Tokyo, Japan; Aldrich, Milwaukee, Wis.; and Osaka Organic Chemical Ind., Ltd., Osaka, Japan.
The grafted polymer optionally contains other ethylenically-unsaturated hydrophilic grafting monomer units-“hydrophilic monomers”. As used herein “hydrophilic monomers” are those polymerizable monomers having a water miscibility (water in monomer) of at least 1 wt. %, preferably at least 5 weight % without reaching a cloud point, are exclusive of poly(alkylene oxide) monomers and contain no acidic functional groups or groups that would retard the grafting polymerization. The grafted copolymer may comprise 0 to 10 wt. % of such monomer units. When present, the polymer generally comprises 1 to 10 wt. % of such of such monomer units.
Examples of suitable hydrophilic monomers include 2-hydroxyethyl(meth)acrylate (HEMA), 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl(meth)acrylate, N-vinyl caprolactam, N-vinyl acetamide, N-vinyl pyrrolidone, acrylonitrile, tetrahydrofurfuryl acrylate, acrylamide, mono- or di-N-alkyl substituted acrylamide, glycerol methacrylate, and combinations thereof. Preferred polar monomers include 2-hydroxyethyl(meth)acrylate (HEMA), N-vinyl pyrrolidone, N-vinyl acetamide, methylacrylamide, and mixtures thereof.
As the polymer is uncrosslinked, the imbibing solution containing the monomer mixture contains no polyethylenically unsaturated monomers; i.e. no crosslinkers.
With regard to the grafting monomers supra, the monomers that are grafted to the surface of the nonwoven substrates usually have either an acrylate or other non-acrylate polymerizable functional group for grafting by e-beam. Methacrylate groups are preferred for grafting of the monomer to the nonwoven substrate surface (using the process described herein) due to the slower, more uniform reactivity and durability of such methacrylates to nonwovens that have been exposed to e-beam irradiation.
As described in further detail below, functionalized substrates of the present invention may be prepared using above-described monomers to provide a grafted polymer on the surface of a porous nonwoven base substrate. When two or more of the above-described grafting monomers are used, the monomers may be grafted onto the nonwoven base substrate in a single reaction step (i.e., exposure to an ionizing radiation) followed by imbibing with all grafting monomers present or in sequential reaction steps (i.e., a first exposure to ionizing radiation followed by imbibing with one or more grafting monomer, then a second exposure to an ionizing radiation and a second imbibing after the second exposure to the ionizing radiation).
It will be further understood that the grafting process will yield a radical species on the surface of the nonwoven substrate. After imbibing with the monomer solution, polymerization will initiate with the formation of a radical on the carbon alpha to the carbonyl of the aminoalkyl (meth)acryloyl monomer of Formula I, that may further polymerize with one of more additional aminoalkyl (meth)acryloyl monomers, one of more optional PEG monomers of Formula II, and one or more optional second hydrophilic monomers, resulting in a grafted polymers having these groups pendent from the polymer chain as simply illustrated below.

