# Patent

## Title
Hydrophilic block copolymers and membranes prepared therefrom (II)

## Abstract

Disclosed is a block copolymer of the formula: A-B-A (I) or A-B (II), wherein block A is: (i) a polymer of allyl glycidyl ether or (ii) a polymer of allyl glycidyl ether wherein one more of the allyl groups have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a, b, and X are defined herein. The block copolymers find use as wetting agents in the preparation of porous membranes from aromatic hydrophobic polymers such as polyethersulfone. Also disclosed are methods of preparing such block copolymers and porous membranes therefrom.

## Background
BACKGROUND OF THE INVENTION
Aromatic polymers such as polysulfone, polyethersulfone, poly(phthalazine ether sulfone ketone), poly(p-phenylene sulfide), polyether imide, polyimide, polyphenylene oxide, polyphenylene ether, and polyether ether ketone are useful for preparing porous membranes due to their chemical stability, processability, mechanical strength, flexibility, and thermal stability. Since these polymers are generally hydrophobic, membranes prepared from these polymers are hydrophobic, and thus lack desirable surface properties such as wettability, low protein adsorption, thromboresistance, and controlled surface chemical reactivity.
Attempts have been made to improve one or more of the surface properties of membranes made from the aromatic polymers. For example, membranes have been treated with high energy radiation or plasma to impart hydrophilicity. In other examples, hydrophilic monomers have been grafted to hydrophobic membrane surfaces. Attempts also have been made to coat the hydrophobic membrane with water soluble polymers such as polyethylene glycol or polyvinyl pyrrolidone. The above attempts for improving properties, particularly hydrophilicity, however, have one or more drawbacks such as lack of reproducibility, lack of stability of the modification, and/or pore clogging.
The foregoing shows that there is an unmet need for hydrophilic membranes formed from aromatic hydrophobic polymers and for a method of imparting hydrophilicity to membranes formed from aromatic hydrophobic polymers.
BRIEF SUMMARY OF THE INVENTION
The invention provides hydrophilic block copolymers which are useful in imparting hydrophilicity to membranes formed from aromatic hydrophobic polymers.
The invention provides a block copolymer of the formula: A-B-A (I) or A-B (II), wherein block A is: (i) a polymer of allyl glycidyl ether, said polymer having allyl groups; or (ii) a polymer of allyl glycidyl ether wherein one more of the allyl groups 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.
The present invention also provides a method of preparing a block copolymer comprising: (i) providing an aromatic hydrophobic polymeric segment having one or more terminal functional groups; and (ii) carrying out ring opening polymerization of allyl glycidyl ether on the aromatic hydrophobic polymeric segment in the presence of a base. Optionally, one or more of the allyl groups are replaced with hydrophilic groups to produce a hydrophilic copolymer.
The present invention also provides a porous membrane comprising an aromatic hydrophobic polymer and a block copolymer as described above, and a method of preparing such porous membranes.
The present invention has one or more of the following advantages. It provides for a facile method for tuning the degree of hydrophilicity desired in a porous membrane. Block copolymers of various degrees of hydrophilicity are produced from aromatic hydrophobic polymers. The composition of the block copolymers are readily characterized by well known techniques. The porous membranes prepared using the block copolymers are low in extractables. The block copolymers have strong adhesion to aromatic hydrophobic polymers. The porous membranes are stable to process conditions such as autoclaving, steaming, and isopropanol (IPA) extraction.



BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
FIG. 1A depicts the SEM image of the cross-section of a porous membrane prepared from a blend of PES and PES-PolyAGE in accordance with an embodiment of the invention. FIG. 1B depicts a higher magnification SEM image of the cross-section depicted in FIG. 1A.
FIG. 2A depicts the SEM image of the cross-section of a porous membrane prepared from a blend of PES and PES-MPS in accordance with an embodiment of the invention. FIG. 2B depicts a higher magnification SEM image of the circled region of the cross-section depicted in FIG. 2A.
FIG. 3 illustrates the microstructure of a hydrophilic porous membrane. 1 represents an aromatic hydrophobic polymer, 2 represents the aromatic hydrophobic polymeric segment of the block copolymer in accordance with an embodiment of the invention, and 3 represents the hydrophilic polymeric segment of the block copolymer.
FIG. 4A depicts the SEM image of the cross-section of a membrane in accordance with an embodiment of the invention. FIG. 4B depicts a higher magnification SEM image of the image depicted in FIG. 4A.



