Method for making porous asymmetric membranes and associated membranes and separation modules
View Patent ↗An method of making a porous asymmetric membrane involves dissolving a poly(phenylene ether), poly(phenylene ether) copolymer, polyethersulfone, polysulfone, polyphenylsulfone, polyimide, polyetherimide, polyvinylidene fluoride, or a combination thereof in a water-miscible polar aprotic solvent to provide a membrane-forming composition; and phase-inverting the membrane-forming composition in a first non-solvent composition composed of water, a water-miscible polar aprotic solvent, or a mixture thereof, and a polymer additive dissolved in the first non-solvent composition. The method can be a method of making a hollow fiber by coextrusion through a spinneret having an annulus and a bore, including coextruding the membrane-forming composition through the annulus, and the first non-solvent composition through the bore, into a second non-solvent composition composed of water, a water-miscible polar aprotic solvent, or a mixture thereof to form the hollow fiber.
1. A method of making a porous asymmetric membrane, wherein the method comprises:
dissolving a hydrophobic polymer comprising a poly(phenylene ether) copolymer in a water-miscible polar aprotic solvent to provide a membrane-forming composition; and
phase-inverting the membrane-forming composition in a first non-solvent composition comprising
water, a water-miscible polar aprotic solvent, or a combination comprising at least one of the foregoing, wherein the hydrophobic polymer is insoluble in the first non-solvent composition, and
a polymer additive soluble in, and dissolved in, the first non-solvent composition, to form the porous asymmetric membrane.
2. The method of claim 1 , further comprising washing the porous asymmetric membrane in a second non-solvent composition.
3. The method of claim 1 , further comprising drying the porous asymmetric membrane.
4. The method of claim 1 , wherein the poly(phenylene ether) copolymer comprises first and second repeat units independently having the structure:
wherein each occurrence of Z 1 is independently halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms;
wherein each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; and
wherein the first and second repeat units are different.
5. The method of claim 1 , wherein the poly(phenylene ether) copolymer comprises:
80 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and
20 to 80 mole percent repeat units derived from a first monohydric phenol having the structure
wherein Z is C 1 -C 12 alkyl or cycloalkyl, or a monovalent radical having the structure
wherein q is 0 or 1, and R 1 and R 2 are independently hydrogen or C 1 -C 6 alkyl;
wherein the poly(phenylene ether) copolymer has an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, measured in chloroform at 25° C.
6. The method of claim 1 , wherein the polymer additive is selected from the group consisting of poly(vinyl pyrrolidone), poly(oxazoline), poly(ethylene glycol), poly(propylene glycol), a poly(ethylene glycol) monoether or monoester, a poly(propylene glycol) monoether or monoester, a block copolymer of poly(ethylene oxide) and poly(propylene oxide), polystyrene-graft-poly(ethylene glycol), polystyrene-graft-poly(propylene glycol), polysorbate, cellulose acetate, glycosaminoglycans and combination thereof.
7. The method of claim 1 , wherein the polymer additive comprises an amphiphilic block copolymer comprising a hydrophobic block and a hydrophilic block.
8. The method of claim 7 , wherein the hydrophobic block comprises polystyrene and the hydrophilic block or graft comprises poly(N,N-dimethylacrylamide) or poly(4-vinylpyridine).
9. The method of claim 1 , wherein the first non-solvent composition comprises 10 to 100 weight percent water and 0 to 90 weight percent N-methyl-2-pyrrolidone, based on the total weight of the first non-solvent composition.
10. The method of claim 1 , wherein:
the hydrophobic polymer comprises a poly(phenylene ether) copolymer comprising 80 to 20 mole percent repeat units derived from 2,6-dimethylphenol and 20 to 80 mole percent repeat units derived from 2-methyl-6-phenylphenol;
the water-miscible polar aprotic solvent is N-methyl-2-pyrrolidone; and
the polymer additive is selected from the group consisting of poly(vinylpyrrolidone), poly(styrene-co-vinylpyrrolidone), polystyrene-block-poly(N,N-dimethylacrylamide) and combination thereof.
11. The method of claim 1 , wherein the poly(phenylene ether) copolymer comprises repeat units derived from 2,6-dimethylphenol and repeat units derived from 2-methyl-6-phenylphenol.
12. The method of claim 1 , wherein the poly(phenylene ether) copolymer comprises 90 to 20 mole percent of repeat units derived from 2,6-dimethylphenol and 10 to 80 mole percent repeat units derived from 2-methyl-6-phenylphenol.