Substrate-(MNR4+)w-(MPEG)x-(Mc)y 

In the formula, the -(MNR4+)w-represent the residue of the grafted aminoalkyl (meth)acryloyl monomer of Formula I having “w” polymerized monomer units where w is at least 2, the -(MPEG)x represents the polymerized monomer of Formulas II having “x” polymerized monomer units, where x may be zero and is preferably at least one, -(Mc)y represents the polymerized second hydrophilic monomers, having y polymerized monomer units, where y may be zero and is preferably at least 1. The polymer may be random or block. The polymer may be directly grafted via the residue of the aminoalkyl (meth)acryloyl monomer, as shown, or may be directly grafted via the -(MPEG)—monomers or the hydrophilic monomers, as described herein.
The process of preparing the grafted nonwoven substrate comprises the steps of providing a nonwoven substrate, exposing the nonwoven substrate to e-beam radiation in an inert atmosphere, and subsequently imbibing the exposed substrate with a solution comprising grafting aminoalkyl (meth)acryloyl monomers to graft polymerize said monomers to the surface of the nonwoven substrate.
In the first step the nonwoven substrate is exposed to ionizing radiation, such as E-beam radiation, in an inert atmosphere. Generally, the substrate is placed in a chamber purged of oxygen. Typically, the chamber comprises an inert atmosphere such as nitrogen, carbon dioxide, helium, argon, etc. with a minimal amount of oxygen (less than 100 ppm), which is known to inhibit free-radical polymerization.
The irradiation step comprises the ionizing irradiation of nonwoven substrate surfaces, preferably with ionizing e-beam or gamma radiation to prepare free radical reaction sites on such surfaces upon which the monomers are subsequently grafted. “Ionizing irradiation” means radiation of a sufficient dosage and energy to cause the formation of free radical reaction sites on the surface(s) of the base substrate. Ionizing radiation may include gamma, electron-beam, x-ray and other forms of electromagnetic radiation. In some instances, corona radiation can be sufficiently high energy radiation. The radiation is sufficiently high energy, that when absorbed by the surfaces of the base substrate, sufficient energy is transferred to that support to result in the cleavage of chemical bonds in that support and the resultant formation of free radical sites on the nonwoven substrate. One or more layers of nonwoven substrates may be subjected to the ionizing radiation.
High energy radiation dosages are measured in kilograys (kGy). Doses can be administered in a single dose of the desired level or in multiple doses which accumulate to the desired level. Dosages can range cumulatively from about 1 kGy to about 200 kGy. The dose can be delivered all at once such as from an E-beam source or accumulated from a slow dose rate over several hours such as dosage delivered from a gamma source. Preferably, the cumulative dosage exceeds 20 kGy (2 Mrads) for substrates resistant to radiation damage.
Electron beam is one preferred method of grafting due to the ready-availability of commercial sources. Electron beam generators are commercially available from a variety of sources, including the ESI “ELECTROCURE” EB SYSTEM from Energy Sciences, Inc. (Wilmington, Mass.), and the BROADBEAM EB PROCESSOR from PCT Engineered Systems, LLC (Davenport, Iowa). For any given piece of equipment and irradiation sample location, the dosage delivered can be measured in accordance with ASTM E-1275 entitled “Practice for Use of a Radiochromic Film Dosimetry System.” By altering extractor grid voltage, beam diameter and/or distance to the source, various dose rates can be obtained.
In the irradiation step the nonwoven substrate is exposed to a sufficient quantity of ionizing radiation, so as to form free radicals on the surfaces of the nonwoven substrate. The chamber may contain at least one device capable of providing a sufficient dose of radiation. A single device is capable of providing a sufficient dose of radiation, although two or more devices, and/or multiple passes through a single device, may be used especially for relatively thick nonwoven substrates. The environment containing the nonwoven substrate comprises an inert atmosphere such as nitrogen, carbon dioxide, helium, argon, etc. with a minimal amount of oxygen, which is known to inhibit free-radical polymerization.
Dose is the total amount of energy absorbed per mass unit. Dose is commonly expressed in kiloGrays (kGy). A Gray is defined as the amount of radiation required to supply 1 joule of energy per kilogram of mass. The total dose received by the substrate depends on a number of parameters including source activity, residence time (i.e. the total time the sample is irradiated), the distance from the source, and attenuation by the intervening cross-section of materials between the source and sample. Dose is typically regulated by controlling residence time, distance to the source, or both.
Generally, it was found that doses in the range of about 20 to 40 kGy were suitable for generating the grafted hydrogel polymer. Total dose requirement for any given composition will vary as a function of desired grafting objectives, monomer selected, substrate used and the dose rate. Thus, a dose rate can be selected based on desired properties for a specified composition. The dose rate is typically in the range of 0.0005 kGy/sec (gamma) to 200 kGy/sec (E-beam).
Other sources of irradiation may be used with equal grafting performance, a desirable source of ionizing radiation comprises an electron beam source because the electron beam can produce high and fast dose delivery rates. Electron beams (e-beams) are generally produced by applying high voltage to tungsten wire filaments retained between a repeller plate and an extractor grid within a vacuum chamber maintained at about 10−6 Torr. The filaments are heated at high current to produce electrons. The electrons are guided and accelerated by the repeller plate and extractor grid towards a thin window of metal foil. The accelerated electrons, traveling at speeds in excess of 107 meters/second (m/sec) and possessing about 100 to 300 kilo-electron volts (keV), pass out of the vacuum chamber through the foil window and penetrate whatever material is positioned immediately beyond the foil window.
The quantity of electrons generated is directly related to the current. As extractor grid voltage is increased, the acceleration or speed of electrons drawn from the tungsten wire filaments increase. E-beam processing can be extremely precise when under computer control, such that an exact dose and dose rate of electrons can be directed against the nonwoven substrate.
The temperature within the chamber is desirably maintained at an ambient temperature by conventional means. Without intending to be limited to any particular mechanism, it is believed that the exposure of the nonwoven substrate to an electron beam results in free radical sites on the substrate surface which can then subsequently react with the grafting monomers in the imbibing step.
The total dose received by nonwoven substrate primarily affects the number of radical sites formed on the surface thereof and subsequently the extent to which the grafting monomers are grafted onto the nonwoven substrate. Dose is dependent upon a number of processing parameters, including voltage, web- or line-speed and beam current. Dose can be conveniently regulated by controlling line speed (i.e., the speed with which the nonwoven substrate passes under the irradiation device), and the current supplied to the extractor grid. A target dose (e.g., <10 kGy) can be conveniently calculated by multiplying an experimentally measured coefficient (a machine constant) by the beam current and dividing by the web speed to determine the exposure. The machine constant varies as a function of beam voltage.
While the controlled amount of electron beam radiation exposure is dependent upon the residence time, the nonwoven substrate is subjected to a controlled amount of dosage ranging from a minimum dosage of about 1 kilogray (kGy) to a practical maximum dosage of less than about 200 kGy, depending on the particular polymer. For radiation sensitive polymers such as propylene polymers the amount typically ranges from a minimum dosage of about 1 kilogray (kGy) to a maximum dosage of less than about 10 kGy. Typically, the total controlled amount of dosage ranges from less than about 9 kGy to about 7 kGy for propylene polymers to avoid degradation. Less radiation sensitive polymers such as nylons or PVDF may be subjected to higher dosages, typically 10 to 70 kGy. Generally, suitable gamma ray sources emit gamma rays having energies of 400 keV or greater. Typically, suitable gamma ray sources emit gamma rays having energies in the range of 500 keV to 5 MeV. Examples of suitable gamma ray sources include cobalt-60 isotope (which emits photons with energies of approximately 1.17 and 1.33 MeV in nearly equal proportions) and cesium-137 isotope (which emits photons with energies of approximately 0.662 MeV). The distance from the source can be fixed or made variable by changing the position of the target or the source. The flux of gamma rays emitted from the source generally decays with the square of the distance from the source and duration of time as governed by the half-life of the isotope.
In the instant method, the irradiated substrate, having free radical sites on the surface of the nonwoven substrate, are imbibed with the monomer solution subsequent to and not concurrent with, the irradiation step. The free radical sites generated on the surface of the nonwoven substrate have average lifetimes ranging from several minutes to several hours and progressively decay to a low concentration within about ten hours at room temperature. Lower temperatures, such as dry ice temperatures, promotes longer radical lifetimes. Alternatively, humidification and nitrous oxide can increase the rate of substrate radical formation via generation of hydroxyl radicals. The effective binding absorption capacity of the grafted nonwoven from the graft polymerization process is little changed after a reaction time of about 12 hours, kept under inert conditions. It has been observed that keeping the graft polymerization process inert for 72 hours results in an increase of about 10 to 20% more yeast/molasses binding capacity (as described in the Example) than the performance of a sample quenched after 12 hours (by exposure to air) at room temperature, presumably due to an increase in grafted polymer.
Generally the irradiated nonwoven substrate is imbibed with the monomer solution immediately after the irradiation step. Generally when using E-beam the irradiated substrate is imbibed within an hour, preferably within ten minutes. Generally, when using gamma as a source, the substrate should be imbibed immediately after irradiation since irradiation residence time will be long. It has been observed that if the substrate is irradiated by ionizing radiation in the presence of the grafting monomers, the filtration performance of the grafted nonwoven substrate is inferior to that article prepared by the instant method.
In the imbibing step the nonwoven substrate is contacted with the imbibing solution containing one or more grafting monomers and in amounts previously described. Suitable methods of imbibing include, but are not limited to, a spray coating, flood coating, knife coating, Meyer bar coating, dip coating, and gravure coating.
The imbibing solution remains in contact with the nonwoven substrate for a time sufficient for the radical sites to initiate polymerization with the grafting monomers. When imbibed with a solution of monomers, grafting reactions are mostly completed after 12 hours exposure; generally about 90+ percent. As a result, the nonwoven substrate comprises grafted polymers and/or copolymers attached to the interstitial and outer surfaces of the nonwoven substrate.
As discussed above, the imbibing solution may comprise one or more grafting monomers suitable for grafting onto surfaces of the nonwoven substrate. Any of the exemplary grafting monomers described above can be included in solution. In addition to the described grafting monomers, the imbibing solution can contain other materials such as, for example, one or more other non-grafting monomers for UV curing, surfactants, dyes, pigments and solvents.
The concentration of each grafting monomer in the imbibing solution may vary depending on a number of factors including, but not limited to, the grafting monomer or monomers in the imbibing solution, the extent of grafting desired, the reactivity of the grafting monomer(s), and the solvent used. Typically, the total concentration of the monomers in the imbibing solution ranges from about 1 wt % to about 100 wt %, desirably, from about 5 wt % to about 30 wt %, and more desirably from about 15 wt % to about 25 wt % based on a total weight of the imbibing solution.
The imbibing solution further comprises an aqueous blend of a water miscible organic solvent and the grafting monomer(s). It has been found that the solvent blend influences the morphology of the grafted polymer and the resulting flux rate when used in separation applications. The ratio of water to organic solvent can vary widely, but is typically greater than 1:1 (v/v) water to organic solvent, preferably greater than 5:1, and more preferably greater than 7:1. The ratios are generally adjusted so that the resulting grafted nonwoven substrate produces pressure and flux responses maximizing the binding capacity for the targeted bioseparation application.
The concentration of the organic solvent in water may be optimized with respect to the fiber size of the nonwoven substrate. In general, the optimum concentration of organic solvent increases as the fiber size decreases. Using a 20% 3-[(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomer imbibing solution, a nonwoven with a 4 μm effective fiber diameter optimally uses 15% organic solvent in water. A 15% MAPTAC monomer imbibing solution for a 1 μm effective fiber diameter nonwoven web optimally uses 30% organic solvent in water.
