# Patent

## Title
Crosslinked cellulosic membranes

## Abstract

Disclosed are crosslinked porous membranes comprising a cellulosic material and an aromatic hydrophobic moiety or a copolymer of the formula A-B-A (I) or A-B (II), wherein block A, for example, polyglycerol, a polymer of allylglycidyl ether, or a copolymer of glycidol and allyl glycidyl ether, or a polymer of allyl glycidyl ether or a copolymer of glycidol and allyl glycidyl ether wherein one or more allyl groups having been replaced by hydrophilic groups. Block B is an aromatic hydrophobic moiety. An example of the aromatic hydrophobic moiety is polyethersulfone. Also disclosed is a method for preparing such membranes.

## Background
BACKGROUND OF THE INVENTION
Porous cellulosic membranes are known to find use in a number of applications such as microfiltration, ultrafiltration, reverse osmosis, gas separation, and diagnostics. Attempts have been made to improve one or more of the properties, e.g., surface or bulk properties, of such membranes. For example, hydrophilic monomers have been grafted to membrane surfaces. Attempts also have been made to coat the membrane with water soluble polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, polyethylene glycol or polyvinyl pyrrolidone. The above attempts, however, have one or more drawbacks such as lack of reproducibility, lack of stability of the modification, and/or pore clogging. Attempts also have been made to modify or improve one or more properties of such membranes, for example, to include reactive functionalities and/or charged groups. Attempts have also been made to improve one or more of the bulk properties such as chemical resistance, mechanical strength, or radiation stability.
Despite these attempts, there exists an unmet need to modify or improve one or more properties of such membranes, for example, to increase the hydrophilicity, to include reactive functionalities or charged groups, to increase chemical resistance, to increase mechanical strength, and/or radiation stability.
BRIEF SUMMARY OF THE INVENTION
The invention provides crosslinked porous membranes, particularly crosslinked hydrophilic cellulosic porous membranes. Thus, the invention provides a crosslinked porous membrane comprising a cellulosic material and
(a) a block copolymer of the formula: A-B-A (I) or A-B (II),
wherein block A is (i) a hydrophilic polymeric segment comprising polyglycerol or poly(allylglycidyl ether); (ii) a copolymer of glycidol and allyl glycidyl ether, the copolymer having one or more allyl groups; or (iii) a copolymer of glycidol and allyl glycidyl ether, wherein one or more of the allyl groups of the copolymer have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula —C(H)(COOH)(NH2), and a group of the formula —C(H)(COOH)(NHAc), or a salt thereof; and
block B is an aromatic hydrophobic polymeric segment; or
(b) Q, which is an aromatic hydrophobic moiety;
wherein Q or the block copolymer is linked to the cellulosic material to form a crosslinked porous membrane.
Advantageously, the present makes it possible to readily tailor the hydrophilicity and bulk properties of the porous membrane as desired. The crosslinked porous membranes are resistant to certain organic solvents, acids, alkalis, and radiation.



BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
FIG. 1A depicts the SEM micrograph of the surface of the porous membrane prepared from cellulose acetate and a block copolymer of polyethersulfone prior to regeneration of cellulose and crosslinking, and FIG. 1B depicts the SEM micrograph of the porous membrane after regeneration of cellulose and crosslinking.
FIG. 2 depicts a crosslinking reaction scheme to prepare a crosslinked porous membrane in accordance with an embodiment of the invention, where crosslinking is carried out through a brominium intermediate.
FIG. 3 depicts a crosslinking reaction scheme to prepare a crosslinked porous membrane in accordance with an embodiment of the invention, where crosslinking is carried out through an epoxy intermediate.
FIG. 4 depicts a crosslinking reaction scheme to prepare a crosslinked porous membrane in accordance with an embodiment of the invention, where crosslinking is carried out through irradiation-induced free radical formation.
FIG. 5 depicts a crosslinking reaction scheme to prepare a crosslinked porous membrane in accordance with an embodiment of the invention, where crosslinking is carried out through the use of polycarboxylic acid.
FIG. 6 depicts a crosslinking reaction scheme to prepare a crosslinked porous membrane in accordance with an embodiment of the invention, where crosslinking is carried out through the use of epichlorohydrin.



DETAILED DESCRIPTION OF THE INVENTION
In accordance with an embodiment, the invention provides a crosslinked porous membrane comprising a cellulosic material and
(a) a block copolymer of the formula: A-B-A (I) or A-B (II),
wherein block A is (i) a hydrophilic polymeric segment comprising polyglycerol or poly(allylglycidyl ether); (ii) a copolymer of glycidol and allyl glycidyl ether, the copolymer having one or more allyl groups; or (iii) a copolymer of glycidol and allyl glycidyl ether, wherein one or more of the allyl groups of the copolymer have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula —C(H)(COOH)(NH2), and a group of the formula —C(H)(COOH)(NHAc), or a salt thereof; and
block B is an aromatic hydrophobic polymeric segment; or
(b) Q, which is an aromatic hydrophobic moiety;
wherein Q or the block copolymer is linked to the cellulosic material to form a crosslinked porous membrane.
In accordance with an embodiment, the cellulosic material is a cellulosic polymer, cellulosic oligomer, or cellulosic monomer.
In an embodiment of the crosslinked porous membrane, the cellulosic polymer is cellulose, or a derivative thereof, for example, cellulose ethers, cellulose esters, cellulose amides, cellulose amines, and cellulose carbamates. Examples of cellulose derivatives include methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose nitrate, and cyanoethyl cellulose, preferably methyl cellulose, ethyl cellulose, propyl cellulose, cellulose acetate, cellulose nitrate, and cyanoethyl cellulose. In an embodiment, the cellulose derivatives, e.g., acetate has 2 to 3, preferably about 2 to 2.8, derivatizing groups, e.g., acetyl groups per D-anhydroglucopyranose unit.
In accordance with an embodiment, the crosslinked porous membrane comprises a cellulosic material and a block copolymer of the formula (I) or (II), wherein block A is a hydrophilic polymeric segment comprising polyglycerol.
In accordance with an embodiment, block A of the copolymer is a hydrophilic polymeric segment comprising polyglycerol having one or more repeat units of the formulas:




In accordance with an embodiment, block A comprises of one or more of the following structures, the point of attachment to the aromatic hydrophobic polymeric segment indicated by the squiggly line below:




In accordance with another embodiment, block A is a copolymer of glycidol and allyl glycidyl ether, the copolymer having one or more allyl groups. In accordance with an embodiment, block A is composed of polyglycerol segments having one or more of the following repeat units:




and of poly allyl glycidyl ether segments having a repeat unit of the formula:





wherein R is allyl.