DETAILED DESCRIPTION OF THE INVENTION
In accordance with an embodiment, the invention provides a block copolymer of the formula: A-B-A (I) or A-B (II), comprising blocks A and B,
wherein block A is:
(i) a polymer of allyl glycidyl ether, said polymer having allyl groups; or
(ii) a polymer of allyl glycidyl ether wherein one more of the allyl groups 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.
In accordance with an embodiment, the polymer of allyl glycidyl ether has a repeat unit of the formula:




wherein R is allyl.

In accordance with another embodiment, block A is a polymer of allyl glycidyl ether wherein one more of the allyl groups have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a and b are independently 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.
In accordance with an embodiment, the zwitterion is 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.
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 segments 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 accordance with an embodiment, the block copolymer of the invention, where polyethersulfone is the aromatic hydrophobic segment, has any of the following structures:










wherein n, m1, and m2 are independently 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 embodiments, block A is present in the block copolymer an amount of about 20% to about 60 mol % and block B is present in an amount of about 40% to about 80 mol %, and 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 45% to about 60 mol %.
The invention further provides a method of preparing a block copolymer of the formula: A-B-A (I) or A-B (II), wherein block A is a polymer of allyl glycidyl ether, said polymer having allyl groups, and block B is an aromatic hydrophobic polymeric segment; the method comprising: (i) providing an aromatic hydrophobic polymeric segment having one or more terminal functional groups selected from hydroxy, mercapto, and amino groups; and (ii) carrying out ring opening polymerization of allyl glycidyl ether on the aromatic hydrophobic polymeric segment.
In accordance with an embodiment, 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, 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. Nos. 4,611,048 and 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.
In an embodiment, the aromatic hydrophobic polymeric segment 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 5003 PS 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.

The opening of the epoxide ring of glycidol is initiated by the nucleophile, i.e., oxide anion, amino group, or sulfide anion, of the aromatic hydrophobic polymeric segment, which is present as the terminal functional group (amino group) or is produced by the reaction of the terminal group (OH or SH) on the aromatic hydrophobic polymeric segment with the base employed in the reaction. The ring opened epoxide continues to open the epoxide of the next allyl glycidyl ether in the presence of a base, and the polymerization of allyl glycidyl ether proceeds in this manner. When SH acts as a nucleophile, the use of a base is optional. When an amino group is the nucleophile, then a base is not required.
The ring opening polymerization can be carried out with any suitable base. For example, the base is 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, and lithium amide, and combinations thereof.
The ring opening polymerization can be carried out in any suitable solvent. For example, the solvent is selected from N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and combinations thereof.
The amount of hydrophobic polymer and allyl glycidyl ether can be present in the polymerization medium at any suitable concentration, for example, from 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 is about 30% by weight.
The ring opening polymerization is conducted such that the ratio of the hydrophobic polymeric segment to allyl glycidyl ether in the reaction mixture is preferably about 1:0.1 to about 1:2, more preferably about 1:0.7 to about 1:1.2, and even more preferably about 1:0.8.
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 propanol. The resulting polymer is dried to remove any residual solvent or nonsolvent.
The block copolymer can be characterized by any suitable analytical technique. For example, the amount of hydrophobic polymeric segment and the amount of the allyl glycidyl ether block can be determined by proton NMR spectroscopy.
In an embodiment, the aromatic hydrophobic polymeric segment of block B has the formula:




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

The invention further provides a method of preparing a block copolymer of the formula A-B-A (I) or A-B (II), wherein block A is a polymer of allyl glycidyl ether wherein one more of the allyl groups 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 a group selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkoxy, alkylthio, 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;
the method comprising:
(i) providing a block copolymer of formula A-B-A (Ia) or A-B (IIa), wherein block A is a polymer of allyl glycidyl ether, said polymer having allyl groups, and block B is an aromatic hydrophobic polymeric segment; and
(ii) reacting one or more of the allyl groups of the block copolymer in (i) with an agent selected from an oxidizing agent, an acid group bearing alkane thiol, a basic group bearing alkane thiol, a zwitterion bearing alkane thiol, 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, or an acyl cysteine.
One or more of the allyl groups on the block copolymers Ia and Ib 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 butyl. 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.
The present invention further provides a porous membrane comprising an aromatic hydrophobic polymer and a block copolymer as described above.
The present invention further provides a method of preparing a porous membrane comprising an aromatic hydrophobic polymer and a block copolymer as described above, comprising: (i) preparing a polymer solution comprising a solvent and said aromatic hydrophobic polymer and said block copolymer;
(ii) casting the polymer solution as a thin film;
(iii) subjecting the thin film to phase inversion to obtain a porous membrane; and optionally
(iv) washing the porous membrane.
The polymer solution contains a polymer and a block copolymer as a wetting agent. Typical polymer solutions comprise at least one solvent, and may further comprise at least one non-solvent. Suitable solvents include, for example, dimethyl formamide (DMF); N,N-dimethylacetamide (DMAc); N-methyl pyrrolidone (NMP); dimethyl sulfoxide (DMSO), methyl sulfoxide, tetramethylurea; dioxane; diethyl succinate; chloroform; and tetrachloroethane; and mixtures thereof. In accordance with an embodiment, the polymer solution contains N,N-dimethylformamide, N-methylpyrrolidone, or a mixture thereof, as the solvent.
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, and lactic acid; and various salts, such as calcium chloride, magnesium chloride, and lithium chloride; and mixtures thereof.
Typical casting solutions contain the polymer as pore-formers in the range of about 10 wt % to about 35 wt % resin, in the range of from about 0.1% to about 10 wt %, preferably from about 0.2% to about 2%, and more preferably from about 0.3% to about 1% of the block copolymer of the invention, in the range of from about 0 to about 90 wt % NMP, in the range of from about 0 to about 90 wt % DMF, and in the range of from about 0 to about 90 wt % DMAc.
Suitable components of solutions are known in the art. Illustrative solutions comprising polymers, and illustrative solvents and nonsolvents include those disclosed in, for example, U.S. Pat. Nos. 4,629,563; 4,900,449; 4,964,990, 5,444,097; 5,846,422; 5,906,742; 5,928,774; 6,045,899; and 7,208,200.
For example, membrane samples can be prepared through a solution processes involving non-solvent-induced polymer precipitation, either by water vapor diffusion or direct quenching in water. Typically, a solution of the polymer, e.g., PES or PPESK, is prepared first with solvent DMAC or DMAC/NMP, pore former PEG400 and other additives. The solution is applied to a glass plate using a doctor blade with 10 ̃15-mil space gap, evenly to form a film of polymer dope. The film is then either placed in a chamber with controlled temperature, air velocity and humidity, or directly immersed into a water bath with a preset temperature, allowing some time for the dope to transform into a solid film. The resulting solid film sample is leached in 50 ̃70% ethanol/water, hot water at a temperature range from 50° C. to 80° C. and then dried in oven at a temperature range from 50-70° C. to afford a sheet of porous polymer membrane.
As an example, a typical formulation consists of PPESK polymer resin at about 15 ̃25 wt %, solvent (NMP/DMAC) of about 200 ̃300 phr, wetting polymer agents at a typical range of 5 ̃25 phr, up to 50 phr. Pore former PEG400 is introduced at a concentration ranging from 50 phr to 100 phr. Other additives at a low percentage 0.5 ̃3.0% can be used as needed for each individual formulation.
In accordance with an embodiment, the polymer solution contains an aromatic hydrophobic polymer or a block copolymer in a mass ratio of from 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.
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 non-solvent vapor, for example, an atmosphere of controlled humidity, following which the cast solution is immersed in a nonsolvent bath such as water bath.
As illustrated in FIG. 3, the microstructure of the porous membrane in accordance with an embodiment of the invention includes the hydrophilic segments 3 on the pore surfaces of the membrane, thereby improving the hydrophilicity of the membrane. The hydrophobic polymeric segment B, 2, of the block copolymer orients itself with the aromatic hydrophobic polymer 1.
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.
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. 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.
Porous membranes according to the invention have a critical wetting surface tension (CWST) of about 70 to about 90 dynes/cm or more, for example, 72, 74, 76, 78, 80, 82, 84, or 86 dynes/cm.
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). Porous 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 porous membrane can have a variety of configurations, including planar, flat sheet, pleated, tubular, spiral, and hollow fiber.