It is believed that by adjusting the amount of water miscible organic solvent in the imbibing solution a greater amount of monomer is grafted to the nonwoven substrate without bridging the fibers of the substrate and closing the voids. If the web voids are bridged, the nonwoven dries to a translucent appearance, and has decreased flux and reduced ability to expand. The smaller the fibers the less monomer it takes to bridge the pores of the nonwoven. Adding more water-miscible organic solvent reduces the bridging, allows for increased grafted polymer content (as a function of weight percent of the nonwoven substrate) and allows for freer expansion of the article.
Any such water miscible organic solvent preferably has no tertiary hydrogen atoms, or other groups that would retard the graft polymerization. In some embodiments, the water miscible solvents are protic group containing organic liquids such as the lower alcohols having 1 to 4 carbon atoms, lower glycols having 2 to 6 carbon atoms, and most preferably lower glycol ethers having 3 to 6 carbon atoms and 1 to 2 ether linkages. In some embodiments higher glycols such as poly(ethylene glycol) may be used. Specific examples are methanol, ethanol, n-butanol, t-butyl alcohol, ethylene glycol, methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol, methyl carbitol, ethyl carbitol, and mixtures thereof.
In other embodiments, non-protic water miscible organic solvents that can also be used such as aliphatic esters and ketones and sulfoxides such as ethyl acetate, propyl acetate, butyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, butoxyethyl acetate, triethyl phosphate, acetone, methyl ethyl ketone, methyl propyl ketone and dimethyl sulfoxide.
Once the nonwoven substrate has been imbibed for a desired period of time, the nonwoven substrate bearing grafted polymer groups may be optionally rinsed to remove residual monomer and/or dried.
In the optional rinsing step, the functionalized nonwoven substrate is washed or rinsed one or more times to remove any unreacted monomers, solvent or other reaction by-products. Typically, the functionalized substrate is washed or rinsed up to three times using a water rinse, an alcohol rinse, a combination of water and alcohol rinses, and/or a solvent rinse (e.g., acetone, methyl ethyl ketone, etc). When an alcohol rinse is used, the rinse may include one or more alcohols including, but not limited to, isopropanol, methanol, ethanol, or any other alcohol that is practical to use and an effective solvent for any residual monomer. In each rinse step, the functionalized substrate may pass through a rinse bath or a rinse spray. In some embodiments, the rinse may comprise an ionic buffer solution that would reduce swelling of the hydrogel, the amount of retained water, and also avoiding weakening the non-woven substrate during this rinse step.
In the optional drying step, the functionalized substrate is dried to remove any rinse solution. Typically, the functionalized substrate is dried in oven having a relatively low oven temperature for a desired period of time (referred to herein as “oven dwell time”). Oven temperatures typically range from about 60° C. to about 120° C., while oven dwell times typically range from about 120 to about 600 seconds. Any conventional oven may be used in the optional drying step. It should also be noted that in other embodiments the drying step can proceed before the rinsing step to eliminate volatile components before extraction of non-grafted residue. Following the optional drying step, the dried functionalized substrate can be taken up in roll form to be stored for future use
The functionalized nonwoven substrates are particularly suited as filter media, such as the filter media found in water filtration devices. As the polymer is grafted to render it hydrophilic, the filter media is durable. In water filtration media, such as filter devices, the filter media is cleaned or sanitized by contact or flushing with aqueous NaOH. The hydrophilic porous substrate described herein, can be contacted or flushed with NaOH and retain the hydrophilic properties as evidenced by the surface energy and wettability.
When used in a filtration application, one or more layers of the functionalized substrate may be used, each of which layers may have the same, or different average fiber size, void volume, degree of polymer grafting, monomer composition of grafted polymer, porosity, tensile strength and surface area. In some embodiments, each subsequent layer may have a smaller effective pore size or smaller average fiber size so that finer contaminants may be filtered. The grafted nonwoven substrate may be configured as planer or lenticular disks. In some embodiments the nonwoven substrate may be pleated. Pleated grafted nonwoven filter elements may be combined as multiple concentric pleated elements. The grafted nonwoven substrate may be wound spirally. Further, the grafted nonwoven substrate may be encapsulated with a porous web to provide support and aid in handling. In filtration applications, the nonwoven may be disposed either vertically, or horizontally.
FIG. 6 depicts an exemplary filter media 120 according to the present disclosure. As shown, filter media 120 comprises a plurality of pleats 126. In some embodiments, pleated filter media 120 may be incorporated into a filter device or other filter device. Examples of pleating configurations and filter devices comprising pleated media may be found, for example, in U.S. Pat. No. 6,521,011 to Sundet et al. It is also envisioned that the plurality of pleats 126 could comprise planarly disposed pleats, as described in U.S. 2011-0226691 (Lucas et al.). In the embodiment shown, filter media 120 comprises a grafted nonwoven substrate 122 together with a microporous membrane layer 124. Typically, microporous membrane layer 124 is positioned downstream of grafted nonwoven substrate 122.
Microporous membrane layer 124 may comprise one or more microporous membranes as described throughout the present disclosure. In some embodiments, microporous membrane layer 124 comprises a single zone having a symmetrically distributed pore size. In other embodiments, microporous membrane layer 124 comprises a single zone comprising an asymmetrically distributed pore size. In still other embodiments, microporous membrane layer 124 comprises multiple discrete zones. In such embodiments, each discrete zone may comprise symmetrically or asymmetrically distributed pore sizes.
In some embodiments, one or more zones of microporous membrane layer 124 may be functionalized to include, for example, enhanced hydrophilic properties. Methods for providing a functionalized microporous membrane are described, for example, elsewhere in the present disclosure.
It is also envisioned that microporous membrane layer 124 may comprise multiple layers of microporous membrane, wherein each layer may comprise a single zone or multiple discrete zones. Each zone may comprise symmetrically or asymmetrically distributed pore sizes, and each layer of microporous membrane may be functionalized or non-functionalized as desired for a specific application. In one embodiment, as described below in the section entitled “Nylon Microporous Membranes D1-D6”, microporous membrane layer 124 may comprise three layers of microporous membrane, wherein each layer comprises three discrete zones.
Grafted nonwoven substrate 122 may comprise one or more nonwoven substrates as described throughout the present disclosure. In some embodiments, grafted nonwoven substrate 122 comprises a single layer of nonwoven. In other embodiments, grafted nonwoven substrate 122 may include additional layers of nonwoven material having the same or different construction. For example, it is envisioned that grafted nonwoven substrate 122 may comprise a non-grafted nonwoven layer positioned upstream of a grafted nonwoven layer. In such an embodiment, the more upstream layer may be provided, for example, with a lower density, or increased porosity, relative to the more downstream layer.
FIG. 7 depicts an exemplary filter device 100 according to the present disclosure. As shown, filter device 100 comprises a filter media 120 provided in the form of a lenticular filter cartridge. Examples of lenticular filter cartridges and methods of making lenticular filter cartridges may be found, for example, in U.S. Pat. Nos. 6,464,084; 6,939,466; 7,178,676; and 6,712,966 to Pulek et al.
As shown, filter device 100 comprises a separator element 140 having a central core 142 in fluid communication with a fluid outlet 116. Typically, separator element 140 comprises a first side 144 and a second side 146 upon which filter media 120 may be disposed. First side 144 and second side 146 are typically not provide filtering functionality, but are provided with a network of apertures through which fluid may freely flow. As depicted, filter media 120 is provided as a first filter media disk 150 positioned on first side 144 and a second filter media disk 154 positioned on second side 146. First and second filter media disks 150 and 154 each respectively comprise an outer circumferential edge 151, 155 and an inner circumferential edge 152, 156. In some embodiments, an edge seal 150 connects the outer circumferential edges 151 and 155 of first and second filter media disks 150 and 154. Typically, inner circumferential edges 152 and 156 are connected to central core 142 of separator element 140.
In a typical application, the downstream surface of filter media 120 is positioned proximal to separator element 140. Filter media 120 comprises grafted nonwoven substrate 122. In the embodiment shown, filter media 120 comprises a grafted nonwoven substrate 122 together with a microporous membrane layer 124. Typically, microporous membrane layer 124 is positioned downstream of grafted nonwoven substrate 122.
With regard to FIG. 8, an exemplary filter device 100 is shown comprising a filter capsule 110 and a filter cap 112 connected to filter capsule 110. As shown, filter cap 112 comprises a fluid inlet 114 and a fluid outlet 116. Filter media 120 is encapsulated in filter capsule 110 and fluidly connects fluid inlet 114 and fluid outlet 116. As seen through the cutaway in FIG. 8, filter media 120 is formed into a first media cylinder 130 comprising a plurality of pleats 126. Examples or filter devices and methods of making filter devices may be found, for example, in U.S. Pat. No. 6,458,269 to Bassett et al. Examples of filter media formed into cylinders comprising a plurality of pleats may be found, for example, in U.S. Pat. No. 6,315,130 to Olsen.
In some embodiments the present disclosure provides a filter cartridge comprising a filter capsule; and a filter cap connected to the filter capsule; wherein the filter cap comprises the fluid inlet and the fluid outlet, and wherein the filter media is encapsulated in the filter capsule. In some embodiments filter cap of the filter device comprises the fluid inlet and the fluid outlet, and wherein the filter media is encapsulated in the filter capsule. In some embodiments the filter media further comprises a microporous membrane layer positioned downstream of the grafted nonwoven substrate.
Therefore the present disclosure provides a filter device comprising a fluid inlet; a fluid outlet; and a filter media fluidly connecting the fluid inlet and the fluid outlet; wherein the filter media comprises the grafted nonwoven substrate. In some embodiments the present disclosure provides a filter device further comprising a separator element (140); and an edge seal (150); the separator element comprising a central core (142) in fluid communication with the fluid inlet; a first side (144); and a second side (146); the filter media comprising a first media disk (150) positioned on the first side of the separator element and having an outer circumferential edge (151) and an inner circumferential edge (152); and a second media disk (154) positioned on the second side of the separator element and having an outer circumferential edge (155) and an inner circumferential edge (156); wherein the outer circumferential edges of the first and second media disks are connected by the edge seal and the inner circumferential edges of the first and second media disks are connected to the central core
FIG. 9 depicts a cross-sectional view of one embodiment of filter device 100 shown in FIG. 8, wherein filter media 120 is formed into first media cylinder 130 comprising a plurality of pleats 126. In the embodiment shown, filter media 120 comprises a grafted nonwoven substrate 122 together with a microporous membrane layer 124. Typically, microporous membrane layer 124 is positioned downstream of grafted nonwoven substrate 122. As shown in FIG. 9, filter device 100 optionally comprises a second media cylinder 132 positioned within first media cylinder 130. In such embodiments, second media cylinder 132 may comprise a plurality of pleats. Examples of filter modules comprising inner and outer media cylinders comprising a plurality of pleats may be found, for example, in U.S. Pat. Pub. No. U.S. 2009/0020472 A1 to Lucas et al.
Therefore in some embodiments, the present disclosure provides a filter device of wherein the filter media further comprises one or more microporous membrane layers positioned downstream of the grafted nonwoven substrate. In some embodiments the present disclosure provides a filter device wherein the filter media comprises a plurality of pleats.
In some embodiments, the present disclosure provides filter device for removing particulate contaminants from a liquid comprises a housing which has a top wall, a bottom wall, a generally cylindrical side wall extending between the top wall and the bottom wall, a filter element disposed within the housing comprising (the grafted nonwoven) and an inlet and an outlet defining a liquid flow path through the filter element (grafted nonwoven). The liquid flow path has an upstream portion adjacent the inlet and a downstream portion adjacent the outlet so that the fluid flows though the (grafted nonwoven). The filter element may also comprise a microporous membrane which may be downstream of the (grafted nonwoven) so that a fluid flows from the inlet, though the grafted nonwoven, and through the microporous membrane to the outlet.