In accordance with another embodiment, block A is a copolymer of glycidol and allyl glycidyl ether, as described above, wherein one or more of the allyl groups of the copolymer have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula —C(H)(COOH)(NH2), and a group of the formula —C(H)(COOH)(NHAc), or a salt thereof.
In accordance with an embodiment, X can be any acidic group, for example, sulfonic acid, phosphoric acid, phosphonic acid, or carboxylic acid, the basic group can be any basic group, for example, an amino group, an alkylamino group, or a dialkylamino group, the cation can be any cationic group, for example, a quaternary ammonium group, and the zwitterion can be, for example, a quaternary ammonium alkyl sulfonate group of the formula —N+(R1R2)(CH2)cSO3−, wherein R1 and R2 are alkyl groups and c is 1 to 3.
One or more of the allyl groups on the block copolymers can be reacted with a suitable agent to effect the desired changes. For example, the allyl group can be converted to 1,2-dihydroxypropyl groups by reacting with an oxidizing agent such as osmium tetroxide, alkaline permanganate, or hydrogen peroxide.
The allyl group can be converted to a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is an acidic group by reacting the allyl group with an acid group bearing thiol such as HS—(CH2)b—X, wherein X is COOH, PO4H, PO3H, or SO3H, wherein b is 1 to 3.
The allyl group can be converted to a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is a basic group by reacting the allyl group with a basic group bearing thiol such as HS—(CH2)b—X, wherein X is NH2, NHR, or NRR, where R is a C1-C6 alkyl group, and b is 1 to 3.
The allyl group can be converted to a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is a cationic group by reacting the allyl group with a cationic group bearing thiol such as HS—(CH2)b—X, wherein X is NH3+, NHRR+, or NRRR+, where R is a C1-C6 alkyl group, and b is 1 to 3.
The allyl group can be converted to a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is a zwitterionic group by reacting the allyl group with a zwitterionic group bearing thiol such as HS—(CH2)b—X, wherein X is group bearing a zwitterion, for example, —N+(R)2—(CH2)c—SO3−, where R is a C1-C6 alkyl group, and b and c are independently 1 to 3.
One or more of the allyl groups can be replaced by reacting with a haloalkane thiol, for example, with a fluoroalkane thiol, a chloroalkane thiol, a bromoalkane thiol, or an iodoalkane thiol. The acyl group of acyl alkane thiol can be formyl, acetyl, propionyl, or butanoyl. The alkoxy part of alkoxy alkane thiol can be a C1-C6 alkoxy group. The alkylthio part of alkylthio alkane thiol can be a C1-C6 alkyl group.
In an embodiment, one or more of the allyl groups can be reacted with a carboxylic alkane thiol or a salt thereof, a phosphoric alkane thiol or a salt thereof, a phosphonic alkane thiol or a salt thereof, a sulfonic alkane thiol or a salt thereof, a (dialkylamino)alkane thiol or a salt thereof, an aminoalkane thiol or a salt thereof, an alkylamino alkane thiol, a dialkylaminoalkane thiol, and a sulfonic alkylammonium alkane thiol or a salt thereof.
In accordance with an embodiment, the aromatic hydrophobic polymeric segment of the block copolymer is selected from polysulfone, polyethersulfone, polyphenylene ether, polyphenylene oxide, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide, preferably polyethersulfone.
Embodiments of the hydrophobic polymer segments include polysulfone (PS), polyethersulfone (PES), polycarbonate (PC), polyether ether ketone (PEEK), poly(phthalazinone ether sulfone ketone) (PPESK), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polyphenylene oxide (PPO), and polyether-imide (PEI), which have the following structures:




The number of repeat units, n, within each of the above aromatic hydrophobic segment can be from about 10 to about 1000, preferably from about 30 to about 300, and more preferably from about 50 to about 250.
In any of the above embodiments, block A is present in an amount of about 20% to about 50 mol % and block B is present in an amount of about 50% to about 80 mol %. Preferably, block A is present in an amount of about 40% to about 55 mol % and block B is present in an amount of about 40% to about 60 mol %.
In accordance with embodiments, the copolymer of formula (I) has a structure:




wherein n is about 10 to about 1000, or





wherein n is about 10 to about 1000. “Pg/PolyAGE” designates a copolymer of glycidol and allyl glycidyl ether.

In accordance with an embodiment, the copolymer of formula (I) has the structure:




wherein R is allyl and/or —(CH2)b—X, and n is about 10 to about 1000. “Pm” designates a copolymer of glycidol and allyl glycidyl ether.

In an embodiment of the block copolymer, X is selected from amino, dimethylamino, —CH2CH2SO3H, —CH2CH2CH2SO3H, —CH2CO2H, and —CH2CH2N+(CH3)3, and combinations thereof.
In accordance with an embodiment, the copolymer of formula (I) has one of the following structures:

















wherein n is about 10 to about 1000.

The block copolymers where block A is polyglycerol, poly(allyl glycidyl ether) or a copolymer of glycidol and allyl glycidyl ether can be prepared by any suitable method, for example, in an embodiment, by a method comprising:
(i) providing an aromatic hydrophobic polymeric segment having one or more terminal functional groups selected from hydroxy, mercapto, or amino groups; and
(ii) carrying out ring opening polymerization of glycidol, allyl glycidyl ether, or a mixture of allyl glycidyl ether and glycidol on the aromatic hydrophobic polymeric segment, if required, in the presence of a base.
In accordance with an embodiment, the aromatic hydrophobic polymeric segment of the block copolymer is selected from polysulfone, polyethersulfone, polyphenylene ether, polyphenylene oxide, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide, preferably polyethersulfone. The aromatic hydrophobic polymeric segment comprises one or more, preferably one or two, terminal functional groups selected from hydroxy, mercapto, or amino groups.
The functional groups can be provided on the aromatic hydrophobic segments by methods known to those skilled in the art. For example, hydroxy-terminated polyether imide synthesis is described in U.S. Pat. No. 4,611,048 and U.S. Pat. No. 7,230,066. Thus, for example, hydroxy-terminated polyether imides can be prepared by the reaction of a bis-ether anhydride and a diamine, followed by reaction with an amino alcohol. Illustratively, a hydroxy-terminated polyether imide can be prepared by the reaction of bis(4-(3,4-dicarboxy-phenoxy)phenyl)propane dianhydride and m-phenylenediamine, followed by reaction with p-aminophenol.
Amine-terminated polyether imides can be prepared by the reaction of a bis-ether anhydride and a diamine. Thus, for example, bis(4-(3,4-dicarboxy-phenoxy)phenyl)propane dianhydride and m-phenylenediamine can be reacted to produce an amine terminated polyether imide. See, for example, U.S. Pat. No. 3,847,867.
Hydroxy-terminated PEEK is described in Journal of Polymer Science Part B 2006, 44, 541 and Journal of Applied Science 2007, 106, 2936. Thus, for example, hydroxy-terminated PEEK with pendent tert-butyl groups can be prepared by the nucleophilic substitution reaction of 4,4′-difluorobenzophenone with tert-butyl hydroquinone with potassium carbonate as catalyst.
Hydroxy-terminated polycarbonate is described in Journal of Polymer Science: Polymer Chemistry Edition 1982, 20, 2289. Thus, for example, hydroxy-terminated polycarbonate can be prepared by the reaction of bisphenol A and phosgene, with in situ blocking of some of the phenolic groups either prior to or during phosgenation. Trimethylchlorosilane, trifluoroacetic anhydride, or trifluoroacetic acid can be used for the blocking. The blocking group can be removed at the end of the polymerization.
Hydroxy-terminated PPO can be prepared as described in U.S. Pat. No. 3,318,959. Thus, for example, poly-2,6-dimethylphenylene ether can be reacted with sodium hydroxide to obtain a PPO having a hydroxyl content of 2.3 to 3 hydroxyl groups per molecule.
Any of the aromatic hydrophobic polymers disclosed above can be employed as the aromatic hydrophobic polymeric segment in the block copolymer. In an embodiment, the aromatic hydrophobic polymeric segment is polyethersulfone having one or more hydroxy groups is of the formula:




wherein n is about 10 to about 1000, preferably about 50 to 175, and more preferably about 60 to about 100.

Polyethersulfone is commercially available, for example, as VIRANTAGETM VW-10700 from Solvay, with the formula




which has a GPC molecular weight 21000 g/mol and OH end groups of 210 μeq/g;

as VIRANTAGE VW-10200 from Solvay with the formula





which has a GPC molecular weight of 44,200 g/mol and OH end groups of 80 μeq/g; and as

SUMIKAEXCELTM 5003PS from Sumitomo with the formula





which has a reduced viscosity of 0.50 [1% PES dissolved in DMF] and OH end groups in the range of 0.6-1.4 per molecule.

Glycidol or 2,3-epoxy-1-propanol contains one epoxide ring and one hydroxyl group as functional end groups. Both functional end groups are capable of reacting with each other to form macromolecules which are glycerol derivatives. The resulting macromolecules continue to react to form polyglycerol. Allyl glycidyl ether contains one epoxide ring, which is capable of undergoing ring opening polymerization.
The opening of the epoxide ring is initiated by the nucleophile, i.e., oxide anion, amino group, or sulfide anion, of the aromatic hydrophobic polymeric segment, which in turn is produced by the reaction of the terminal hydroxide or mercapto group on the aromatic hydrophobic polymeric segment with the base employed in the reaction. Depending on the reactivity of the terminal mercapto group, a base may or may not be required; however, the use of a base is preferred. The ring opened epoxide continues to open the epoxide of the next glycidol and/or allyl glycidyl ether in the presence of a base, and the polymerization of glycidol and allyl glycidyl ether proceeds in this manner.
When a base is required, the ring opening polymerization can be carried out with any suitable base, for example, a base selected from potassium carbonate, sodium carbonate, cesium carbonate, sodium tertiary butoxide, potassium tertiary butoxide, tetramethylammonium hydroxide, ammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium carbonate, barium hydroxide, cesium hydroxide, lithium carbonate, magnesium carbonate, magnesium hydroxide, sodium amide, lithium amide, and combinations thereof.
In accordance with an embodiment, the ring opening polymerization can be carried in a suitable solvent, particularly a polar aprotic solvent. Examples of suitable solvents include N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and mixtures thereof.
The amount of the aromatic hydrophobic polymer, glycidol, and/or allyl glycidyl ether can be present in the polymerization medium at any suitable concentration, for example, each can be present at a concentration of about 5% to about 60% or more, preferably about 10% to about 50%, and more preferably about 20% to about 40%, by weight. In an embodiment, the concentration of each is about 30% by weight.
The ring opening polymerization is conducted such that the ratio of the hydrophobic polymeric segment to glycidol and allyl glycidyl ether in the reaction mixture is preferably about 1:0.1:0.1 to about 1:2:2, more preferably about 1:0.7:0.7 to about 1:1.2:1.2, and even more preferably about 1:0.8:0.8.
The ring opening polymerization is conducted at a suitable temperature, for example, from 25° C. to about 130° C., preferably about 50° C. to about 120° C., and more preferably about 90° C. to 110° C.
The polymerization can be carried out for any suitable length of time, for example, about 1 hr to about 100 hrs, preferably about 2 hrs to about 40 hrs, more preferably about 3 to about 20 hrs. The polymerization time can vary depending on, among others, the degree of polymerization desired and the temperature of the reaction mixture.
The block copolymer can be isolated from the reaction mixture by precipitation with a nonsolvent, e.g., methanol, ethanol, or isopropanol. The resulting block copolymer is dried to remove any residual solvent or nonsolvent.
In the above block copolymer of the formula: A-B-A (I) or A-B (II), one or more of the allyl groups of the copolymer can be replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is a group selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula —C(H)(COOH)(NH2), and a group of the formula —C(H)(COOH)(NHAc), or a salt thereof, by reacting the block copolymer with an agent selected from an oxidizing agent, a carboxyl alkane thiol or a salt thereof, a sulfonic alkane thiol or a salt thereof, a (dialkylamino)alkane thiol or a salt thereof, a haloalkane thiol, hydroxyalkane thiol, an acyl alkane thiol, an alkoxy alkane thiol, an alkylthio alkane thiol, an aldehydo alkane thiol, an amidoalkane thiol, a carbamoyl alkane thiol, an ureido alkane thiol, a cyanoalkane thiol, a nitro alkane thiol, an epoxy alkane thiol, cysteine, an acyl cysteine, an aminoalkane thiol or a salt thereof, an alkylamino alkane thiol, a dialkylaminoalkane thiol, and a sulfonic alkylammonium alkane thiol or a salt thereof.
In another embodiment, the invention provides a crosslinked porous membrane comprising a cellulosic material and an aromatic hydrophobic moiety Q.
In accordance with the invention, Q can be polymeric, oligomeric, or monomeric.
Any suitable Q can be present. For example, Q is a polymeric or oligomeric moiety selected from polysulfone, polyethersulfone, polyphenylene ether, polyphenylene oxide, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide, preferably polyethersulfone.
In accordance with an embodiment, oligomeric moieties have a degree of polymerization of 2 to about 50, preferably about 3 to about 25.
As disclosed above with respect to the aromatic hydrophobic polymeric segment, polymers or oligomers with terminal functional groups, hydroxy, mercapto, or amino, are known in the art, from which such moieties can be generated.
Q can also be a monomeric moiety of any of the above polymeric or oligomeric moieties. Such monomeric compounds are known to those skilled in the art.
