Zwitterion-containing membranes

Patent metadata

Field	Value
Publication number	US-10150088-B2
Application number	US-201415034454-A
Country	US
Kind code	B2
Filing date	Nov 7, 2014
Priority date	Nov 8, 2013
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

Disclosed is a statistical copolymer that includes both zwitterionic repeat units and hydrophobic repeat units and a filtration membrane that contains a selective layer formed of the statistical copolymer. Also disclosed are methods of preparing the above-described filtration membrane.

First claim

What is claimed is:

1. A statistical copolymer comprising
zwitterionic repeat units, each containing independently sulfobetaine, carboxybetaine, or pyridinium alkyl sulfonate, and
hydrophobic repeat units, each formed independently from styrene, fluorinated styrene, methyl methacrylate, acrylonitrile, or trifluoroethyl methacrylate, wherein the statistical copolymer has a molecular weight of 10,000 to 10,000,000 Dalton, the zwitterionic repeat units and the hydrophobic repeat units each constitute 25-75% by weight of the statistical copolymer, and the hydrophobic repeat units are capable of forming a homopolymer that has a glass transition temperature of 0° C. or higher.

2. The statistical copolymer of claim 1 , wherein the statistical copolymer has a molecular weight of 20,000 to 2,000,000 Dalton, the zwitterionic repeat units constitute 30-75% by weight of the statistical copolymer, and the hydrophobic repeat units constitute 25-70% by weight of the statistical copolymer.

3. The statistical copolymer of claim 2 , wherein the statistical copolymer has a molecular weight of 30,000 to 500,000 Dalton, the zwitterionic repeat units constitute 30-70% by weight of the statistical copolymer, and the hydrophobic repeat units constitute 30-70% by weight of the statistical copolymer.

4. The statistical copolymer of claim 1 , wherein the zwitterionic repeat units each are formed independently from sulfobetaine acrylate, sulfobetaine acrylamide, carboxybetaine acrylate, carboxybetaine methacrylate, carboxybetaine acrylamide, 3-(2-vinylpyridinium-1-yl)propane-1-sulfonate, 3-(4-vinylpyridinium-1-yl)propane-1-sulfonate, or sulfobetaine methacrylate; and the hydrophobic repeat units each are formed independently from methyl methacrylate, acrylonitrile, or trifluoroethyl methacrylate.

5. The statistical copolymer of claim 4 , wherein the statistical copolymer has a molecular weight of 20,000 to 2,000,000 Dalton, the zwitterionic repeat units constitute 30-75% by weight of the statistical copolymer, and the hydrophobic repeat units constitute 25-70% by weight of the statistical copolymer.

6. The statistical copolymer of claim 5 , wherein the statistical copolymer has a molecular weight of 30,000 to 500,000 Dalton, the zwitterionic repeat units constitute 30-70% by weight of the statistical copolymer, and the hydrophobic repeat units constitute 30-70% by weight of the statistical copolymer.

7. The statistical copolymer of claim 1 , wherein the statistical copolymer is poly((methyl methacrylate)-random-(sulfobetaine methacrylate)), poly((trifluoroethyl methacrylate)-random-(sulfobetaine methacrylate)), poly((acrylonitrile)-random-(sulfobetaine methacrylate)), poly((trifluoroethyl methacrylate)-random-(3-(2-vinylpyridinium-1-yl)propane-1-sulfonate)), or poly((acrylonitrile)-random-(3-(4-vinylpyridinium-1-yl)propane-1-sulfonate)).

8. The statistical copolymer of claim 1 , wherein the statistical copolymer has a molecular weight of 20,000 to 2,000,000 Dalton, the zwitterionic repeat units constitute 30-75% by weight of the statistical copolymer, the hydrophobic repeat units constitute 25-70% by weight of the statistical copolymer, and the glass transition temperature is 25° C. or higher.

9. The statistical copolymer of claim 8 , wherein the statistical copolymer has a molecular weight of 30,000 to 500,000 Dalton, the zwitterionic repeat units constitute 30-70% by weight of the statistical copolymer, the hydrophobic repeat units constitute 30-70% by weight of the statistical copolymer, and the glass transition temperature is 25° C. or higher.