FIG. 10 depicts a cross-sectional view of an alternative embodiment of a filter device 100 as shown in FIG. 8, wherein filter device further comprises a core 160, and wherein the filter media 120 is spirally wound about core 160. Core 160 typically does not provide filtering functionality, but is provided with a network of apertures through which fluid may freely flow. Examples of spirally wound filter cartridges and methods of making spirally wound filter cartridges may be found, for example, in U.S. Pat. No. 6,391,200 to Pulek et al. In the embodiment shown, filter media 120 comprises a grafted nonwoven substrate 122 together with a microporous membrane layer 124. Typically, microporous membrane layer 124 is positioned downstream of grafted nonwoven substrate 122. In some embodiments, a drainage layer may be further provided to help facilitate fluid flow between adjacent layers of spirally-wrapped filter media 120.
In some embodiments the present disclosure provides a filter device comprising a core (160), wherein the filter media is spirally wound about the core.
In some embodiments the functionalized nonwoven substrate may be combined with conventional filter elements, such as microporous membranes. In particular, a filter comprising one or more layers of the instant functionalized nonwoven substrate can serve as a “prefilter” for removing contaminants and or protecting downstream processing, including additional downstream filters. In the case of monoclonal antibody production, the instant functionalized nonwoven may serve as a prefilter protecting finer downstream microporous filtering membranes, which are readily clogged with cellular debris, agglomorates, DNA fragments, and host cell proteins. Fine size exclusion membranes serve to guarantee the functionality of the separation medium and the interstitial spacing pathways of a packed Protein A column located downstream of the membranes.
Microporous membranes are known to quickly foul with biocontaminants and therefore often need a pre-filter commonly called depth filters. The functionalized nonwoven substrate described herein can effectively replace current cellulose/diatomaceous earth depth filters. A microporous membrane with an absolute pore size rating used in conjunction beneath the media is desirable because the functionalized nonwoven substrate will protect the microporous membrane, thereby extending the useful life of the microporous membrane, and in turn, the membrane will capture any breakthrough contamination from the open hydrogel network permitting a longer useful life of the grafted nonwoven (as measured by turbidity reduction of the filtrate).
When used in filtration, a fluid containing a biological sample of interest and contaminants can be passed through the responsive functionalized nonwoven article separating the two. In some embodiments contaminates will be retained in the grafted polymer hydrogel network and the biological sample of interest will pass. The interstitial pores or voids of the grafted polymer hydrogel may be changed in response to the biological contamination of the fluid or the presence of a “trigger”, (e.g. ionic strength, polar organic or inorganic species, molasses, salt, buffer, proteins, cell debris, viruses, etc). It is observed that the clean water flux (with no trigger) is low with high back pressure. Increased hydraulic pressure causes the hydrogel to collapse or compress further reducing flux. This collapse or compression further shortens the dwell time by decreasing the z direction mean flow path and reducing the retaining volume for accumulating biocontaminants. Therefore, the grafted nonwoven works better at low pressures thereby reducing shear to any shear sensitive proteins during the early filtration steps.
The polymer grafted nonwoven article described herein is capable of retaining particles and insoluble contaminates from a biological fluid phase throughout its expanded matrix. When some small amount of polar “trigger” is present the hydraulic pressure is rapidly relieved. It is believed that each quaternary ammonium monomer unit serves as a point charge in the grafted polymer chain, and is surrounded by an ionic electric double layer entirely composed of water, the hydration layer. This forms a “radius of shear” resisting water flux and serves to compress the nonwoven hydrogel network from the hydraulic pressure. Small ionic differences cause disruption of the inner and outer shell of the double layer allowing increased flux. During filtration when the back pressure is relieved after exposure to a “trigger”, the nonwoven structure can expand back because of the lack of hydraulic pressure.
In filtration applications, naturally occurring macromolecules such as proteins acquire a charge (negative as contaminates) when dispersed in water—due to the pKa of the protein and the pH of the buffered solution. For example, negatively charged cell debris is bound by charge-affinity to the hydrogel, allowing passage of such entities as positive charged monoclonal antibodies (mAb). As more and more material is progressively passed through the depth of the filter, the discontinuous gel collapses as negatively charged contaminates such as cell debris is captured and positively charged materials such as monoclonal antibodies are passed. This continues until the dynamic capacity of the filter element is reached.
In biofiltration applications, high filtration pressure is undesirable because it could result in the shearing and subsequent denaturing of the proteins. Excessive pressure generated from pumping clean water can cause the expanded nonwoven to collapse under hydraulic pressure making flow even more restrictive and undesirable because it shortens affinity dwell time by decreasing the z direction mean flow path and reduces the retaining volume for accumulating biocontamination. Hence, the article of this invention becomes capable of retaining particles and insoluble contaminates from a mobile phase throughout its expanded matrix at lower filtration pressures.
The instant polymer-functionalized nonwoven article will load contamination without undue pressure build-up over the lifetime of the article. A normal fouling mechanism in filter media is when the media sifts particles out of a mobile phase; the particles can cake in the pores or on the major surface of the media. Flux is then reduced and pressure builds up and this can be exacerbated if the cake layer can be compressed. The instant polymer-functionalized nonwoven article allows contamination to impinge on the discontinuous hydrogel matrix where the contamination easily is diffused into the matrix resisting fouling from caking or compression. As contamination is added, more room is obtained in the interstitial spaces of the nonwoven from the loading and adsorption of contamination on the hydrogel polymer tendrils.
In bioseparation applications, generally “normal flow” filtration is conducted in either a constant rate or constant pressure mode. In constant rate mode, a set volume of fluid is delivered from a pump and the pressure in a filter is allowed to increase as the filter fouls and the filtering process is stopped at a nominal pressure value to keep the target protein intact; usually to no more than about 30 psi. In constant pressure mode a set pressure is applied to a fluid and allowed to flow until the delivery rate ceases or becomes to low to be practical and the filtration process is stopped. Typical flow rates used in affinity chromatography from low to high are about 50 to 600 LMH (liters/(meter2-hour), or a frontal fluid velocity of 0.08 to 1 ml/(min-cm2). 47 mm test housings have about 13 cm2 of usable surface area so a rate of 13 ml/min is equivalent performance to the stated high 600 LMH used in commercial procedures. Depending on the number of layers, thickness of each layer, fiber size and amount of grafting, the clean water flux of this invention has been observed as high as 75 psi at 1 ml/(min-cm2) (13 ml/min). The introduction of a polar trigger will cause this pressure to be reduced to less than 1 psi. Flushing out the buffer (serving as a trigger) with clean water results in returning of the higher pressures.
The polymer grafted nonwoven substrate described herein may be combined with microporous membranes, including symmetric or asymmetric microporous membranes (having a gradient porosity), and single or multiple layers of such membranes. Useful microporous membranes include those made from nylon, polyether sulfone, polyvinylidine fluoride, polypropylene, ethylene-trichlorofluoroethylene, with single layer, multiple layers, and the like. Preferably, these membranes are hydrophilic. The microporous membranes may have symmetric pore size ranges of 0.01 to 150 μm, preferably 0.1 to 100 μm and thicknesses of 25 to 500 μm. In another embodiment the grafted nonwoven substrate may be combined with asymmetric microporous membranes having gradient average pore sizes of 0.01 to 150 μm. In other embodiments, multiple layers of microporous membranes may be used in combination, with each layer having successively finer porosity, such from 15 to 0.02 μm, preferably 10 to 0.8 μm and total thicknesses of 75 to 1200 μm. Multiple layers of microporous membranes having both symmetric and gradient porosities may be used in combination. Further, the microporous membranes may be polymer grafted to alter the surface characteristics thereof, such as hydrophilicity, hydrophobicity or charge binding capacity.
Further, one or more layers of the grafted nonwoven substrate may be combined with one of more layers of a microporous membrane. For example one to five layers of grafted nonwoven substrate may be combined with the microporous layer(s). Each layer of the grafted nonwoven substrate may be the same or different. In some embodiments the layers may be the same, or may differ in terms of the particular nonwoven substrate, thickness of the nonwoven substrate, polymer used therein, fiber size, porosity, void volume, loft, tensile strength, surface area, grafting weight or density, degree of polymer grafting, and/or monomer concentration in the grafting polymer.
Examples of useful commercial membrane include LifeAssureTM or SterAssureTM cast nylon microporous membranes available from CUNO Inc., Meriden, Conn. Useful microporous membranes are disclosed in U.S. 6,413,070, 6,513,666, 6,776,940, 6,056,529 and 6,264,044 (Meyering et al.,), U.S. 5,006,247 (Dennison et al.), U.S. 3,876,738 (Marinaccio et al.), U.S. 4,707,265, (Barnes et al.), and U.S. 4,473,474 (Ostreicher et al.). Useful graft polymer functionalized microporous membranes are disclosed in U.S. 2010/0261801 (Weiss et al.).
The combination of the microporous membranes with the grafted nonwoven will protect the microfiltration membrane thereby extending its useful life and the membrane will capture any breakthrough contamination that passes through the open hydrogel network improving the efficiency of the grafted nonwoven. Contaminants may be measured using techniques known in the art including turbidity reduction, UV, DNA quantitation and ELISA methods.
Many bioseparation methods use a 0.2 μm sterilization grade microporous membrane before a capture step, such as with a Protein A column. Such two dimensional membranes, functioning by particle size exclusion at the membrane surface, quickly foul with heavily contaminated bioprocessing feed-streams found just after centrifugation and therefore needs a pre-filter commonly called depth filters. Centrifugation using a continuous disk-stack type centrifuge is widely adopted as a first step for large volume clarification. The most effective centrifuges do not efficiently remove all the cellular components from the preceding cell culture, lysis, and harvest operations. Therefore, a need exists for a depth filter to reduce soluble and insoluble contaminants (such as cell debris, growth media constituents, DNA, and soluble host cell proteins) to increase the quality of separation (such as at a downstream Protein A column) and to prevent the protecting sterilization grade membrane from premature fouling.
The polymer functionalized nonwoven substrate is ideally suited for depth filter application, which captures contaminants within the medium, i.e. between an upstream surface and a downstream surface of the medium. The article provides a high media packing density in an adsorptive depth-type filter module which provides improved filtration efficiency. The article further provides increased surface area for a given media mass in an adsorptive depth-type filter module which provides higher flow rate (flux). Typically there is a trade-off between achieving these desirable filter characteristics of high efficiency and high flux. However the present functionalized nonwoven substrate provides a depth-type filter module that has high media packing density without sacrificing flux.
It is believed that the polymer functionalized nonwoven substrate functions predominately by adsorption, diffusion, and impingement mechanisms and is therefore different from conventional depth filters which operate by a combination of size exclusion, trapping and adsorption. The advantage of the instant grafted nonwoven as a pre-layer is that the pre-layer is fully utilized throughout it's depth with a range of contaminant species. A conventional depth filter, which operates by a combination of adsorption, trapping and size exclusion, will inevitably plug in the upper layers with certain contaminants, and the depth of the media will not be fully utilized.
EXAMPLES
Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, Mo., or may be synthesized by conventional methods.
The following solutions and test procedures were used to evaluate membranes of the present invention.
Buffer Solution.
