Porous membranes and associated separation modules and methods

• US 10,307,717 B2
• Filed: 11/21/2016
• Issued: 06/04/2019
• Est. Priority Date: 03/29/2016
• Status: Expired due to Fees

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Berzinis, Albin Peter, de Grooth, Joris, de Brouwer, Johannes, Zhou, Miejuan, Bajaj, Pooja, Halbfinger, Rachel Elizabeth, Narang, Kristi Jean
• Primary Examiner(s): Mullis, Jeffrey C
• Application Number:
  US15/356,836
• Publication Number:
  US 20170282128A1
• Time in Patent Office: 925 Days
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2323/22 Specific non-solvents or non-solvent system
• 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 61/145 Ultrafiltration
• CPC Class Codes: B01D 67/00091 by evaporation
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 67/0095 Drying
• 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 71/261 Polyethylene
• CPC Class Codes: B01D 71/262 Polypropylene
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/701 Polydimethylsiloxane
• CPC Class Codes: B01D 71/80 Block polymers
• CPC Class Codes: C08J 2201/0544 the non-solvent being aqueous
• CPC Class Codes: C08J 2207/00 Foams characterised by their intended use
• CPC Class Codes: C08J 2371/12 Polyphenylene oxides
• CPC Class Codes: C08J 2471/02 Polyalkylene oxides
• CPC Class Codes: C08J 9/28 : by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Abstract

A porous membrane is made from a poly(phenylene ether) copolymer containing 10 to 40 mole percent repeat units derived from 2-methyl-6-phenylphenol and 60 to 90 mole percent repeat units derived from 2,6-dimethylphenol; and a block copolymer containing backbone or pendant blocks of poly(C_2-4 alkylene oxide). The porous membrane is made by dissolving the poly(phenylene ether) copolymer in a water-miscible polar aprotic solvent to form a membrane-forming composition; and phase-inverting the membrane forming-composition in a first non-solvent composition to form the porous membrane. A method of making a hollow fiber by coextrusion through a spinneret having an annulus and a bore, includes coextruding the membrane-forming composition through the annulus, and a first non-solvent composition through the bore, into a second non-solvent composition to form the hollow fiber.

Claims

1. A porous membrane comprising:

a poly(phenylene ether) copolymer consisting essentially of 10 to 40 mole percent repeat units derived from 2-methyl-6-phenylphenol and 60 to 90 mole percent repeat units derived from 2,6-dimethylphenol; and

a hydrophilic block copolymer comprising a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer having a number average molecular weight of 1,000 to 14,000 daltons, and comprising, based on the weight of the block copolymer, 5 to 50 weight percent of poly(ethylene oxide) blocks;

a poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) block copolymer having a number average molecular weight 500 to 12,000 daltons, and comprising, based on the weight of the block copolymer, 5 to 50 weight percent of poly(ethylene oxide) blocks;

or a combination comprising at least one of the foregoing;

wherein the weight average molecular weight of the poly(phenylene ether) copolymer is greater than or equal to 75,000 daltons and less than or equal to 500,000 daltons, measured by gel permeation chromatography against polystyrene standards.

2. The porous membrane of claim 1, 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.

3. The porous membrane of claim 1, comprising 30 to 70 weight percent of the poly(phenylene ether) copolymer, and 30 to 70 weight percent of the block copolymer, based on the total weight of the porous membrane.

4. The porous membrane of claim 1, having a contact angle which is 20 to 80 degrees lower than the contact angle of a porous membrane formed from the poly(phenylene ether) copolymer alone.

14. The porous membrane of claim 1, wherein the poly(phenylene ether) copolymer consists of 10 to 40 mole percent 2-methyl-6-phenylphenol and 60 to 90 mole percent 2,6-dimethylphenol.

15. The porous membrane of claim 1, wherein the weight average molecular weight of the poly(phenylene ether) copolymer is greater than or equal to 75,000 daltons and less than or equal to 300,000 daltons.

16. The porous membrane of claim 1, wherein the porous membrane comprises 30 to 60 weight percent of the poly(phenylene ether) copolymer, and 40 to 70 weight percent of the block copolymer, based on the total weight of the porous membrane.

17. The porous membrane of claim 1, wherein the poly(phenylene ether) copolymer consists of 10 to 30 mole percent 2-methyl-6-phenylphenol and 70 to 90 mole percent 2,6-dimethylphenol.

18. The porous membrane of claim 1, wherein the weight average molecular weight of the poly(phenylene ether) copolymer is greater than or equal to 100,000 daltons and less than or equal to 300,000 daltons.

5. A method of making a porous membrane, the method comprising:

dissolving a poly(phenylene ether) copolymer consisting essentially of 10 to 40 mole percent repeat units derived from 2-methyl-6-phenylphenol and 60 to 90 mole percent repeat units derived from 2,6-dimethylphenol and a hydrophilic block copolymer comprising a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer having a number average molecular weight of 1,000 to 14,000 daltons, and comprising, based on the weight of the block copolymer, 5 to 50 weight percent, of poly(ethylene oxide) blocks;

a poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) block copolymer having a number average molecular weight 500 to 12,000 daltons, and comprising, based on the weight of the block copolymer, 5 to 50 weight percent of poly(ethylene oxide) blocks;

or a combination comprising at least one of the foregoing in a water-miscible polar aprotic solvent to form a membrane-forming composition; and

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

wherein the weight average molecular weight of the poly(phenylene ether) copolymer is greater than or equal to 75,000 daltons and less than or equal to 500,000 daltons, measured by gel permeation chromatography against polystyrene standards.

6. The method of claim 5, further comprising washing the porous membrane in a second non-solvent composition.

7. The method of claim 5, further comprising drying the porous membrane.

8. The method of claim 5, wherein the membrane-forming composition comprises, based on the total weight of the composition, 1 to 50 weight percent, of the poly(phenylene ether) copolymer and block copolymer comprising blocks of poly(C_2-4 alkylene oxide) combined, and 50 to 99 weight percent of the water-miscible polar aprotic solvent, and has a viscosity of 1 to 100 pascal-seconds.

9. The method of claim 5, wherein the first non-solvent composition comprises, based on the total weight of the first non-solvent composition, 10 to 100 weight percent water, and 0 to 90 weight percent N-methyl-2-pyrrolidone.

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 poly(phenylene ether) copolymer consisting essentially of 10 to 40 mole percent repeat units derived from 2-methyl-6-phenylphenol and 60 to 90 mole percent repeat units derived from 2,6-dimethylphenol, and a hydrophilic block copolymer comprising a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer having a number average molecular weight of 1,000 to 14,000 daltons, and comprising, based on the weight of the block copolymer, 5 to 50 weight percent, of poly(ethylene oxide) blocks;

a poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) block copolymer having a number average molecular weight 500 to 12,000 daltons, and comprising, based on the weight of the block copolymer, 5 to 50 weight percent of poly(ethylene oxide) blocks;

or a combination comprising at least one of the foregoing 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;

wherein the weight average molecular weight of the poly(phenylene ether) copolymer is greater than or equal to 75,000 daltons and less than or equal to 500,000 daltons, measured by gel permeation chromatography against polystyrene standards.

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.

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