10. A filtration membrane comprising a selective layer formed of a statistical copolymer comprising zwitterionic repeat units and hydrophobic repeat units, wherein the filtration membrane has a molecular weight cut-off of 100 to 10000 Dalton, the selective layer contains effective pores formed by self-assembly of the zwitterionic repeat units and having effective pore sizes of 0.5 to 3 nm, and the statistical copolymer has a molecular weight of 10,000 to 10,000,000 Dalton, the zwitterionic repeat units and the hydrophobic repeat units each constituting 25-75% by weight of the statistical copolymer, and the hydrophobic repeat units being capable of forming a homopolymer that has a glass transition temperature of 0° C. or higher.

11. The filtration membrane of claim 10 , wherein the zwitterionic repeat units each contain independently sulfobetaine, carboxybetaine, phosphorylcholine, or pyridinium alkyl sulfonate; and the hydrophobic repeat units each are formed independently from styrene, fluorinated styrene, methyl methacrylate, acrylonitrile, or trifluoroethyl methacrylate.

12. The filtration membrane of claim 11 , wherein the statistical copolymer has a molecular weight of 20,000 to 2,000,000 Dalton, the zwitterionic repeat units constitute 30-75% by weight of the statistical copolymer, the hydrophobic repeat units constitute 25-70% by weight of the statistical copolymer, and the effective pore size is 0.5 to 2.5 nm.

13. The filtration membrane of claim 12 , wherein the statistical copolymer has a molecular weight of 30,000 to 500,000 Dalton, the zwitterionic repeat units constitute 30-70% by weight of the statistical copolymer, the hydrophobic repeat units constitute 30-70% by weight of the statistical copolymer, and the effective pore size is 0.5 to 2 nm.

14. The filtration membrane of claim 11 , wherein the zwitterionic repeat units each are formed independently from sulfobetaine acrylate, sulfobetaine acrylamide, phosphorylcholine acrylate, phosphorylcholine acrylamide, phosphorylcholine methacrylate, carboxybetaine acrylate, carboxybetaine methacrylate, carboxybetaine acrylamide, 3-(2-vinylpyridinium-1-yl)propane-1-sulfonate, 3-(4-vinylpyridinium-1-yl)propane- 1 -sulfonate, or sulfobetaine methacrylate; and the hydrophobic repeat units each are formed independently from methyl methacrylate, acrylonitrile, or trifluoroethyl methacrylate.

15. The filtration membrane of claim 14 , wherein the statistical copolymer has a molecular weight of 20,000 to 2,000,000 Dalton, the zwitterionic repeat units constitute 30-75% by weight of the statistical copolymer, the hydrophobic repeat units constitute 25-70% by weight of the statistical copolymer, and the effective pore size is 0.5 to 2.5 nm.

16. The filtration membrane of claim 14 , wherein the statistical copolymer has a molecular weight of 30,000 to 500,000 Dalton, the zwitterionic repeat units constitute 30-70% by weight of the statistical copolymer, the hydrophobic repeat units constitute 30-70% by weight of the statistical copolymer, and the effective pore size is 0.5 to 2 nm.

17. The filtration membrane of claim 10 , further comprising a support layer, wherein the selective layer is disposed on a surface of the support layer and the support layer has an effective pore size larger than that of the selective layer and is formed of polyethersulfone, polyphenylenesulfone, polyphenylenesulfidesulfone, polyacrylonitrile, cellulose ester, polyphenyleneoxide, polypropylene, polyvinyledenefluoride, polyvinylchloride, polyarylsulfone, polyphenylene sulfone, polyetheretherketone, polysulfone, polyamide, polyimide, or a combination thereof.

18. The filtration membrane of claim 17 , wherein the zwitterionic repeat units each contain independently sulfobetaine, carboxybetaine, phosphorylcholine, or pyridinium alkyl sulfonate; and the hydrophobic repeat units each are formed independently from styrene, fluorinated styrene, methyl methacrylate, acrylonitrile, or trifluoroethyl methacrylate.

19. The filtration

Assignees

• Univ Tufts

Inventors

• Alexiou Ayse Asatekin
• Bengani Prity

Classifications

• B01D71/42

  Polymers of nitriles, e.g. polyacrylonitrile · CPC title

• C08F220/18

  with acrylic or methacrylic acids · CPC title

• B01D71/68

  Polysulfones; Polyethersulfones · CPC title

• B01D71/28

  Polymers of vinyl aromatic compounds · 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