A 1-liter buffer solution is prepared by adding 8 grams sodium chloride, 0.2 grams potassium_chloride, 1.44 grams dibasic sodium phosphate, and 0.21 grams sodium phosphate monohydrate to a graduated cylinder followed by 800 milliliters (mls.) of deionized (DI) water at 21° C. The pH was adjusted to a range of 6.8 to 7.4 using hydrochloric acid or sodium hydroxide solution as necessary, after which the volume was adjusted to 1 liter with deionized (DI) water.
1× Yeast/Molasses Feedstock.
Feedstock was prepared by adding 20 grams of Brewer's Yeast to 250 ml of the buffer solution with stirring for 30 minutes at 21° C. The mixture was further blended using a high-shear mixer for 2 minutes, followed by sonication for 10 minutes using a sonicator, (VIRTIS VEIRSONIC 600, from SP Industries Company, Gardiner, N.Y.) at a sonic horn setting of 7.5 watts. Approximately 33 mL. of sonicated yeast solution was centrifuged for 5 minutes at 3000 rpm to create a yeast supernatant. 25 ml of the supernatant was decanted into 1-liter graduated cylinder. 2 grams of molasses was added to the supernatant, the supernatant diluted with buffer solution to 1 liter, then stirred until a uniform feedstock was formed. The feedstock had an average turbidity of about 26 Nephelometric Turbidity Units (NTU). It should be noted that there can be large variations in turbidity following these procedures due to lot to lot variations from the Brewers Yeast.
2× Yeast/Molasses Feedstock.
This feedstock was made according to the same process used to prepare the 1× Yeast/Molasses Feedstock, except 50 mls., rather than 25 mls., of supernatant from centrifuge was decanted into 1-liter graduated cylinder. The molasses concentration remained the same. This feedstock had an average turbidity of about 48 NTU.
Molasses Only Feedstock.
Six grams of molasses were added to 1 liter of deionized water and mixed until homogeneous. The average turbidity of the feedstock was about 14 NTU.
Filtration Test I.
MASTERFLEX pump head and drive units (Cole-Parmer, Illinois) were used to conduct filtration experiments. Downstream turbidity measurements were taken using a Hach Turbidimeter with a flow through cell (Hach Company, Loveland, Colo.).
The following multi-zone nylon membranes, commercially available from CUNO, Inc., were placed, with the largest pore size facing up, in the bottom frit of a 47 millimeter filter holder (CUNO, Inc.) according to the following sequence: STERASSURE GRADE PSA020 (pore structures 0.65 μm/0.65 μm/0.2 μm/0.2 μm/0.65 μm/0.65 μm); LIFEASSURE GRADE BLA045 (pore structures 0.8 μm/0.8 μm/0.45 μm); LIFEASSURE BLA080 (pore structures 2.5 μm/2.5 μm/0.8 μm).
Three 47 mm disks were punched out of a grafted nonwoven test sample (described in Example 1) and loaded into the filter holder on top of the membranes, so the grafted nonwoven substrate was upsteam in the filter holder. The filter holder's o-ring was then placed on top of the grafted nonwoven article and the filter holder clamped together. The filter holder was then filled with deionized water and the grafted nonwoven allowed to expand for about 10 minutes until it reached equilibrium. The filter holder was emptied of water through the top inlet and then charged with the molasses feedstock (supra). The molasses feedstock was pumped at constant flow rate of 13 mL/minute, and the volume output and pressure data recorded until a test pressure of 25 pounds per square inch (psi) (172.4 kiloPascals (kPa)) was reached.
Filtration Test II.
Filtration Test II followed a similar process as generally described in Filtration Test I, wherein the MASTERFLEX apparatus was replaced with a FILTER-TEC 3-pressure zone, dead-end filtration system and software, (Scilog, Inc., Middleton, Wis.) and the filtration system was divided into three pressure zones for testing and measurement.
Pressure zone 1 (P1), retained six discs of grafted nonwoven substrates (described in the Examples below) retained in three CUNO stainless steel filter holders; two per holder. Pressure zone 1 is the topmost or upstream layer in the filtration assembly, immediately adjacent the inlet fluid stream
Pressure zone 2 (P2) retained nylon microporous membranes (described below as D4, D5 or D6 membranes in a 47 mm stainless steel filter holder (Part No. 2220, obtained from Pall Corporation, East Hills, N.Y.). In Examples 4, 5 and 9, a D4 microporous membrane was placed on top of D5 membrane so the small pore region layer of D4 was adjacent to the large pore region layer of D5, and the large pore region of D4 facing the inlet fluid stream. They were both placed into a single Pall Life membrane holder. Pressure zone 2 is the middle layer in the filtration assembly, immediately adjacent and downstream of pressure zone 1.
Pressure zone 3 (P3) retained a 0.2 μm SUPOR-200 membrane (Pall Corporation). Pressure zone 3 is the bottom layer in the filtration assembly, immediately adjacent pressure zone 2.
The yeast/molasses feedstock 1× or 2×, as specified in the Examples, was pumped at a constant flow rate of 13 or 15 mls./minute until a pressure of 25 psi (172.4 kPa) was reached in any one of the pressure zones.
Using the FILTER-TEC Scilog filtration equipment, three pressure zones are used. Pressure zone one (P1) monitors the grafted nonwoven substrate layer(s). Pressure zone two (P2) monitors the pressure of the grafted nylon microporous Membrane(s) (D4, D5 or D6). Pressure zone three (P3) monitors the Pall 0.2 micron sterilization grade filter. All the holders are connected in series and this configuration allows for the independent monitoring the three pressure zones. The Scilog equipment is set at a constant flow rate while the pressure and volume output data is automatically tabulated. The test procedure ends when a pressure of 25 psi is reached for any of the pressure zones
Static Protein Absorption Test.
Static binding capacity was calculated by measuring the UV absorption of bovine serum albumin protein (BSA). A BSA solution, 4 mg/ml BSA, grade A7030 (98%+Purity), 50 grams in a pH 8 buffered, 10 millimolar (mM) solution of 3-(4-morpholino) propanesulphonic acid (MOPS) was prepared. A UV spectrophotometer measurement was taken of the starting BSA fluid to obtain a peak absorption height at 280 nm. 40 ml of the BSA buffered solution was then charged into a 50 ml vial. A 47 mm disk of the grafted nonwoven substrate was added into the vial, capped and allowed to rock for approximately 12 hours on a rocking mixer, model VARI-MIX, from Barnstead International, Dubuque, Iowa. A sample of the BSA test fluid was pipetted from the vial and loaded into the cuvette of the UV spectrophotometer and a measurement is taken. The BSA static binding capacity, reported as milligrams per milliliter (mg/ml), was obtained from a percentage of the original absorption height calculated by subtracting from the starting peak height the remaining peak at 280 nm wavelength using the UV spectrophotometer measurements of the before and after test solution.
Preparation of Nylon Nonwoven Substrate A.
B-24KTM nylon-6 polymer (BASF Corporation Engineering Plastics Wyandotte, Mich.) was used to produce meltblown nonwoven substrate. The melt temperature was 295° C. with a mass flow rate of 0.25 grams/hole/minute on a standard meltblowing drilled orifice die. Hot air at 350° C. and 975 cubic feet per minute (SCFM) (27.8 cubic meters per minute (CMM)), per meter of die width, at was used to attenuate the fibers. The fibers with a face velocity at impact of 1200 meters per minute (m/min) were collected 0.30 meters from the die on a foraminous stainless steel belt and were bonded under 200° C. air drawn through the web at a face velocity of 137 m/min for 0.14 seconds, followed by cooling air at 29° C., at the same face velocity, for 0.8 seconds. The collected web basis weight was 48 grams per square meter and had an effective fiber diameter of 4.1 μm. The collected web had a thickness of 0.4 mm before calendaring between two 25 cm diameter smooth steel rolls set at 82° C. running at 1.5 m/min with a nip pressure of 170 Newtons per lineal centimeter of web (N/lcm). The resulting web thickness was 0.25 mm.
Nylon Nonwoven Substrate B.
Nylon Nonwoven Substrate B was prepared according to the process generally described to make Nylon Nonwoven Substrate A, wherein B-3TM nylon-6 (BASF Corporation) was used in place of the B-24K. The melt temperature was 265° C. with a mass flow rate of 0.25 g/hole/minute on a standard meltblowing drilled orifice die. Hot air at 1000 SCFM (28 CMM per meter of die width) at a temperature of 350 degrees C. was used to attenuate the fibers. The fibers were collected 0.43 meters away from the die on a foraminous stainless steel belt and were bonded under 200 degree C. air drawn through the web at 137 (meters per minute) face velocity for 0.14 seconds followed by cooling air at 29 degrees C. at the same face velocity for 0.8 seconds. The collected web was 50 grams per square meter and had an effective fiber diameter of 5.8 microns. The collected web had a thickness of 0.81 mm before calendaring between two 25 cm diameter smooth steel rolls set at 82 degrees ° C. running at 1.5 M/min with a nip pressure of 176N per lineal centimeter of web. The resulting web thickness was 0.25 mm.
Ethylene Vinyl Alcohol Copolymer (EVAL) Nonwoven Substrate C.
EVAL Nonwoven Substrate C was prepared according to the process generally described to make Nylon Nonwoven Substrate A, wherein POVAL C109B EVAL polymer pellets, (Kuraray America, Inc., Houston, Tex.) was used in place of the B-24K, and a perforated drum replaced the foraminous stainless steel belt as the collector.
The nonwoven substrate was prepared at a melt temperature of 240° C. and a mass flow rate of 0.35 g/hole/minute. Hot air, delivered at a rate equivalent to 4.5 cubic meters of air at 0° C. at 101.3 kN/m2 (1 atmosphere) per meter of die face per minute and heated to 285° C., was used to attenuate the fibers. The fibers were collected 17 cm from the die face utilizing a perforated drum collector to produce a web.
The nonwoven substrate produced had an effective fiber diameter of 12.6 μm. The web had a basis weight of about 50 gsm and a thickness of 0.6 mm. The web was then calendared between two 25 cm diameter smooth chrome steel rolls with a gap set at 0.04 mm, at 60° C. temperature, running at 1.5 M/min with a nip pressure between the rolls of 105N per lineal centimeter. The resulting thickness of the web was 0.33 mm.
Nylon Microporous Membranes D1-D6.
Three zone, reinforced asymmetric microporous nylon membrane were prepared using the process described in U.S. Pat. No. 6,776,940 (Meyering et al.). As described, a single base polymer dope formulation was split into three parts and applied to a three-way thermal manipulation apparatus. The dope formulation was heated to three different temperatures to achieve three distinct zones. Each of the temperatures used was selected to produce pore sizes in each zone for forming an asymmetric microporous membrane. The first zone (upper zone) had the largest pore size, the second (middle) zone had an intermediate pore size and the third zone (lower zone) had the smallest pore size. The membrane was a single layer having three consecutive progressively smaller pore size exclusion zones.
D1 microporous membrane had an average pore size for the three zones of approximately 0.45; 0.30; and 0.20 μm.
D2 microporous membrane had an average pore size for the three zones of approximately 1.0; 0.8; and 0.65 μm.
D3 microporous membrane had an average pore size for the three zones of approximately 5.0; 2.4; and 1.2 μm.
D4 microporous membrane was formed by laminating the smaller pore size surface of D3 to the larger pore size surface of D2 using formulations and methods generally described in U.S. Pat. No. 3,876,738 (Marinaccio et al.) and the processes generally described in Defensive Publication T-103,601(Repetti). Briefly, the Marinaccio reference method comprises casting a polymer dope in a thin layer, quenching the dope in a solvent bath to form a continuous microporous membrane, and rinsing the membrane in a water bath to remove residual solvent. This is the wet-as-cast membrane, before it has an opportunity to dry. Wet-as-cast layers of Marinaccio membranes have the ability to form strong physical bonding between individual layers when laminated in the manner described in Defensive Publication T-103,601(Repetti). Briefly, the individual layers (individual three zone membranes) were wet laminated wherein membranes that have been cast and quenched but not dried are joined under mild pressure and then dried together.
A process and apparatus to accomplish multilayer wet lamination and drying is described in U.S. Pat. No. 4,707,265, but it is understood that other commercial multilayer web converting and drying apparatus can be beneficially employed, such as tentering ovens. The wet layers were positioned in physical contact such that the lower surface (smaller pore sizes) of the top layer was in contact with the upper surface (larger pore sizes) of the bottom layer. Trapped air was removed from the laminated layers and the double layer combination membrane was carried through a drying apparatus under restraint to control and minimize shrinking in the crossweb or downweb directions to form the double layer combination membrane. The average pore size for the six zones were approximately 5.0; 2.4; 1.2; 1.0; 0.8; and 0.65 μm.
D5 microporous membrane was formed using the same process for D4, except the D2 was laminated D1. The average pore size for the six zones were approximately 1.0; 0.8; 0.65; 0.45; 0.30; and 0.20 micrometers.
D6 microporous membrane was a triple layer asymmetric membrane, formed using the same process for Example D4, wherein D3 (top layer) was laminated D2 (intermediate layer), which in turn, was laminated to D1 (bottom layer). The bottom surface of D3 having the smaller pore size was laminated adjacent to the top surface of D2 having the largest pore size, and the top surface of D3 was laminated adjacent to the bottom surface of D2 having the small pore size. D6 had nine independent porous zones with the top surface having the largest pore size progressively extending to smaller pore sizes in the bottom layer. The average pore size for the nine zones were approximately 5.0; 2.4; 1.2; 1.0; 0.8; 0.65; 0.45; 0.30; and 0.20 μm.

