Porous asymmetric polyphenylene ether membranes and associated separation modules and methods

• US 10,252,220 B2
• Filed: 04/30/2015
• Issued: 04/09/2019
• Est. Priority Date: 05/01/2014
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Berzinis, Albin Peter, Bajaj, Pooja, Halbfinger, Rachel Elizabeth, Bikel, Matias
• Primary Examiner(s): Menon, Krishnan S
• Application Number:
  US15/302,276
• Publication Number:
  US 20170056835A1
• Time in Patent Office: 1,440 Days
• Field of Search: None
• CPC Class Codes: A61M 1/1621 Constructional aspects thereof semi-permeable membranes for separation processes characterised by their properties B01D69/00; semi permeable membranes characterised by their material B01D71/00
• CPC Class Codes: B01D 2323/02 Hydrophilization
• CPC Class Codes: B01D 2323/04 Hydrophobization
• CPC Class Codes: B01D 2323/21839 Polymeric additives
• CPC Class Codes: B01D 2323/22 Specific non-solvents or non-solvent system
• CPC Class Codes: B01D 2323/36 Introduction of specific chemical groups
• CPC Class Codes: B01D 2323/40 in-situ membrane formation
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 2325/34 Molecular weight or degree of polymerisation
• CPC Class Codes: B01D 2325/36 Hydrophilic membranes
• CPC Class Codes: B01D 2325/38 Hydrophobic membranes
• CPC Class Codes: B01D 2325/39 Amphiphilic membranes
• CPC Class Codes: B01D 61/14 Ultrafiltration; Microfiltration
• CPC Class Codes: B01D 61/145 Ultrafiltration
• CPC Class Codes: B01D 61/364 Membrane distillation
• CPC Class Codes: B01D 63/02 Hollow fibre modules
• CPC Class Codes: B01D 67/00111 Polymer pretreatment in the casting solutions
• CPC Class Codes: B01D 67/0016 Coagulation
• CPC Class Codes: B01D 67/00165 Composition of the coagulation baths
• CPC Class Codes: B01D 67/0095 Drying
• CPC Class Codes: B01D 69/02 : characterised by their properties
• CPC Class Codes: B01D 69/06 : Flat membranes
• CPC Class Codes: B01D 69/08 : Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/088 : Co-extrusion; Co-spinning
• CPC Class Codes: B01D 69/125 : In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 69/1251 : by interfacial polymerisation
• CPC Class Codes: B01D 71/281 : Polystyrene
• CPC Class Codes: B01D 71/283 : Polyvinylpyridine
• CPC Class Codes: B01D 71/52 : Polyethers
• CPC Class Codes: B01D 71/5211 : Polyethylene glycol or polyethyleneoxide
• CPC Class Codes: B01D 71/56 : Polyamides, e.g. polyester-amides
• CPC Class Codes: B01D 71/76 : Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 rubbers in general B01D71/24
• CPC Class Codes: B01D 71/78 : Graft polymers
• CPC Class Codes: B01D 71/80 : Block polymers
• CPC Class Codes: C02F 1/441 : by reverse osmosis
• CPC Class Codes: C02F 2101/32 : Hydrocarbons, e.g. oil
• CPC Class Codes: C07K 1/34 : by filtration, ultrafiltration or reverse osmosis
• CPC Class Codes: C08B 37/0003 : General processes for their isolation or fractionation, e.g. purification or extraction from biomass
• CPC Class Codes: Y02W 10/37 : using solar energy

Abstract

A porous asymmetric membrane comprises a hydrophobic polymer comprising a poly(phenylene ether) or poly(phenylene ether) copolymer; and a polymer additive. A separation module can be fabricated from the porous asymmetric membrane. A method of forming the porous asymmetric membrane comprises: dissolving a hydrophobic polymer comprising a poly(phenylene ether) or poly(phenylene ether) copolymer and, a polymer additive in a water-miscible polar aprotic solvent to form a porous asymmetric membrane-forming composition; and phase-inverting the porous asymmetric membrane forming-composition in a first non-solvent composition to form the porous asymmetric membrane. The polymer additive comprises hydrophilic functional groups, copolymerized hydrophilic monomers, or blocks of hydrophilic monomer repeat units. For example, the polymer additive can comprise a hydrophilic polymer or amphiphilic polymer. The porous asymmetric membrane can be a flat membrane or hollow fiber.