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 the preparation of a block copolymer of polyethersulfone and allyl glycidyl ether in accordance with an embodiment of the invention.
BASF ULTRASON 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 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 2
This example illustrates the preparation of another block copolymer of polyethersulfone and allyl glycidyl ether in accordance with an embodiment of the invention.
BASF ULTRASON 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 an 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 3
This example illustrates the preparation of a hydrophilic block copolymer, PES-MAA, in accordance with an embodiment of the invention.
15 g of the copolymer PES-PolyAGE from Example 2 was dissolved in DMAc (30 mL) at 80° C. After complete dissolution of the polymer, the solution was purged with nitrogen for five minutes and thioglycolic acid (or mercaptoacetic acid) (15 mL) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (750 mg) were added. The reaction mixture was stirred at 80° C. overnight. The hot solution was added drop-wise to ethanol (250 mL), and the resulting precipitate was further stirred in ethanol for 2 hours. The precipitate was filtered, rinsed with 0.1 M NaOH (150 mL), water (300 mL), and ethanol (100 mL), and dried in a vacuum oven at 50° C. overnight to obtain 17 g of the desired product PES-MAA. Proton NMR characterization showed the presence of 62 mol % of PES, 30 mol % of mercaptoacetic acid, and 8 mol % of allylglycidyl ether remaining in the product (PES-MAA), which corresponds to a 74% conversion of the allyl groups of PES-PolyAGE during the thiol-ene reaction with the mercaptoacetic acid (MAA).
EXAMPLE 4
This example illustrates the preparation of a hydrophilic block copolymer, PES-MPS, in accordance with an embodiment of the invention.
30 g of PES-PolyAGE from Example 2 was dissolved in DMAc (80 mL) at 60° C. After complete dissolution of the polymer, the solution was purged with nitrogen for five minutes. Mercaptopropane sulfonic acid sodium salt (15 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (200 mg) were added and the reaction mixture stirred at 60° C. overnight. The hot solution was precipitated by drop-wise addition to isopropanol (IPA) (750 mL). The precipitate was further stirred in IPA for 5 hours, filtered and dried in a vacuum oven at 50° C. overnight to yield 36 g of PES-MPS. Characterization by proton NMR confirmed the complete disappearance of the allyl groups in the thiol-ene reaction. The PES-MPS copolymer had 62 mol % of PES and 38 mol % of mercaptopropane sulfonic group.
EXAMPLE 5
This example illustrates the preparation of a hydrophilic block copolymer, PES-MEDMA, in accordance with an embodiment of the invention.
16.1 g of PolyAGE from Example 2 was dissolved in DMAc (60 mL) at 80° C. After complete dissolution of the polymer, the solution was purged with nitrogen for 5 minutes. 2-(dimethylamino)ethane thiol hydrochloride (16.1 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (80.5 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 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 PES-MEDMA with 62 mol % of PES, 32 mol % of dimethylamino-ethane thiol group and 6 mol % of remaining allyl glycidyl group determined by proton NMR.
EXAMPLE 6
This example illustrates the preparation of a hydrophilic block copolymer, PES-ACys, in accordance with an embodiment of the invention.
3 g of PES-PolyAGE from Example 2 was dissolved in DMAc (10 mL) at 100° C. After complete dissolution of the polymer, the solution was purged with nitrogen for 5 minutes. Acetyl-L-cysteine (3 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (50 mg) were added to the reaction mixture and the mixture was stirred at 100° C. overnight. The product formed was precipitated in IPA (100 mL). After stirring for an additional 3 hrs in IPA (50 mL), the precipitate was filtered and washed with 50% IPA in water (200 mL), and dried in a vacuum oven overnight at 50° C. to obtain 3.4 g of PES-ACys. Proton NMR characterization showed the presence of 62 mol % of PES and 30 mol % of acetyl-L-cysteine, with 8 mol % of the allyl groups remaining.
EXAMPLE 7
This example illustrates the preparation of a hydrophilic block copolymer, PES-MES, in accordance with an embodiment of the invention.
15 g of PES-PolyAGE from Example 2 was dissolved in DMAc (40 mL) at 80° C. After complete dissolution of the polymer, the solution was purged for five minutes. Sodium-2-mercaptoethanesulfonate (11.7 g) and 2,2′-azobis(2-methylpropionamidine)dihydrochloride (250 mg) were added and the reaction mixture was stirred at 80° C. overnight. The hot solution was then precipitated by drop-wise addition to IPA (250 mL), the precipitate was further stirred in IPA for 2 hours, then filtered, and dried in a vacuum oven at 50° C. overnight. 16 g of PES-MES was obtained with 62 mol % of PES, 25 mol % of mercaptoethanesulfonic acid and 13 mol % of the allyl groups as determined by proton NMR.
EXAMPLE 8
This example illustrates the preparation of a hydrophilic block copolymer, PES-MEA, in accordance with an embodiment of the invention.
3 g of PES-PolyAGE from Example 2 was dissolved in DMAc (10 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 solution was precipitated by drop-wise addition to ethanol (250 mL). The resulting precipitate was reconstituted in ethanol (50 mL) and further stirred for 2 hours. The resulting precipitate was filtered and dried in a vacuum oven at 50° C. overnight to yield 3.3 g of PES-MEA with 62 mol % of PES, 34 mol % of aminoethanethiol group and 4 mol % of allyl groups as determined by proton NMR.
EXAMPLE 9
This example illustrates the preparation of porous membranes comprising a blend of PES and the polymer of Example 1 (PES-PolyAGE) or a blend of PES and the block copolymer of Example 4 (PES-MPS).
Membrane casting solutions were prepared by mixing the polymers, solvent, nonsolvent, and pore former, as set forth in Table 1 below.