Graft Functionalization of Microporous Membranes D4-D6

D4-D6 microporous membranes were functionalized by imbibing the membrane with a grafting solution consisting of 15% [3-(methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) monomer, 15% methanol, 10% polyethylene glycol (PEG 4000, average molecular weight 4,000 grams/mole) and 60% water by weight. The membrane was sandwiched between two 4 mil. (101.6 μm) polyethylene terephthalate (PET) liners, rolled with a rubber roller to remove air and excess solution and irradiated directly by passing through an electron beam at a web speed of 20 feet per minute (fpm) (6.1 m/min) and receiving a dosage of approximately 40 kilograys (kGy) at an accelerating voltage of 300 kilovolts with the large pore size facing up to the beam. The membranes were washed three times by rinsing in deionized water and then air dried.
Example 1
A 30 cm by 43 cm sample of Nylon Nonwoven Substrate B was purged of air under a nitrogen atmosphere in a glove box and inserted into a ZIPLOCTM plastic bag and sealed. The sealed bag was then removed from the glove box and irradiated to a dose level of 40 kGy by passing it through the electron beam set with an accelerating voltage of 300 kV and a web speed of 20 feet/minute. After returning the sealed bag to the nitrogen atmosphere-controlled glove box, the irradiated nonwoven substrate was removed and placed inside a non-irradiated, nitrogen purged, ZIPLOCTM bag.
The freshly prepared nonwoven sample was imbibed with 100 grams of the nitrogen purged imbibing solution comprising 15% 3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomer, 15% methanol, 10% polyethylene glycol with hydroxy end groups, average molecular weight 4,000 g/mole (PEG 4000) and 60% water by weight, and the bag resealed after expelling most of the nitrogen. During this step the oxygen level within the glove box was generally maintained below 40 parts per million (ppm).
The sample was maintained flat in the bag and evenly saturated for four hours by occasionally rotating the bag. The resulting grafted nylon nonwoven substrate was removed from the bag and carefully washed by soaking it for 10 minutes in a tray containing 2 liters of fresh deionized water. The substrate was removed from the tray, compressed between multiple layers of paper towels and the washing process repeated two more times with fresh DI water and air dried. The grafted nonwoven substrate was subjected to the Filtration Test I using the Molasses Feedstock. Results are shown in FIG. 1 with a comparative ZetaPlusTM B0204 60ZA, and B0204 90ZA depth filtration media (available from CUNO Inc.) that was tested similarly.
Examples 2a-e and 3a-e
Using the same grafting procedure as Example 1 grafted nonwoven substrates were prepared. In Examples 2a-e, the imbibing solutions each contained 15% MAPTAC and 10% PEG 4000, while the amounts of water and methanol were varied as shown in Table 1. In Examples 3a-e, imbibing solutions each contained 15% MAPTAC, 10% PEG 4000 and 5% hydroxyethyl acrylate (HEA), while the amounts of water and methanol were varied as shown in Table 1 The static binding capacity was tested using the Static Protein Absorption Test Procedure and the results shown TABLE 1.