The present invention further provides a method of preparing crosslinked porous membranes as described above, comprising:
(i) providing a casting solution comprising a solvent, a cellulosic material, and (a) a block copolymer of formula (I) or (II) or (b) an aromatic hydrophobic compound comprising an aromatic hydrophobic moiety Q and one or more functional groups attached to Q, wherein the functional groups are selected from hydroxy, mercapto, and amino;
(ii) casting the casting solution as a thin film;
(iii) subjecting the thin film to phase inversion to obtain an uncrosslinked porous membrane;
(iv) increasing the number of hydroxyl groups on the cellulosic material present in the uncrosslinked porous membrane if the cellulosic material is a cellulose derivative; and
(v) crosslinking the uncrosslinked porous membrane.
The casting solution contains a cellulosic material and a block copolymer of formula (I) or (II) or an aromatic hydrophobic compound comprising an aromatic hydrophobic moiety Q and one or more functional groups attached to Q, wherein the functional groups are selected from hydroxy, mercapto, and amino.
Typical casting solutions comprise at least one solvent where the cellulosic material is soluble, and may further comprise at least one nonsolvent.
Examples of solvents include methylene chloride, trifluoroethanol, a mixture of DMSO and paraformaldehyde, N-methylmorpholine N-oxide, 5-8% LiCl in DMAc, aqueous solution of cuprammonium hydroxide, acetone, methyl acetate, methyl formate, propylene oxide, dioxolane, dioxane, a mixture of methylene chloride and methanol, dimethyl formamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), methyl sulfoxide, tetramethylurea, diethyl succinate, chloroform, and tetrachloroethane, acetic acid, acetone, ionic liquids and mixtures thereof.
Suitable nonsolvents include, for example, water; various polyethylene glycols (PEGs; e.g., PEG-200, PEG-300, PEG-400, PEG-1000); various polypropylene glycols; various alcohols, e.g., methanol, ethanol, isopropyl alcohol (IPA), amyl alcohols, hexanols, heptanols, and octanols; alkanes, such as hexane, propane, nitropropane, heptanes, and octane; and ketone, ethers and esters such as acetone, butyl ether, ethyl acetate, and amyl acetate; acids, such as acetic acid, citric acid, lactic acid, and water; and various salts, such as calcium chloride, magnesium chloride, and lithium chloride; and mixtures thereof.
In accordance with an embodiment, casting solution contains a cellulosic material in the range of about 5 wt % to about 35 wt %, and the block copolymer in the range of about 0.1% to about 35 wt %.
In accordance with an embodiment, the casting solution contains a cellulosic material and a block copolymer in a mass ratio of about 20% to about 80% to about 80% to about 20%.
In accordance with another embodiment, casting solution contains a cellulosic material in the range of about 5 wt % to about 35 wt %, and aromatic hydrophobic compound comprising Q and the functional groups in the range of about 0.1% to about 35 wt %.
In accordance with another embodiment, the casting solution contains a cellulosic material and aromatic hydrophobic compound comprising Q and the functional groups in a mass ratio of about 20% to about 80% to about 80% to about 20%.
The casting solution is cast as a flat sheet on a glass plate or on a moving substrate such as a moving belt. Alternatively, the casting solution is cast as a hollow fiber or tube.
Phase inversion can be effected by any known method. Phase inversion can include evaporation of the solvent and nonsolvent (dry process); exposure to a nonsolvent vapor, such as water vapor, which absorbs on the exposed surface (vapor phase-induced precipitation process); quenching in a nonsolvent liquid, generally water (wet process); or thermally quenching a hot film so that the solubility of the polymer is suddenly greatly reduced (thermal process).
In an embodiment, phase inversion is effected by exposing the cast solution to a nonsolvent vapor, for example, an atmosphere of controlled humidity, following which the cast solution is immersed in a nonsolvent bath such as water bath.
In accordance with an embodiment, the cellulosic material is a cellulose derivative, for example, cellulose acetate.
The number of hydroxyl groups in the cellulose derivative can be increased by a suitable reaction. For example, if the cellulosic material is a cellulose ester such as cellulose acetate, the number of hydroxyl groups can be increased by hydrolyzing the ester with an alkali such as sodium or potassium hydroxide. Thus, for example, regenerated cellulose can be produced from a cellulose ester. Production of cellulosic materials with increased hydroxyl groups offers a number of advantages, including increased number of hydroxyl sites for crosslinking with the block copolymer or the aromatic hydrophobic compound comprising Q and the functional groups. In embodiments, the increased number of hydroxyl groups on the cellulose derivative also improves the chemical resistance of the resulting crosslinked porous membrane.
The uncrosslinked membrane can be crosslinked by any suitable method. For example, crosslinking can be effected by reaction with a crosslinking agent selected from epichlorohydrin, a polycarboxylic acid, and a cyclic brominium intermediate or by exposure to a radiation such as gamma or UV radiation, e-beam, or a polyfunctional vinyl or acrylic crosslinking agent. FIG. 2-6 illustrate reactions by which crosslinking can be effected in accordance with embodiments of the invention.
In an embodiment, the regeneration of cellulose from the cellulose derivative and the crosslinking of the membrane are carried out in one step or in one pot.
In accordance with an embodiment, the structure of a crosslinked membrane comprising cellulosic material and a block copolymer is as follows:




Examples of structures of other crosslinked porous membranes in accordance with an embodiment of the invention are disclosed in FIG. 2-6.
Crosslinked porous membranes according to embodiments of the invention find use in as microfiltration or ultrafiltration membranes or in the preparation of nanofiltration membranes, reverse osmosis membranes, gas separation membranes, pervaporation or vapor permeation membranes, dialysis membranes, membrane distillation, chromatography membranes, and/or forward osmosis membranes and pressure retarded osmosis membranes.
Crosslinked porous membranes according to embodiments of the invention have a pore size of about 0.05 μm to about 10 μm or more and find use as microfiltration membranes. Crosslinked porous membranes according to certain embodiments of the invention have a pore size of about 1 nm to about 0.5 μm and find use as nanofiltration membranes.
Crosslinked porous membranes according to embodiments of the invention can be used in a variety of applications, including, for example, diagnostic applications (including, for example, sample preparation and/or diagnostic lateral flow devices), ink jet applications, filtering fluids for the pharmaceutical industry, filtering fluids for medical applications (including for home and/or for patient use, e.g., intravenous applications, also including, for example, filtering biological fluids such as blood (e.g., to remove leukocytes)), filtering fluids for the electronics industry (e.g., filtering photoresist fluids in the microelectronics industry), filtering fluids for the food and beverage industry, clarification, filtering antibody- and/or protein-containing fluids, filtering nucleic acid-containing fluids, cell detection (including in situ), cell harvesting, and/or filtering cell culture fluids. Alternatively, or additionally, membranes according to embodiments of the invention can be used to filter air and/or gas and/or can be used for venting applications (e.g., allowing air and/or gas, but not liquid, to pass therethrough). Membranes according to embodiments of the inventions can be used in a variety of devices, including surgical devices and products, such as, for example, ophthalmic surgical products.
In accordance with embodiments of the invention, the crosslinked porous membrane can have a variety of configurations, including planar, flat sheet, pleated, tubular, spiral, and hollow fiber.
Crosslinked porous membranes according to embodiments of the invention are typically disposed in a housing comprising at least one inlet and at least one outlet and defining at least one fluid flow path between the inlet and the outlet, wherein at least one inventive membrane or a filter including at least one inventive membrane is across the fluid flow path, to provide a filter device or filter module. In an embodiment, a filter device is provided comprising a housing comprising an inlet and a first outlet, and defining a first fluid flow path between the inlet and the first outlet; and at least one inventive membrane or a filter comprising at least one inventive membrane, the inventive membrane or filter comprising at least one inventive membrane being disposed in the housing across the first fluid flow path.
Preferably, for crossflow applications, at least one inventive membrane or filter comprising at least one inventive membrane is disposed in a housing comprising at least one inlet and at least two outlets and defining at least a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, wherein the inventive membrane or filter comprising at least one inventive membrane is across the first fluid flow path, to provide a filter device or filter module. In an illustrative embodiment, the filter device comprises a crossflow filter module, the housing comprising an inlet, a first outlet comprising a concentrate outlet, and a second outlet comprising a permeate outlet, and defining a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, wherein at least one inventive membrane or filter comprising at least one inventive membrane is disposed across the first fluid flow path.
The filter device or module may be sterilizable. Any housing of suitable shape and providing an inlet and one or more outlets may be employed.
The housing can be fabricated from any suitable rigid impervious material, including any impervious thermoplastic material, which is compatible with the fluid being processed. For example, the housing can be fabricated from a metal, such as stainless steel, or from a polymer, e.g., transparent or translucent polymer, such as an acrylic, polypropylene, polystyrene, or a polycarbonate resin.
The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.
EXAMPLE 1
This example illustrates a method of preparing a block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of BASF E6020 grade polyethersulfone was dissolved in DMAc (250 mL) at 100° C. in a 500 mL flask. Complete dissolution was achieved in 2 hours under vigorous agitation. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (70 mL). The reaction mixture was maintained at 100° C. with constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (90:10 v/v). The precipitate obtained was filtered via a fritted Buchner filter, washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was then dried to yield 140 g of the desired product with 40 mol % of PES and 60 mol % of glycidyl as determined by proton NMR.
EXAMPLE 2
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Sumitomo 5003PS grade polyethersulfone was dissolved in DMAc (250 mL) at 100° C. in a 500 mL flask. Complete dissolution was achieved in 2 hours under vigorous agitation. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. with constant agitation for 5 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (90:10 v/v). The precipitate obtained was filtered via a fritted Buchner filter, washed with water (500 mL) and IPA (250 mL). The resulting white solid was dried to yield 130 g of the desired product with 40 mol % of PES and 60 mol % of glycidyl as determined by proton NMR.
EXAMPLE 3
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (20 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (4 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to yield 105 g of the desired product with 90 mol % of PES and 10 mol % of glycidyl as determined by proton NMR.
EXAMPLE 4
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (15 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (4 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 107 g of the desired product with 90 mol % of PES and 10 mol % of glycidyl as determined by proton NMR.
EXAMPLE 5
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (25 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (5 mL) and allowed to cool down to room temperature. The product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 107 g of the desired product with 85 mol % of PES and 15 mol % of glycidyl as determined by proton NMR.
EXAMPLE 6
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (35 mL). The reaction mixture was maintained at 100° C. under constant agitation for 5 hours. The reaction mixture was quenched by the addition of acetic acid (5 mL) and allowed to cool down to room temperature. The resulting product was then precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 110 g of the desired product with 80 mol % of PES and 20 mol % of glycidyl as determined by proton NMR.
EXAMPLE 7
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (50 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (8 mL) and allowed to cool down to room temperature. The product obtained was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter and washed with IPA (500 mL). The resulting solid was dried to yield 110 g of the desired product with 67 mol % of PES and 33 mol % of glycidyl as determined by proton NMR.
EXAMPLE 8
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (60 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction was quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The product obtained was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20 v/v). The precipitate obtained was filtered via a fritted Buchner filter, and washed with DI water (250 mL) and IPA (500 mL). The resulting solid was dried to obtain 110 g of the desired product with 53 mol % of PES and 47 mol % of glycidyl as determined by proton NMR.
EXAMPLE 9
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (80 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20, v/v). The precipitate obtained was filtered via a fritted Buchner filter and washed with DI water (500 mL) and IPA (500 mL). The resulting solid was dried to obtain 120 g of the desired product with 35 mol % of PES and 65 mol % of glycidyl as determined by proton NMR.
EXAMPLE 10
This example illustrates a method of preparing a block copolymer which is partially soluble in water.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA. The precipitate obtained was then filtered via a fitted Buchner filter and washed with DI water (500 mL) and IPA (500 mL). The resulting solid was dried to obtain 110 g of the desired product with 25 mol % of PES and 75 mol % of glycidyl as determined by proton NMR.
EXAMPLE 11
This example illustrates a method of preparing a block copolymer which is soluble in water.
100 g of Solvay VIRANTAGE VW-10700 RP grade polyethersulfone with a molecular weight of 22KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (150 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA. The precipitate obtained was filtered via a fritted Buchner filter and washed with DI water (500 mL) and IPA (500 mL). The resulting solid was dried to obtain 130 g of the desired product with 10 mol % of PES and 90 mol % of glycidyl as determined by proton NMR.
EXAMPLE 12
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (40 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (4 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to yield 105 g of the desired product with 85 mol % of PES and 15 mol % of glycidyl as determined by proton NMR.
EXAMPLE 13
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (50 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (6 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 105 g of the desired product with 80 mol % of PES and 20 mol % of glycidyl as determined by proton NMR.
EXAMPLE 14
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (60 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was then quenched by the addition of acetic acid (8 mL) and allowed to cool down to room temperature. The resulting product was precipitated by slow addition of the reaction mixture to 1.5 L of DI water. The precipitate obtained was filtered via a fitted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 110 g of the desired product with 70 mol % of PES and 30 mol % of glycidyl as determined by proton NMR.
EXAMPLE 15
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (70 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was then quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20 v/v). The resulting precipitate was filtered via a fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 115 g of the desired product with 55 mol % of PES and 45 mol % of glycidyl as determined by proton NMR.
EXAMPLE 16
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Solvay VIRANTAGE VW-10200 RP grade polyethersulfone with a molecular weight of 45KD was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (120 mL). The reaction mixture was maintained at 100° C. under constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (10 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of DI water: IPA (80:20 v/v). The precipitate obtained was filtered via a fritted Buchner filter and washed with water (500 mL) and IPA (250 mL). The resulting solid was dried to obtain 140 g of the desired product with 30 mol % of PES and 70 mol % of glycidyl as determined by proton NMR.
EXAMPLE 17
This example illustrates a method of preparing a block copolymer which is partially soluble in water.
100 g of BASF E6020 grade polyethersulfone was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. The complete dissolution was achieved in 2 hours under vigorous agitation. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (110 mL). The reaction mixture was maintained at 100° C. and constant agitation for 8 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (90:10 v/v). The precipitate obtained was filtered via a fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was dried to obtain 150 g of the desired product with 20 mol % of PES and 80 mol % of glycidyl as determined by proton NMR.
EXAMPLE 18
This example illustrates a method of preparing another block copolymer which is partially soluble in water.
100 g of BASF E7020 grade polyethersulfone was dissolved in DMAc (300 mL) at 100° C. in a 500 mL flask. Potassium carbonate (2 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. and constant agitation for 12 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (80:20 v/v). The precipitate obtained was filtered via fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was dried to obtain 150 g of the desired product with 30 mol % of PES and 70 mol % of glycidyl as determined by proton NMR.
EXAMPLE 19
This example illustrates a method of preparing another block copolymer of formula (I) wherein block B is polyethersulfone and block A is polyglycerol.
100 g of Sumitomo 5400P grade polyethersulfone was dissolved in DMAc (230 mL) at 100° C. in a 500 mL flask. Potassium carbonate (1.5 g) was added to the mixture and the reaction mixture was mixed for 30 minutes followed by the addition of glycidol (100 mL). The reaction mixture was maintained at 100° C. under constant agitation for 12 hours. The reaction mixture was quenched by the addition of acetic acid (20 mL) and allowed to cool down to room temperature. The resulting product was precipitated by a slow addition of the reaction mixture to 1.5 L of IPA: water (80:20 v/v). The precipitate obtained was filtered via a fritted Buchner filter, and washed with water (500 mL) and IPA (250 mL). The resulting white solid powder was dried to obtain 140 g of the desired product with 35 mol % of PES and 65 mol % of glycidyl as determined by proton NMR.
EXAMPLE 20
This example illustrates some of the properties of the block copolymers. Table 1 sets forth the water solubility.