TABLE 1







Compositions of Membrane Casting Solutions










PES-PolyAGE from
PES-MPS from



Example 1
Example 4



%
%















PEG 400
64.50
64.52



H2O
3.00
3.00



DMF
10.00
10.00



NMP
7.60
7.60



PES
6.95
10.40



Glycerin
1.00
1.00



PES-P
6.95
3.48



Total
100.00
100.00










The casting solutions were cast as thin films at 10-mil dope thickness using vapor-induced phase separation process, with a casting temperature of 30° C., relative humidity of 70%, and dry bulb temperature of 25° C. The dopes were placed in a water vapor chamber for 15 seconds and immersed in water bath at a temperature of 13° C.
CWST was measured on the dried membranes. Samples of the membrane were also tested for IPA extractables. 6 discs of 47 mm diameter were dried for 1 hour at 80° C. and then Soxhlet extracted with IPA for 3 hours followed by a final 1 hour dry cycle at 80° C. The % extractables were calculated. The CWSTs were again measured on several of the discs after the IPA extraction. The results obtained are set forth in Table 2. A polyethersulfone membrane prepared using polyvinyl pyrrolidone as a wetting agent was used as the control.







TABLE 2







IPA Extractables











PES-PVP
**50% PES-
**25% PES-



K90
PolyAGE from
MPS from



Control
Example 1
Example 4














CWST
87
59
77


(dynes/cm)


IPA Extractables
2.44
1.19
1.24


(%)