TABLE 1









BSA static binding



Example
Imbibing solution
capacity (mg/ml)




















2a
12% methanol
90




58% water



2b
14% methanol
101




56% water



2c
16% methanol
102




54% water



2d
18% methanol
91




52% water



2e
20% methanol
82




50% water



3a
12% methanol
103




58% water



3b
14% methanol
133




56% water



3c
16% methanol
125




54% water



3d
18% methanol
114




52% water



3e
20% methanol
120




50% water










Example 4
Using the same general grafting procedure as in Example 1, Nylon Nonwoven Substrate B was replaced with Nylon Nonwoven Substrate A, and the grafting solution comprised 20% 3-[(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomer, 15% methanol, 10% polyethylene glycol with hydroxy end groups, average molecular weight 4,000 g/mole (PEG 4000) and 55% water by weight.
In Example 4a 50 gram per square meter (gsm) sample of Nylon Nonwoven Substrate A was purged of air and inserted into Ziploc bags in a glove box under nitrogen atmosphere and sealed. The Ziploc bag was then removed from the glove box, and irradiated to a dose level of 60 kGy (kilogray) at an accelerating voltage of 300 kilovolts, by passing it through the electron beam. After returning the sealed bag to the glove box, the irradiated nonwoven substrate removed and placed inside a non-irradiated, nitrogen purged, ZIPLOCTM bag.
The freshly prepared nonwoven sample was imbibed with the grafting solution and the bag resealed after expelling most of the nitrogen. The sample was maintained flat in the bag and evenly saturated for four hours by occasionally rotating the bag. The resulting grafted nylon nonwoven substrate was removed from the bag, washed and dried as in Example 1.
The resulting grafted substrate was evaluated according to Filtration Test II, using the 1× Yeast/Molasses Feedstock pumped at 15 ml/minute. Results are shown in FIG. 2 where FF=Flow Rate and P1-P3 are the pressure zones. It can be seen that the P1 and P2 zone pressures are nearly identical for the entire test, indicating there is no pressure drop across any of the grafted nonwoven substrates in series. After about 900 ml of solution, the pressure starts building on the microporous membranes D4 and D5 (P2) indicating fouling is becoming noticeable on the grafted nonwoven substrates. The test procedure ends when a pressure of 25 psi (172.4 kPa) is reached for any of the pressure zones. The test also reveals that the pressure in zone 3 (P3) on the 0.2 um Pall membrane did not increase, indicating the grafted nonwoven substrates (P1) and multi-zone membrane media upstream was managing the filtering workload from the surrogate yeast cell centrate solution. The total volume throughput was slightly over 1400 ml. Several repeat trials provided an average exit turbidity (after all filters) of about 1 NTU or less.
Example 5
Example 4 was repeated wherein the 1× Yeast/Molasses Feedstock was fed at a constant flow rate of 7.5 ml/min. The test results show that the reduction in flow rate (frontal velocity) increases the amount of contact residence time that the feedstock has with the grafted nonwoven filtration media to allow for better absorption. The onset of pressure recorded in P2 was delayed to about 1300 ml and the system had a total throughput of about 2200 ml, during which time the Pall membrane (P3) remained protected by the upstream grafted nonwoven substrate (P1) and microporous membrane (P2).
Comparative Example 6
Depth Filtration Media
Filtration Test II was repeated, wherein depth filtration media, except ZetaPlusTM B0204 60ZA, and B0204 90ZA depth filtration media (available from CUNO Inc.) were loaded into a single depth filter holder in pressure zone 1 (P1). Pressure zone 2 (P2) was a D4 membrane was placed on top of a D5 membrane and pressure zone 3 (P3) was Pall Life membrane holder.
The yeast/molasses 1× test fluid was pumped with the Scilog equipment at 15 ml/min. (Many repeat tests were performed with a total throughput range of between 400 ml and 800 ml with an average of 600 ml.) The pressure zones of the D4 and D5 membranes and the 0.2 um membrane did not show an increase. Turbidity was less than 2 NTU at the system exit. Results are shown in FIG. 3.
Comparative Example 7
Membranes Only
Comparative Example 6 was repeated omitting the grafted nonwoven substrate. Membranes D4 and D5 were loaded, large pore size up, into filter holders in pressure zones 1 and 2, and the Pall microporous membrane in pressure zone 3. The yeast/molasses 1× test fluid was pumped with the Scilog equipment at 15 ml/min.
The filtration system had a total throughput of about 68 ml before reaching a pressure of 25 psi (172.4 kPa). No pressure increase was observed at the 0.2 um sterilization membrane at this low volume.
Comparative Example 8
Sterilization Grade Membrane Only
Comparative Example 7 was repeated, omitting the grafted nonwoven substrate and membranes D4 and D5. A Pall 0.2 (Supor-200) membrane was loaded into a membrane filter holder. The yeast/molasses 1× test fluid was pumped with the Scilog equipment at 15 ml/min.
The onset of pressure began immediately and the filtration system didn't stabilize to a constant rate volume. The total throughput was only about 10 ml before reaching a pressure of 25 psi. This comparative example the grafted nonwoven substrates in combination with the membranes reduce the biofiltration burden before the feedstock reaches a sterilization grade membrane (the Pall Supor-200 membrane).
Example 9
The general procedure of Example 4 was used except the imbibing solution 20% 3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomer, 5% poly(ethylene glycol) methyl ether methacrylate monomer (PEGMEMA, Mw 475, Sigma-Aldrich), 15% methanol, 10% polyethylene glycol (PEG 4000) and 50% water by weight. The constant flow rate was 13 ml/min. The test results were recorded in the graph of FIG. 4.
While the onset of pressure began in P2, the system had a total throughput of about 1900 ml. The graft-copolymerization of the non-charged, hydrophilic PEGMEMA monomer resulted in a slight decrease in efficiency and shifted some of the filtration burden to the 0.2 um sterilization grade microporous filter. The increased throughput is believed to be the result of the PEGMEMA copolymer in the grafted nonwoven. The slight decrease in efficiency is inferred from the lack of delay time in the onset of increasing pressures (P2) and the resulting angle of pressure increases on all the membranes that are recorded as throughput (time) on the graph. Turbidity was less than 2 NTU at the system exit.
Examples 10a & 10b
EVAL Nonwoven Substrate C was grafted according to the imbibing process described in Example 1. The resultant membrane was then evaluated according to Filtration Test II, but without the 0.2 μm Pall membrane in pressure zone 3, using the molasses only feedstock. Example 10a employed six layers of grafted EVAL Nonwoven Substrate C, whereas Example 10b used 10 layers of this grafted nonwoven substrate.
Example 10a had a throughput of 1 liter, with an NTU of approximately 0.8, while Example 10b had a throughput of 1.6 liters and a similar NTU value. The tests ended at 25 psi pressure due to fouling of the D4 and D5 membranes.
Comparative Examples 11a-b and Examples 11c-d
Metanil Yellow Dye Comparative
An aqueous solution of 80 part per million (ppm) of Metanil Yellow dye, obtained from Alfa Aesar, Ward Hill, Mass., was prepared. Another 80 ppm aqueous solution of Metanil Yellow was also prepared in 150 mM sodium chloride.
A MasterflexTM pump head and drive unit was used to pump the dye solutions at 30 ml/minute for the experiments. A single depth filter holder was used for these examples. The solution was filtered through the media and a cuvette sample of the filtrate was taken every minute; the filtrate was analyzed with an UV photospectrometer at the 455 nm wavelength.
As a controls, filtration media ZETAPLUS-B0204 60ZA and ZETAPLUS-B0204 90ZA (Cuno Inc.) were loaded into a single depth filter holder, with the 60ZA as the upper media. The Metanil Yellow only solution was then filtered and a cuvette sample of the filtrate was taken every minute and analyzed with an UV photospectrometer at 455 nanometeres (nm) wavelength (11a) and recorded. The process was then repeated using the Metanil Yellow-sodium chloride solution (11b).
The procedure of comparative Examples 11a-b was repeated for Examples 11c-d using membrane D6, followed by three layers of grafted nonwoven substrates of Example 1 were loaded into a single depth filter holder. The no salt Metanil Yellow dye filtered (Example 11c) and again repeated using the Metanil Yellow-sodium chloride solution (11d). Results are shown in FIG. 5.
At the 0.8 absorption reading, Example 11c took about twice the time to reach the same breakthrough as the control (ZetaPlusTM 11a). Example 11d was found to have improved performance binding the dye in the presence of salt.
Example 12
The general procedure of Example 4 was used except the imbibing solution was 35% 3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomer, 15% methanol, and 50% water by weight and the E-beam dosage was 120 kGy dose. Since 100 grams of monomer solution (35 grams monomer) were used to imbibe the web and the mass of the nonwoven web was about 6.5 grams, the input grafting ratio was about 5.39:1 monomer/nonwoven. The grafted nonwoven was equilibrated for at least 24 hours at ambient room temperature at 20% relative humidity and then weighed The total average weight ratio of the washed and dried grafted nonwoven web was 4.98:1 monomers grafted/nonwoven.
The resulting grafted nonwoven substrate was evaluated according to Filtration Test II, using the 2× Yeast/Molasses Feedstock pumped at 13 ml/minute. The total volume throughput was 1385 ml. (Turbidity of the feedstock and throughput performance is related. This example used the 2× concentration of yeast/molasses so the throughput would be about half of a 1× test result. An estimated throughput of 2,770 ml is appropriate comparing this example to Example 4 if a 1× feedstock solution was used here. The exit turbidity (after all filters) was about 1 NTU.
Example 13
A Cobalt 60 (Co60) panorama gamma irradiator, delivering about 5 kGy/per hour to the offline carrier, was sued as the irradiating source. A 4.6 L aluminum canister was made with a machined removable base plate allowing the 6 inch plastic core to be clamped to the center of the base plate isolating the center of the plastic core. The base plate and aluminum cap used to hold the 3 inch plastic core were grooved to hold o-rings to ensure a seal (the long bolt used to clamp the plastic core with the core cap has a washer fitted with an o-ring also). Therefore, the canisters effective volume where the nonwoven resides is about 4 liters.
The 50 gsm nylon nonwoven substrate (Substrate A) was wound on the plastic core had a weight of about 560 grams and had an outside diameter of almost 7.5 inches. The plastic core and nylon nonwoven are cut to the same width so when the roll is clamped onto the base plate the edge of the wound nylon web is in contact with the base plate. The base plate was machined with ports to allow for valves and pathways for fluid to flow directly into the edge of the nylon roll. The base plate also has 2 groves machined (4 and 6 inch diameters) allowing fluid from the ports to easily disperse around the edge of the nonwoven roll that is in contact with the base plate. Therefore, fluid entering the canister through the base plate ports must enter the edge of the nylon nonwoven substrate. The base plate is also machined with another grove fitted with an o-ring to hold the canister top cover to the base plate. The canister top is made to be bolted to the base and is also ported for valves. The net effect of this canister is to provide a holding device for a roll of nonwoven capable of maintaining pressure or vacuum.
A vacuum was applied to the aluminum canister containing the nonwoven substrate roll with a portable vacuum pump followed by a nitrogen purge of the canister. This procedure was repeated 3 times to remove oxygen from the canister creating an inert environment inside. Vacuum was then pulled on the container and was sealed by closing the valves and then additionally capping the valve fittings. The canister with the nonwoven web was exposed to the gamma source for a total of 6 hours receiving an accumulated dose of about 28 kGy. The offline carrier containing the carrier was turned halfway through the exposure to even out the dose distribution.
Separately, the imbibing solution was mixed in a commercial pressure vessel and purged by bubbling nitrogen for 2 hours. The pressure vessel was then charged and sealed with about 24 psi of nitrogen.
Immediately after the aluminum container was removed from the gamma source, the solution feed lines leading from the pressure vessel were filled with the imbibing solution and connected with the aluminum canister base plate minimizing any air entrainment. The base plate valve is opened slowly and the portion of the canister containing the nonwoven substrate is filled with solution, completely saturating the nonwoven substrate with 4.5 liters of the monomer solution comprising 20% 3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomer, 15% methanol, and 65% water by weight. The canister was then sealed and the contents allowed reacting for 12 hours before being opened. The grafted nonwoven substrate was washed and allowed to air dry for at least 24 hours at ambient room temperature at 20% relative humidity and then weighed.
Virtually all the initial imbibing solution is contained in the hydrogel network. Approximately 3800 grams of monomer solution (about 760 grams monomer) were used to fill the canister and imbibe the nonwoven substrate. Since the mass of the nonwoven web was about 560 grams and the amount of monomer used was about 760 grams the input grafting ratio was about 1.36:1 monomer/nonwoven. The total average weight ratio of the washed and dried grafted nonwoven web was 1.10:1 grafted polymer/nonwoven. The resulting gamma grafted substrate was evaluated according to Filtration Test II, using the 2× Yeast/Molasses Feedstock pumped at 13 ml/minute and was found to have an average throughput of 596 ml+/−51 ml (average of 5 tests random sampled from inside to outside of roll).
Example 14
This gamma grafted example was made like example 13 except the canister was irradiated for 8 hours (about 37 kGy), the grafting solution comprised 25% 3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomer, 15% methanol, and 60% water by weight, the nonwoven substrate was loosely wrapped (460 grams), allowed to react 72 hours before being opened, last vacuum step was omitted allowing nitrogen atmosphere to remain in the canister and the canister was placed in a box and packed with dry ice during the irradiation step to extend the lifetimes of the radicals formed on the surface of the nonwoven substrate.
Separately, the imbibing solution was mixed in a commercial pressure vessel and purged by bubbling nitrogen for 2 hours. The pressure vessel was then charged and sealed with about 24 psi of nitrogen.
A makeshift “sight glass” was made out of fittings and 3 feet of 1⁄4 inch poly tubing allowing for visual sight of liquid as it enters the tube (keeping any fluid out of the vacuum pump and gauges).
Immediately after the aluminum container was removed from the gamma source, the canister was unpacked from the remaining dry ice. The canister was then warmed by flowing hot water over the canister for two minutes to prevent freezing of the coating solution. The sight glass was connected to the top port of the aluminum canister and vacuum pump connected to the other side of the sight glass. Vacuum was then pulled on the aluminum canister and sight glass, and then isolated leaving the entire apparatus under vacuum. The solution feed lines leading from the pressure vessel were filled with the imbibing solution and connected with the aluminum canister base plate minimizing any air entrainment. The base plate valve is opened slowly and the portion of the canister containing the nonwoven web is completely filled with solution. When liquid was seen flowing in the tubular sight glass, the valves were closed. Therefore, the nonwoven substrate in the canister was completely saturated with the monomer solution. The canister was then sealed by capping the closed valve fittings and the canister contents were allowed to react for 72 hours before being opened, then washed, dried as in Example 13 and was equilibrated for at least 24 hours at ambient room temperature at 20% relative humidity and then weighed.
The input grafting ratio for this example was about 2.07:1 monomer/nonwoven. The total average weight ratio of the washed and dried grafted nonwoven web was 2.03:1 grafted polymer/nonwoven. Any moisture that is hygroscopically bound to the grafted coating is included in the weight calculation for determining the graft ratios.)
The resulting gamma grafted substrate was evaluated according to Filtration Test II, using the 2× Yeast/Molasses Feedstock pumped at 13 ml/minute and was found to have an average throughput of 1035 ml+/−119 ml (average of 5 tests random sampled from inside to outside of roll).