Claims

1. A porous asymmetric membrane, comprising a poly(phenylene ether) copolymer comprising repeat units derived from 2,6-dimethylphenol and repeat units derived from 2-methyl-6-phenylphenol, and having an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, measured in chloroform at 25°

C. and a weight average molecular weight of 100,000 to 500,000 daltons, measured by gel permeation chromatography against polystyrene standards; and

an amphiphilic copolymer comprising a hydrophobic block and a hydrophilic block or graft.

2. The porous asymmetric membrane of claim 1, wherein the 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-phenol.

3. The porous asymmetric membrane of claim 1, wherein the amphiphilic copolymer comprises a block copolymer of poly(ethylene oxide) and poly(propylene oxide), polystyrene-graft-poly(ethylene glycol), or a combination thereof.

4. The porous asymmetric membrane of claim 1, wherein the hydrophobic block comprises polystyrene and the hydrophilic block or graft comprises poly(N,N-dimethylacrylamide) or poly(4-vinylpyridine).

5. The porous asymmetric membrane of claim 1, having a contact angle of 40 to 80 degrees.

13. A separation module comprising the porous asymmetric membrane of claim 1.

16. The porous asymmetric membrane of claim 1, wherein the poly(phenylene ether) copolymer has a solubility in a water-miscible polar aprotic solvent of greater than 100 grams per kilogram at 25°

C.

17. The porous asymmetric membrane of claim 1, wherein the poly(phenylene ether) copolymer has a solubility in a water-miscible polar aprotic solvent selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, of 100 to 400 grams per kilogram at 25°

C.

18. The porous asymmetric membrane of claim 1, wherein the hydrophilic block of the amphiphilic block copolymer comprises an ethylenically unsaturated monomer selected from methoxy-capped poly(ethylene oxide) methacrylate, 4-vinylpyridine, N-vinylpyrrolidone, N,N-dimethylacrylamide, 4-acryloylmorpholine, or a combination comprising at least one of the foregoing.

19. The porous asymmetric membrane of claim 1, wherein the amphiphilic copolymer comprises a block copolymer of poly(ethylene oxide) and poly(propylene oxide).

6. A method of forming a porous asymmetric membrane, the method comprising:

dissolving a poly(phenylene ether) copolymer comprising repeat units derived from 2,6-dimethylphenol and repeat units derived from 2-methyl-6-phenylphenol, and having an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, measured in chloroform at 25°

C. and a weight average molecular weight of 100,000 to 500,000 daltons, measured by gel permeation chromatography against polystyrene standards; and

an amphiphilic copolymer comprising a hydrophobic block and a hydrophilic block or graft in a water-miscible polar aprotic solvent to form a porous asymmetric membrane-forming composition; and

phase-inverting the porous asymmetric membrane forming-composition in a first non-solvent composition to form the porous asymmetric membrane.

7. The method of claim 6, further comprising washing the porous asymmetric membrane in a second non-solvent composition.

8. The method of claim 6, further comprising drying the porous asymmetric membrane.

9. The method of claim 6, 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. A method of making a hollow fiber by coextrusion through a spinneret comprising an annulus and a bore, wherein the method comprises coextruding:

a membrane-forming composition comprising a hydrophobic polymer comprising a poly(phenylene ether) or poly(phenylene ether) copolymer comprising repeat units derived from 2,6-dimethylphenol and percent repeat units derived from 2-methyl-6-phenylphenol, and having an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, measured in chloroform at 25°

C. and a weight average molecular weight of 100,000 to 300,000 daltons, measured by gel permeation chromatography against polystyrene standards; and

an amphiphilic copolymer comprising a hydrophobic block and a hydrophilic block or graft dissolved in a water-miscible polar aprotic solvent through the annulus, and

a first non-solvent composition comprising water, a water-miscible polar aprotic solvent, or a combination comprising at least one of the foregoing, in the first non-solvent composition, through the bore,

into a second non-solvent composition comprising water, a water-miscible polar aprotic solvent, or a combination comprising at least one of the foregoing, to form the hollow fiber.

11. The method of claim 10, further comprising washing the hollow fiber in a third non-solvent composition.

12. The method of claim 10, further comprising drying the hollow fiber.

14. A hollow fiber made by the method of claim 10.

15. A separation module comprising the hollow fiber of claim 14.