Amphiphilic block copolymer; composition, membrane, and separation module thereof; and methods of making same

• US 10,358,517 B2
• Filed: 04/30/2015
• Issued: 07/23/2019
• 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): Boyle, Kara B
• Application Number:
  US15/303,561
• Publication Number:
  US 20170037177A1
• Time in Patent Office: 1,545 Days
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 2325/38 Hydrophobic membranes
• CPC Class Codes: B01D 61/14 Ultrafiltration; Microfiltration
• CPC Class Codes: B01D 67/00091 by evaporation
• CPC Class Codes: B01D 67/0095 Drying
• CPC Class Codes: B01D 71/5211 Polyethylene glycol or polyethyleneoxide
• CPC Class Codes: C08F 283/08 on to polyphenylene oxides
• CPC Class Codes: C08G 2261/128 graft
• CPC Class Codes: C08G 65/485 Polyphenylene oxides
• CPC Class Codes: C08L 2205/05 containing polymer components which can react with one another
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 33/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 71/12 Polyphenylene oxides
• CPC Class Codes: C08L 71/126 modified by chemical after-treatment

Abstract

An amphiphilic block copolymer comprises a poly(phenylene ether) block or a poly(phenylene ether) copolymer block and a hydrophilic block or graft. A method of making the amphiphilic block copolymer comprises polymerization of a hydrophilic ethylenically unsaturated monomer in the presence of poly(phenylene ether) or a poly(phenylene ether) copolymer to make the amphiphilic block copolymer. A porous asymmetric membrane comprises a poly(phenylene ether) or poly(phenylene ether) copolymer, and the amphiphilic block copolymer comprising a poly(phenylene ether) block or a poly(phenylene ether) copolymer block, and a hydrophilic block or graft. The porous asymmetric membrane is made by phase-inversion of a dope solution of the poly(phenylene ether) or poly(phenylene ether) copolymer and the amphiphilic block copolymer in a coagulation bath.

Claims

1. An amphiphilic block copolymer, comprising

a hydrophobic block comprising a poly(phenylene ether) block or a poly(phenylene ether) copolymer block having repeat units of the structure:

2. The amphiphilic block copolymer of claim 1, comprising 20 to 50 weight percent of the hydrophobic block and 50 to 80 weight percent of the hydrophilic block or graft.

3. The amphiphilic block copolymer of claim 1, wherein the hydrophobic block 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

4. The amphiphilic block copolymer of claim 1, wherein the hydrophobic block of the amphiphilic copolymer 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 amphiphilic block copolymer of claim 4, wherein the second monohydric phenol comprises 2-methyl-6-phenylphenol.

6. The amphiphilic block copolymer of claim 1, 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.

7. A method of making the amphiphilic block copolymer of claim 1, comprising polymerization of the hydrophilic ethylenically unsaturated monomer in the presence of a hydrophobic polymer comprising a poly(phenylene ether) or a poly(phenylene ether) copolymer having repeat units of the structure:

8. The method of claim 7, wherein the polymerization is controlled radical polymerization.

9. The method of claim 8, wherein the controlled radical polymerization is atom transfer radical polymerization, reversible addition fragmentation transfer polymerization, or stable free radical polymerization.

10. The method of claim 7, wherein the polymerization is graft polymerization.

11. The method of claim 7, wherein the hydrophilic ethylenically unsaturated monomer comprises methoxy-capped poly(ethylene oxide) methacrylate, 4-vinylpyridine, vinyl pyrrolidone, N,N-dimethylacrylamide, 4-acryloylmorpholine, or a combination comprising at least one of the foregoing.

13. A porous asymmetric membrane-forming composition comprising:

a hydrophobic polymer comprising a poly(phenylene ether) or poly(phenylene ether) copolymer;

the amphiphilic block copolymer of claim 1; and

a water-miscible polar aprotic solvent,

wherein the hydrophobic polymer and amphiphilic block copolymer are dissolved in the water-miscible polar aprotic solvent.

19. The amphiphilic block copolymer of claim 1, wherein the hydrophobic block of the amphiphilic copolymer comprises the poly(phenylene ether) copolymer block.

12. A porous asymmetric membrane comprising:

a hydrophobic polymer comprising a poly(phenylene ether) or poly(phenylene ether) copolymer; and

an amphiphilic block copolymer comprising

an amphiphilic block copolymer comprising

a hydrophobic block comprising a poly(phenylene ether) or poly(phenylene ether) copolymer having repeat units of the structure;

15. The porous asymmetric membrane of claim 12, wherein the hydrophobic polymer comprises a poly(phenylene ether) having repeat units having the structure:

16. The porous asymmetric membrane of claim 12, 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

17. The porous asymmetric membrane of claim 12, 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.

18. The porous asymmetric membrane of claim 17, wherein the second monohydric phenol comprises 2-methyl-6-phenylphenol.

20. The porous asymmetric copolymer of claim 12, wherein the hydrophobic block of the amphiphilic copolymer comprises the poly(phenylene ether) copolymer block.

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

dissolving

a hydrophobic polymer comprising a poly(phenylene ether) or poly(phenylene ether) copolymer and

wherein each occurrence of Z¹ is independently halogen, unsubstituted or substituted C_1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C_1-12 hydrocarbylthio, C_1-12 hydrocarbyloxy, or C_2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and

each occurrence of Z² is independently hydrogen, halogen, unsubstituted or substituted C_1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C_1-12 hydrocarbylthio, C_1-12 hydrocarbyloxy, or C_2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.

21. A method of making the amphiphilic block copolymer of claim 14, wherein the hydrophobic block of the amphiphilic copolymer comprises the poly(phenylene ether) copolymer block.