## Claims

1. Filtration media comprising:
a) a nonwoven substrate having average fiber diameter of 1 to 6 micrometers, and a void volume of 50 to 95%, a tensile strength of at least 4.0 Newtons prior to grafting and a polymer grafted to the surface of the nonwoven substrate

wherein the grafted polymer comprises polymerized monomer units of:
a) 80 to 98 wt. % of grafting aminoalkyl (meth)acryloyl monomers,
b) 2 to 20 wt. % of grafting poly(alkylene oxide) monomers;
c) 0 to 10 wt. % of second hydrophilic monomers.

2. The filtration media of claim 1 wherein the nonwoven substrate has a surface area of 15 to 50 m2 per square meter of nonwoven substrate.

3. The filtration media of claim 1 wherein the nonwoven substrate has a mean pore size of 1-40 microns according to ASTM F 316-03 5.

4. The filtration media of claim 1 wherein the nonwoven substrates have a solidity of less than 20%.

5. The filtration media of claim 1 wherein the weight of the grafted polymer is 0.5 to 5 times the weight of the nonwoven substrate.

6. The filtration media of claim 1 wherein the nonwoven substrate is prepared from a hydrophilic thermoplastic polymer.

7. The filtration media of claim 1 wherein the grafted polymer is of the formula.


-(MNR4+)w-(MPEG)x-(Mc)y 

wherein
-(MNR4+)w- represent the residue of the grafted aminoalkyl (meth)acryloyl monomer having w polymerized monomer units where w is at least 2,
-(MPEG)x represents the polymerized poly(alkylene oxide) monomer having x polymerized monomer units, where x may be zero;
-(Mc)y represents the polymerized hydrophilic monomer having y polymerized monomer units, where y may be zero.

8. The filtration media of claim 7 wherein the grafted polymer is a random or block copolymer.

9. The filtration media of claim 1 wherein the grafted polymer is uncrosslinked grafted brush polymer.

10. The filtration media of claim 1 wherein the nonwoven substrate has a basis weight of 10 to 400 g/m2.

11. The filtration media of claim 1 wherein the nonwoven substrate is a nylon nonwoven substrate.

12. The filtration media of claim 1 wherein the nonwoven substrate is a polyamide nonwoven substrate.

13. The filtration media of claim 1 wherein said polymer further comprises poly(alkylene oxide) monomer units grafted to the surface of the nonwoven substrate.

14. The filtration media of claim 1 wherein the polymer grafted to the surface of the nonwoven substrate consists essentially of aminoalkyl (meth)acryloyl monomer units, and said nonwoven substrate is a polyolefin nonwoven substrate.

15. A filter device comprising
a fluid inlet;
a fluid outlet; and
a filter media fluidly connecting the fluid inlet and the fluid outlet;
wherein the filter media comprises the grafted nonwoven substrate of claim 1.

16. The filter device of claim 15 wherein the filter media further comprises a microporous membrane layer positioned downstream of the grafted nonwoven substrate.

17. The filter device of either of claim 15 wherein the filter media comprises a plurality of pleats.

18. The filter device of claim 15 further comprising
a filter capsule; and
a filter cap connected to the filter capsule;
wherein the filter cap comprises the fluid inlet and the fluid outlet, and wherein the filter media is encapsulated in the filter capsule.

19. The filter device of claim 18 wherein the filter media further comprises a microporous membrane layer positioned downstream of the grafted nonwoven substrate.

20. The filter device of any of claim 18 wherein the filter media is formed into a first media cylinder comprising a plurality of pleats.

21. The filter device of claim 20 further comprising a second media cylinder positioned within the first media cylinder, the second media cylinder comprising a second filter media comprising a plurality of pleats.

22. The filter device of claim 18 further comprising a core, wherein the filter media is spirally wound about the core.