**Relative to the amount of PES matrix.






As indicated, the porous membrane prepared with PES-PolyAGE from Example 1 had a CWST of 59 dynes/cm and a low extractables level of 1.19%; it was instantly wetted by water. The porous membrane prepared with PES-MPS from Example 4 had a CWST of 77 dynes/cm and a low extractables level of 1.19%; it was also instantly wetted by water. For comparison, a polyethersulfone membrane prepared using polyvinylpyrrolidone has a CWST of 87 dyne/cm; however, the IPA extractables were high at 2.44%.
The morphology of the membranes was characterized using a Hitachi-3400II SEM with samples pre-sputtered with platinum/gold. SEM images of the cross-section of the membrane prepared from a blend of PES and PES-PolyAGE are shown in FIGS. 1A and 1B. SEM images of the cross-section of the membrane prepared from a blend of PES and PES-MPS are shown in FIGS. 2A and 2B.
EXAMPLE 10
This example illustrates the preparation of porous membranes comprising a blend of PPESK and PES-PolyAGE as wetting agent.
A casting solution containing a PPESK resin at 25 wt %, solvent NMP/DMAc (v/v) at 300 phr, the PES-PolyAGE of Example 2 at 15 wt % was prepared and cast as a 15 mil thick film at 28° C., air temperature 32° C., relative humidity 72%. The dope was placed in an environmental chamber for 15 seconds and immersed in water at room temperature. The morphology of the membrane was characterized by SEM. FIG. 4A depicts the SEM image of the cross-section of a membrane in accordance with an embodiment of the invention. FIG. 4B depicts a higher magnification SEM image of the image depicted in FIG. 4A. The membrane had a symmetrical pore structure distribution from side to side. The pores were in cellular forms with low interconnectivity.
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 block copolymer of the formula: A-B-A (I) or A-B (II),
wherein block A is:
(i) a polymer of allyl glycidyl ether, said polymer having allyl groups; or
(ii) a polymer of allyl glycidyl ether wherein one more of the allyl groups 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 selected from polysulfone, polyethersulfone, polyphenylene ether, polycarbonate, poly(phthalazinone ether sulfone ketone), polyether ketone, polyether ether ketone, polyether ketone ketone, polyimide, polyetherimide, and polyamide-imide;
wherein said polyphenylene ether is of the formula




 wherein n is the number of repeat units.

2. The block copolymer of claim 1, wherein the polymer of allyl glycidyl ether has a repeat unit of the formula:




wherein R is allyl.

3. The block copolymer of claim 1, wherein block A is a polymer of allyl glycidyl ether wherein one more of the allyl groups have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH2)a—S—(CH2)b—X, wherein a and b are independently 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.

4. The block copolymer of claim 1, wherein the zwitterion is 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.

5. The block copolymer of claim 1, wherein the aromatic hydrophobic polymeric segment is polyethersulfone.

6. The block copolymer of claim 1, which has one of the following structures:










wherein n, m1, and m2 are independently about 10 to about 1000.

7. The block copolymer of claim 1, wherein block A is present in an amount of about 20% to about 60 mol % and block B is present in an amount of about 40% to about 80 mol %.

8. The block copolymer of claim 7, wherein block A is present in an amount of about 40% to about 55 mol % and block B is present in an amount of about 45% to about 60 mol %.

9. A method of preparing a block copolymer of claim 1; the method comprising:
(i) providing an aromatic hydrophobic polymeric segment having one or more terminal functional groups selected from hydroxy, mercapto, and amino groups; and
(ii) carrying out ring opening polymerization of allyl glycidyl ether on the aromatic hydrophobic polymeric segment.

10. The method of claim 9, wherein the ring opening polymerization is carried out in the presence of a base.

11. The method of claim 10, wherein the base is 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, and lithium amide, and combinations thereof.

12. The method of claim 9, wherein the ring opening polymerization is carried out in a solvent selected from N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and combinations thereof.

13. The method of claim 9, wherein the aromatic hydrophobic polymeric segment has the formula:




wherein n is about 10 to about 1000.

14. A porous membrane comprising an aromatic hydrophobic polymer and a block copolymer of claim 1.

15. A method of preparing a porous membrane comprising an aromatic hydrophobic polymer and a block copolymer of claim 1, comprising:
(i) preparing a polymer solution comprising a solvent and said aromatic hydrophobic polymer and said block copolymer;
(ii) casting the polymer solution as a thin film;
(iii) subjecting the thin film to phase inversion to obtain a porous membrane; and optionally
(iv) washing the porous membrane.

16. A porous membrane comprising an aromatic hydrophobic polymer and a block copolymer of the formula: A-B-A (I) or A-B (II),
wherein block A is:
(i) a polymer of allyl glycidyl ether, said polymer having allyl groups; or
(ii) a polymer of allyl glycidyl ether wherein one more of the allyl groups 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.

17. The porous membrane of claim 16, wherein block copolymer has one of the following structures:









wherein n, m1, and m2 are independently about 10 to about 1000.

18. A block copolymer of the formula: A-B-A (I) or A-B (II), wherein block A is:
a polymer of allyl glycidyl ether wherein one more of the allyl groups 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 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.