Multiblock copolymers and methods of use

Patent metadata

Field	Value
Publication number	US-10022679-B2
Application number	US-201414774936-A
Country	US
Kind code	B2
Filing date	Mar 11, 2014
Priority date	Mar 11, 2013
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

The present invention relates to polymer compositions and their manufacture. Specifically, the invention relates to multiblock polymers and copolymers, their fabrication, modification and/or functionalization and use as membranes or films.

First claim

What is claimed is:

1. A multiblock copolymer membrane comprising a self-assembled nanoporous active selective layer comprising pores characterized by an average pore diameter of less than 5 nm, wherein the multiblock copolymer is a block terpolymer selected from the group consisting of polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) [PI-PS-PDMA], polyisoprene-b-polystyrene-b-poly(tert-butylmethacrylate) [PI-PS-PtBMA], poly(isoprene)-b-polystyrene)-b-poly((4-vinyl)pyridine), poly(isoprene)-b-poly(styrene)-b-poly((2-vinyl) pyridine), poly(isoprene)-b-poly(styrene)-b-poly(ethylene oxide), poly(isoprene)-b-poly(styrene b-poly(methyl methacrylate), poly(isoprene)-b-poly(styrene)-b-poly(acrylic acid), poly(isoprene)-b-poly(styrene)-b-poly(dimethylethyl amino ethyl methacrylate), poly(isoprene)-b-poly(styrene)-b-poly(hydroxystyrene), poly(isoprene-b-poly(α-methyl styrene)-b-poly((4-vinyl)pyridine), poly(isoprene)-b-poly(α-methyl styrene)-b-poly((2-vinyl) pyridine), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(ethylene oxide), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(methyl methacrylate), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(acrylic acid), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(dimethylethyl amino ethyl methacrylate), poly (butadiene)-b-poly(styrene)-b-poly((4-vinyl)pyridine), poly(butadiene)-b-poly(styrene)-b-poly((2-vinyl) pyridine), poly(butadiene)-b-poly(styrene)-b-poly(ethylene oxide), poly(butadiene)-b-poly(styrene)-b-poly(methyl methacrylate), poly(butadiene)-b-poly(styrene)-b-poly(acrylic acid), poly(butadiene)-b-poly(styrene)-b-poly(dimethylethyl amino ethyl methacrylate), poly(butadiene)-b-poly(styrene)-b-poly(hydroxystyrene), poly(butadiene)-b-poly(α-methyl styrene)-b-poly((4-vinyl)pyridine), poly(butadiene)-b-poly(α-methyl styrene)-b-poly((2-vinyl) pyridine), poly(butadiene)-b-poly(α-methyl styrene)-b-poly(ethylene oxide), poly(butadiene)-b-poly(α-methyl styrene)-b-poly(methyl methacrylate), poly(butadiene)-b-poly(α-methyl styrene)-b-poly(acrylic acid), and poly(butadiene)-b-poly(α-methyl styrene)-b-poly(dimethylethyl amino ethyl methacrylate).

2. The multiblock copolymer membrane of claim 1 , wherein the average pore diameter of the nanoporous active selective layer is less than 1 nm.

3. The multiblock copolymer membrane of claim 1 , wherein the multiblock copolymer is selected from the group consisting of polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) [PI-PS-PDMA], polyisoprene-b-polystyrene-b-poly(tert-butylmethacrylate) [PI-PS-PtBMA], poly(isoprene)-b-poly(styrene)-b-poly((4-vinyl)pyridine), poly(isoprene)-b-poly(styrene)-b-poly((2-vinyl) pyridine), poly(isoprene)-b-poly(styrene)-b-poly(acrylic acid), poly(isoprene)-b-poly(styrene)-b-poly(dimethylethyl amino ethyl methacrylate), poly(isoprene)-b-poly(styrene)-b-poly(hydroxystyrene), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(acrylic acid), poly(butadiene)-b-poly(styrene)-b-poly((4-vinyl)pyridine), poly(butadiene)-b-poly(styrene)-b-poly((2-vinyl) pyridine), poly(butadiene)-b-poly(styrene)-b-poly(ethylene oxide), poly(butadiene)-b-poly(styrene)-b-poly(methyl methacrylate), poly(butadiene)-b-poly(styrene)-b-poly(acrylic acid), poly(butadiene)-b-poly(styrene)-b-poly(dimethylethyl amino ethyl methacrylate), poly(butadiene)-b-poly(styrene)-b-poly(hydroxystyrene) and poly(butadiene)-b-poly(α-methyl styrene)-b-poly(acrylic acid).