TABLE 1







Solubility of block copolymers













PES segment 
Pg segment 





(mol % by 
(mol % by 




PES MW
NMR)
NMR)
Water Solubility







PES-22KD
85
15
No



PES-22KD
80
20
No (Hydrophilic)



PES- 22KD
70
33
No (Hydrophilic)



PES-22KD
53
47
No (Hydrophilic)



PES-22KD
25
75
Yes



PES-45KD
80
20
No (Hydrophilic)



PES-45KD
70
30
No (Hydrophilic)



PES-45KD
55
45
No (Hydrophilic)



PES-45KD
48
52
No (Hydrophilic)










EXAMPLE 21
This example illustrates the preparation of a block copolymer of formula (I) wherein block B is polyethersulfone and block is poly(allyl glycidyl ether), i.e., PES-PolyAGE.
BASF ULTRASONTM E6020 polyethersulfone (100 g) was added slowly to DMAc (250 g) in a 1 L reactor with overhead stirrer at 110° C. After complete dissolution of the polymer, K2CO3 (2.5 g) was added. After additional 2.5 hrs of stirring at 110° C., allyl glycidyl ether (100 mL) was added, and reaction mixture stirred at 110° C. for 19 hours. The hot reaction mixture was added to a vigorously stirring IPA (3 L), and stirring was continued for three more hours. The reaction mixture was filtered and the resulting product resuspended in IPA (1.5 L). After additional 3 hours of stirring, the product was filtered and washed in 30% IPA in water and in IPA (200 mL). The resulting product was dried in a vacuum oven at 50° C. overnight to obtain 105 g of an A-B-A type copolymer of PES and allyl glycidyl ether, PES-PolyAGE. Proton NMR characterization of the copolymer showed the presence of 10 mol % of allyl glycidyl ether and 90 mol % of PES.
EXAMPLE 22
This example illustrates the preparation of another block copolymer of formula (I) wherein block B is polyethersulfone and block is poly(allyl glycidyl ether), i.e., PES-PolyAGE.
BASF ULTRASONTM E7020 (200 g) polyethersulfone was added slowly to DMAc (600 mL) in a 1 L reaction flask at 110° C. After complete dissolution of the polymer, K2CO3 (10 g) was added. After an additional 1 hr of stirring at 110° C., the reaction mixture was purged with nitrogen for 10 minutes, and allyl glycidyl ether (200 g) was added. The reaction mixture was stirred at 110° C. for 72 hours and precipitated in methanol (2 L), filtered and the solid obtained was re-suspended in methanol (750 mL). After additional 5 hours of stirring, the product obtained was filtered, and washed in 30% methanol in water and in methanol (100 mL). The product obtained was dried in a vacuum oven at 50° C. overnight yielding 260 g of the desired product, an A-B-A type copolymer of PES and allyl glycidyl ether. Proton NMR characterization showed that the block copolymer had 62 mol % of PES and 38 mol % of allyl glycidyl ether.
EXAMPLE 23
This example illustrates the preparation of a block copolymer PES-Pg/PolyAGE.
BASF ULTRASONTM E6020 (500 g) polyethersulfone was added slowly to DMAc (1.5 L) in a 3 L reactor fitted with an overhead stirrer at 110° C. After complete dissolution of the polymer, K2CO3 (12.5 g) was added. After additional 2.5 hrs of stirring at 110° C. a mixture of allyl glycidyl ether (400 mL) and glycidol (100 mL) were added, and the reaction mixture stirred at 110° C. for 12 hours. The hot reaction mixture was added slowly to vigorously stirred distilled water (15 L). The product obtained was filtered, and further stirred in ethanol (5 L) overnight. The precipitate was filtered, washed with ethanol (2 L) and dried in a vacuum oven at 50° C. overnight to yield 760 g of the block copolymer product (PES-Pg/PolyAGE) with 61 mol % of PES block and 39 mol % of block A containing polymerized glycidol and allyl glycidyl ether, as determined by proton NMR spectroscopy.
EXAMPLE 24
This example illustrates the preparation of another block copolymer PES-Pg/PolyAGE.
Sumitomo 5003PS (200 g) polyethersulfone was added slowly to DMAc (0.5 L) at 110° C. After complete dissolution of the polymer, K2CO3 (12.5 g) was added. After additional 2.5 hrs of stirring at 110° C. a mixture of allyl glycidyl ether (160 mL) and glycidol (40 mL) were added, and the reaction mixture stirred at 110° C. for 12 hours. The hot reaction mixture was added slowly to vigorously stirred distilled water (7 L). The product obtained was filtered, and further stirred in ethanol (1.5 L) overnight. The precipitate was filtered, washed with ethanol (0.75 L) and dried in a vacuum oven at 50° C. overnight to yield 260 g of the block copolymer product, PES-Pg/PolyAGE, with 57 mol % of PES and 43 mol % of block A containing polymerized glycidol and allyl glycidyl ether, as determined by proton NMR spectroscopy.
EXAMPLE 25
This example illustrates the preparation of another block copolymer PES-Pm-MEA.
30 g of PES-Pg/PolyAGE from Example 23 was dissolved in DMAc (100 mL) at 80° C. After complete dissolution of the polymer, the solution was purged with nitrogen for 5 minutes. Aminoethanethiol hydrochloride (3 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (50 mg) were added and the reaction mixture was stirred at 80° C. for 21 hours. The hot reaction mixture was precipitated by drop-wise addition to ethanol (750 mL). The resulting precipitate was reconstituted in ethanol (250 mL) and further stirred for 2 hours. The resulting precipitate was filtered and dried in a vacuum oven at 50° C. overnight to yield 32 g of the desired product, PES-Pm-MEA, with 61 mol % of PES, 28 mol % of aminoethanethiol group and 11 mol % of allyl group, as determined by proton NMR spectroscopy.
EXAMPLE 26
This example illustrates the preparation of another block copolymer PES-Pm-MDMAE.
20 g of PES-Pg/PolyAGE from Example 23 was dissolved in DMAc (160 mL) at 80° C. After complete dissolution of the polymer, the solution was purged with nitrogen for 5 minutes. 2-(dimethylamino)ethane thiol hydrochloride (15 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (80 mg) were added and the reaction mixture was stirred at 80° C. overnight. The hot reaction mixture was precipitated by drop-wise addition to IPA (550 mL). The resulting precipitate was further stirred in IPA (100 mL) for 2 hours. The precipitate was filtered and washed with deionized water (1000 mL) followed by IPA (500 mL). The resulting product was dried in a vacuum oven at 50° C. overnight yielding 23 g of the desired product, PES-Pm-MDMAE, with 61 mol % of PES, 34 mol % of dimethylamino-ethane thiol group and 5 mol % of remaining allyl glycidyl group, as determined by proton NMR spectroscopy.
