Composite membrane with support comprising poly(phenylene ether) and amphilphilic polymer; method of making; and separation module thereof

Patent metadata

Field	Value
Publication number	US-2017043301-A1
Application number	US-201515303556-A
Country	US
Kind code	A1
Filing date	Apr 30, 2015
Priority date	May 1, 2014
Publication date	Feb 16, 2017
Grant date	—

Abstract

A porous composite membrane includes a porous support layer of a poly(phenylene ether) or poly(phenylene ether) copolymer; and an amphiphilic copolymer having a hydrophobic block and a hydrophilic block or graft, wherein the hydrophobic block includes a polystyrene block, a poly(phenylene ether) block, or a poly(phenylene ether) copolymer block; and an ultrathin, cross-linked, water permeable layer, which is the reaction product of an electrophilic monomer and a nucleophilic monomer, in contact with a side of the porous support layer. The reaction product can be a polyamide that is the interfacial condensation product of: an aromatic, polyfunctional acyl halide comprising of 3 to 6 acyl halide groups per aromatic ring and an aromatic polyamine comprising at least two primary amine groups and a maximum number of primary amine groups that is less than or equal to the number of acyl halide groups on the polyfunctional acyl halide.

First claim

1 . A porous composite membrane comprising:
a porous support layer comprising, consisting essentially of, or consisting of a hydrophobic polymer comprising, consisting essentially of, or consisting of a poly(phenylene ether) or poly(phenylene ether) copolymer; and an amphiphilic copolymer comprising a hydrophobic block and a hydrophilic block or graft wherein the hydrophobic block comprises a polystyrene block, a poly(phenylene ether) block or a poly(phenylene ether) copolymer block; and an ultrathin, cross-linked, water permeable layer in contact with a side of the porous support layer, and comprising the reaction product of an electrophilic monomer and a nucleophilic monomer.

2 . The porous composite membrane of claim 1 , wherein the hydrophobic polymer comprises a poly(phenylene ether) comprising having repeat units 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; and
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.

3 . The porous composite membrane of claim 1 , wherein the hydrophobic polymer comprises a poly(phenylene ether) copolymer comprising:
100 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 0 to 80 mole percent repeat units derived from a second monohydric phenol having the structure

wherein Z is C 1-12 alkyl or cycloalkyl, or a monovalent group 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 mole percents are based on the total moles of all repeat units; and
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.

4 . The porous composite membrane 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 the second monohydric phenol.

5 . The porous composite membrane of claim 4 , wherein the second monohydric phenol is 2-methyl-6-phenylphenol.

6 . The porous composite membrane of claim 1 , wherein the hydrophobic polymer has an intrinsic viscosity of 0.7 to 1.5 deciliters per gram, measured in chloroform at 25° C.

7 . The porous composite membrane of claim 1 , wherein the solubility of the hydrophobic polymer in the water-miscible polar aprotic solvent is 50 to 400 grams per kilogram at 25° C., based on the combined weight of the poly(phenylene ether) copolymer and the solvent.

8 . The porous composite membrane of claim 1 , wherein the amphiphilic block copolymer comprises 20 to 50 weight percent of the hydrophobic block and 50 to 80 weight percent of the hydrophilic block or graft.

9 . The porous composite membrane of claim 1 , wherein the hydrophobic block of the amphiphilic block copolymer comprises polystyrene.

10 . The porous composite membrane of claim 1 , wherein the hydrophobic block of the amphiphilic block copolymer comprises a poly(phenylene ether) block comprising having repeat units 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; and
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.

11 . The porous composite membrane of claim 1 , wherein the hydrophobic block of the amphiphilic block copolymer comprises a poly(phenylene ether) copolymer block comprising:
100 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 0 to 80 mole percent repeat units derived from a second monohydric phenol having the structure

wherein Z is C 1-12 alkyl or cycloalkyl, or a monovalent group 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 all mole percents are based on the total moles of all repeat units; and
wherein the poly(phenylene ether) copolymer block is derived from a poly(phenylene ether) copolymer having an intrinsic viscosity of 0.1 to 0.5 deciliters per gram, measured in chloroform at 25° C.

12 . The porous composite membrane of claim 1 , wherein the hydrophobic block of the amphiphilic block copolymer comprises a poly(phenylene ether) copolymer block comprising:
80 to 20 mole percent repeat units derived from 2,6-dimethylphenol; and 20 to 80 mole percent repeat units derived from the second monohydric phenol.

13 . The porous composite membrane of claim 12 , wherein the second monohydric phenol is 2-methyl-6-phenylphenol.

14 . The porous composite membrane of claim 1 , wherein the hydrophilic block or graft of the amphiphilic block copolymer comprises a polymerized hydrophilic ethylenically unsaturated monomer.

15 . The porous composite membrane of claim 14 , wherein the hydrophilic ethylenically unsaturated monomer comprises 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.

16 . The porous composite membrane of claim 1 , wherein the hydrophilic block or graft of the amphiphilic block copolymer comprises poly(ethylene oxide) or a copolymer of ethylene oxide with 1,2-propylene oxide, 1,2-butylene oxide, styrene oxide, or a combination comprising at least one of the foregoing, wherein the hydrophilic block or graft comprises sufficient ethylene oxide repeat units for the hydrophilic block to be hydrophilic.

17 . The porous composite membrane of claim 1 , wherein the hydrophobic block or graft of the amphiphilic block copolymer comprises polystyrene, and the hydrophilic block of the amphiphilic block copolymer comprises poly(ethylene oxide).

18 . The porous composite membrane of claim 1 , wherein any hydrophilic polymer is excluded.

19 . The porous composite membrane of

Assignees

• Sabic Global Technologies Bv

Inventors

• Berzinis Albin Peter
• Bajaj Pooja
• Halbfinger Rachel Elizabeth
• Bikel Matias

Classifications

• B01D2323/02

  Hydrophilization · CPC title

• B01D71/80

  Block polymers · CPC title

• B01D71/76

  Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 (rubbers in general B01D71/24) · CPC title

• B01D2325/36

  Hydrophilic membranes · CPC title

• B01D2323/40

  in-situ membrane formation · CPC title