EXAMPLE 27
This example illustrates the preparation of another block copolymer PES-Pm-MES.
30 g of PES-Pg/PolyAGE from Example 23 was dissolved in DMAc (150 mL) at 80° C. After complete dissolution of the polymer, the solution was purged for five minutes. Sodium-2-mercaptoethansulfonate (25 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (500 mg) were added and the reaction mixture was stirred at 80° C. overnight. The hot reaction mixture was precipitated by drop-wise addition to IPA (250 mL). The precipitate was further stirred in IPA for 2 hours, filtered, and dried in a vacuum oven at 50° C. overnight. 34 g of the desired product, PES-Pm-MES, was obtained with 61 mol % of PES, 35 mol % of mercaptoethanesulfonic acid and 4 mol % of allyl group, as determined by proton NMR spectroscopy.
EXAMPLE 28
This example illustrates the preparation of another block copolymer PES-Pm-MPS.
40 g of PES-Pg/PolyAGE from Example 23 was dissolved in DMAc (250 mL) at 80° C. After complete dissolution of the polymer, the solution was purged for five minutes. Mercaptopropane sulfonic acid sodium salt (25 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (500 mg) were added and the reaction mixture was stirred at 80° C. overnight. The hot reaction mixture was precipitated by drop-wise addition to IPA (750 mL). The precipitate was further stirred in IPA for 2 hours, filtered, and dried in a vacuum oven at 50° C. overnight. 48 g of the desired product, PES-Pm-MPS, was obtained with 61 mol % of PES, 36 mol % of mercaptopropanesulfonic acid and 3 mol % of allyl group, as determined by proton NMR spectroscopy.
EXAMPLE 29
This example illustrates the preparation of another block copolymer PES-Pm-MAA.
20 g of PES-Pg/PolyAGE from Example 23 was dissolved in DMAc (100 mL) at 80° C. After complete dissolution of the polymer, the solution was purged for five minutes. Mercaptoacetic acid sodium (15 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (200 mg) were added and the reaction mixture was stirred at 80° C. overnight. The hot reaction mixture was precipitated by drop-wise addition to ethanol (550 mL). The precipitate was further stirred in ethanol for 2 hours, filtered, and dried in a vacuum oven at 50° C. overnight. 22 g of the desired product, PES-Pm-MAA, was obtained with 61 mol % of PES, and 38 mol % of mercaptoacetic acid, as determined by proton NMR spectroscopy. No free allyl group was observed.
EXAMPLE 30
This example illustrates the preparation of a crosslinked porous membrane in accordance with an embodiment of the invention.
An ultrafiltration membrane was prepared as follows. 112.5 g of cellulose acetate [Eastman CA-398-30, 39.8% acetyl content, 3.5% Hydroxyl content, Tg of 189° C., melting point 230-250° C., viscosity 114 poise (ASTM Method 1343) as a measurement of molecular weight], 112.5 g of copolymer from Example 1, and 172.1 g of citric acid (99.9% anhydrous) were dissolved in 1083.8 g of NMP (ACS reagent grade) at 30° C. Complete dissolution was achieved after stirring at 1200 rpm for 1 h. The solution was stirred at 800 rpm overnight, followed by degassing at a 17 inch-Hg vacuum for 4 hours.
The casting solution at 23.1° C. was cast as a 6 mil thick film on a moving polyester belt and the film was subjected to phase inversion by immersing into a water bath whose temperature was controlled at 22° C., at a line speed of 7 ft per minute, to obtain an uncrosslinked porous membrane.
A reaction mixture was made up by first heating up 915 g of H2O to 48° C., followed by adding 10 g of sodium acetate anhydrous, which in turn was followed by the addition of a total of 75 grams of epichlorohydrin. This was followed by the addition of 8 g of NaOH in small aliquots at a time, allowing time for dissolution. Epichlorohydrin is the crosslinking agent. NaOH serves to increase the number of hydroxyl groups in cellulose acetate.
The uncrosslinked porous membrane was immersed into the above reaction mixture with the temperature maintained at 48° C. with stirring at 300 rpm for a period of 16 hours. The resulting product was washed with water to obtain a crosslinked porous membrane.
EXAMPLE 31
This example illustrates the preparation of another crosslinked porous membrane in accordance with an embodiment of the invention.
An ultrafiltration membrane was prepared as follows. 112.5 g of cellulose acetate used in Example 30 and 112.5 g of the copolymer from Example 23, and 172.1 g citric acid (99.9% anhydrous) were dissolved in 1083.8 grams of NMP (ACS reagent grade) at 30° C. Complete dissolution was achieved after stirring at 1200 rpm for 1 h. The solution was stirred at 800 rpm overnight, followed by degassing at 17 inch Hg vacuum for 4 hours.
The casting solution at 23.1° C. was cast as a 6 mil thick film on a moving polyester belt and the film was subjected to phase inversion by immersing into a water bath whose temperature was controlled at 22° C., at a line speed of 7 ft per minute, to obtain an uncrosslinked porous membrane.
A reaction mixture was made up by first heating up 915 g of H2O to 48° C., followed by adding 10 g of sodium acetate anhydrous, which in turn was followed by the addition of a total of 75 grams of epichlorohydrin. This was followed by the addition of 8 g of NaOH in small aliquots at a time, allowing time for dissolution. The order of addition of the reagents is important. Epichlorohydrin is the crosslinking agent. NaOH serves to increase the number of hydroxyl groups in cellulose acetate.
The uncrosslinked porous membrane was immersed into the above reaction mixture with the temperature maintained at 48° C. with stirring at 300 rpm for a period of 16 hours. The resulting product was washed with water to obtain a crosslinked porous membrane.
EXAMPLE 32
This example illustrates some of the properties of the crosslinked porous membrane in accordance with an embodiment of the invention.
Samples of the crosslinked porous membrane prepared as in Example 30 were exposed to a 10% solution of N,N-dimethylformamide and 1N sodium hydroxide. The mass balance, water flux, and BSA passage characteristics of the membranes after the above exposure were tested. The percent weight change results are set forth in Table 2.







TABLE 2







Change in Weight upon Exposure to DMF and NaOH














Cellulose/
Cellulose/Block



Polyether-
Regenerated
PES cross-
Copolymer


Exposure
sulfone*
Cellulose* *
linked* * *
crosslinked





10% DMF
+3.2%
−0.1%
+4.6%
−1.0%


1N NaOH
+1.4%
−4.1%
−2.5%
−0.2%





In Tables 1-3:


*Polyethersulfone Omega 30K UF membrane from Pall


**Regenerated cellulose Delta 30K UF membrane from Pall


***prepared as a comparative example following the same procedure except that the polyethersulfone used was a homopolymer and not modified to a block copolymer.






As can be seen from the data set forth in Table 2, the polyethersulfone membrane gained weight upon exposure to DMF and NaOH. The regenerated cellulose membrane was stable to DMF exposure; however, with NaOH, it lost weight. When the polyethersulfone was a homopolymer, the crosslinked membrane gained weight in DMF and lost weight in NaOH. However, the crosslinked membrane in accordance with an embodiment of the invention, employing a block copolymer where B was polyethersulfone, was stable to DMF and NaOH, as evidenced by the significantly small change in weights.
The membranes were tested for BSA passage and water flux after the exposure as described above. The results obtained are set forth in Table 3 and Table 4, respectively.







TABLE 3







Change in BSA Passage upon Exposure to DMF and NaOH














Cellulose/
Cellulose/Block



Polyether-
Regenerated
PES cross-
Copolymer


Exposure
sulfone*
Cellulose* *
linked* * *
crosslinked





10% DMF
+1102.76%
 −9.45%
−1.22%
 −7.71%


1N NaOH
 +176.50%
−68.50%
−8.47%
−41.23%
















TABLE 4







Change in Water Flux upon Exposure to DMF and NaOH














Cellulose/
Cellulose/Block



Polyether-
Regenerated
PES cross-
Copolymer


Exposure
sulfone
Cellulose
linked
crosslinked





10% DMF
 −6.20%
 +5.51%
−99.64%
 +0.36%


1N NaOH
−37.31%
−15.87%
−98.81%
+280.88%









As can be seen from the data set forth in Tables 3 and 4, the crosslinked porous membrane of the invention is stable to DMF. Exposure to NaOH advantageously increases the water flux and at the same time decreases the BSA passage or increases BSA rejection.
FIG. 1A depicts the SEM micrograph of the surface of the porous membrane prepared from cellulose acetate and a block copolymer of polyethersulfone prior to regeneration of cellulose and crosslinking, and FIG. 1B depicts the SEM micrograph of the porous membrane after regeneration of cellulose and crosslinking. The SEM micrograph shows that the porous membrane after the regeneration and crosslinking has a typical UF cross-sectional structure without blockage from excessive crosslinking.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms “a” and “an” and “the” and “at least one” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “at least one” followed by a list of one or more items (for example, “at least one of A and B”) is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

## Claims

1. A crosslinked porous membrane comprising a cellulosic material and
(a) a block copolymer of the formula: A-B-A (I) or A-B (II),
wherein block A is (iii) a copolymer of glycidol and allyl glycidyl ether, wherein one or more of the allyl groups of the copolymer have been replaced with a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a is 3 and b is 1 to 3, and X is selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula —C(H)(COOH)(NH2), and a group of the formula —C(H)(COOH)(NHAc), or a salt thereof; and
block B is an aromatic hydrophobic polymeric segment;
wherein the block copolymer is linked to the cellulosic material to form a crosslinked porous membrane.

2. The crosslinked porous membrane of claim 1, wherein the cellulosic material is a cellulosic polymer, cellulosic oligomer, or cellulosic monomer.

3. The crosslinked porous membrane of claim 1, wherein the cellulosic material is a cellulosic polymer selected from cellulose, cellulose ethers, cellulose esters, cellulose amides, cellulose amines, and cellulose carbamates.

4. The crosslinked porous membrane of claim 3, wherein the cellulosic polymer is selected from cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose nitrate, and cyanoethyl cellulose.

5. The crosslinked porous membrane of claim 1, wherein block A is a hydrophilic polymeric segment comprising polyglycerol.

6. The crosslinked porous membrane of claim 5, wherein block A is a hydrophilic polymeric segment comprising polyglycerol having a repeat unit of the formula:

7. The crosslinked porous membrane of claim 1, wherein block A is a copolymer of glycidol and allyl glycidyl ether, the copolymer having one or more allyl groups.

8. The crosslinked porous membrane of claim 1, wherein the aromatic hydrophobic polymeric segment is selected from polysulfone, polyethersulfone, polyphenylene ether, polyphenylene oxide, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide.

9. The crosslinked porous membrane of claim 8, wherein the aromatic hydrophobic polymeric segment is polyethersulfone.

10. The crosslinked porous membrane of claim 5, wherein block A is present in an amount of about 20% to about 50 mol % and block B is present in an amount of about 50% to about 80 mol %.

11. A method of preparing a crosslinked porous membrane according to claim 1, comprising:
(i) providing a casting solution comprising a solvent, a cellulosic material, and (a) a block copolymer of formula (I) or (II);
(ii) casting the casting solution as a thin film;
(iii) subjecting the thin film to phase inversion to obtain an uncrosslinked porous membrane;
(iv) increasing the number of hydroxyl groups on the cellulosic material present in the uncrosslinked porous membrane if the cellulosic material is a cellulose derivative; and
(iv) crosslinking the uncrosslinked porous membrane.

12. The method of claim 11, wherein the polymer solution comprises a solvent, said cellulosic material, and (a) a block copolymer of formula (I) or (II), wherein the cellulosic material is cellulose acetate.

13. The method of claim 12, wherein the number of hydroxyl groups on the cellulose acetate is increased by reaction with an alkali.

14. The method of claim 11, wherein the crosslinking is effected by reaction with a crosslinking agent selected from epichlorohydrin, a polycarboxylic acid, and a cyclic brominium intermediate or by exposure to a radiation, e-beam, or a polyfunctional vinyl or acrylic crosslinking agent.