4. A multiblock copolymer membrane comprising a self-assembled nanoporous active selective layer comprising pores characterized by an average pore diameter of less than 5 nm, wherein the multiblock terpolymer is a block terpolymer selected from the group consisting of PI-PS-PDMA and PI-PS-PtBMA.

5. A device comprising the multiblock copolymer membrane of claim 1 .

6. The multiblock copolymer membrane of claim 1 , wherein the membrane has been chemically functionalized with a moiety selected from the group consisting of an alcohol, hydroxyl, carbonyl, aldehyde, thiol, ketone, acyl halide, carbonate, carboxylate, carboxylic acid, ester, methoxy, hydroperoxide, peroxide, ether, hemiacetal, hemiketal, acetal, ketal, acetal, orthoester, heterocycle, orthocarbonate ester, amide, amine, imine, imide, azide, cyanate, nitrate, nitrile, nitrite, nitro compound, nitroso compound, pyridine, pyridine derivative, thiol, sulfide, thioether, disulfide, sulfoxide, sulfone, sulfinic acid, sulfonic acid, thiocyanate, thione, thiol, phosphine, phosphane, phosphonic acid, phosphate, phosphodiester, boronic acid, boronic ester, bonnie acid, borinic ester, carboxylic acid, alkyl group, and any combination thereof.

7. A method for separating, purifying, filtering or concentrating a liquid solution, comprising contacting the membrane of claim 1 with the liquid solution.

8. The multiblock copolymer membrane of claim 1 , wherein the membrane is an organic membrane comprising a nanoporous active selective layer, wherein the nanoporous active selective layer comprises a plurality of pores, the pores characterized by:
(i) substantially uniform pore diameters of less than 5 nm; and
(ii) substantially uniform pore orientations which are approximately perpendicular to surfaces of the membrane.

9. The organic membrane of claim 8 , wherein the pores are characterized by substantially uniform pore diameters of less than 1 nm.

10. A device comprising the organic membrane of claim 8 .

11. A method for separating, purifying, filtering or concentrating a liquid solution, comprising contacting the organic membrane of claim 8 with the liquid solution.

12. A method for forming the multiblock copolymer membrane of claim 1 , the method comprising the steps of:
a) synthesizing a self-assembled A-B-C multiblock copolymer; and
b) fabricating a nanostructured membrane from the self-assembled A-B-C multiblock copolymer using a self-assembly and non-solvent induced phase separation.

13. The method of claim 12 , wherein the synthesizing the self-assembled A-B-C multiblock copolymer is carried out through a controlled reversible addition-fragmentation chain transfer polymerization mechanism.

14. The method of claim 12 , wherein the nanostructured membrane is characterized by an average pore diameter of about 0.5-3 nm.

15. A nanostructured membrane of a self-assembled A-B-C multiblock copolymer, wherein the copolymer comprises a terpolymer, and the terpolymer comprises polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) [PI-PS-PDMA] or polyisoprene-b-polystyrene-b-poly(tert-butylmethacrylate) [PI-PS-PtBMA].

16. A nanostructured membrane of a self-assembled A-B-C multiblock copolymer, wherein the copolymer comprises a terpolymer, and the terpolymer comprises polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) [PI-PS-PDMA], polyisoprene-b-polystyrene-b-poly(tert-butylmethacrylate) [PI-PS-PtBMA], poly(isoprene)-b-poly(styrene)-b-poly((4-vinyl)pyridine), poly(isoprene)-b-poly(styrene)-b-poly((2-vinyl) pyridine), poly(isoprene)-b-poly(styrene)-b-poly(ethylene oxide), poly(isoprene)-b-poly(styrene)-b-poly(methyl methacrylate), poly(isoprene)-b-poly(styrene)-b-poly(acrylic acid), poly(isoprene)-b-poly(styrene)-b-poly(dimethylethyl amino ethyl methacrylate), poly(isoprene)-b-poly(styrene)-b-poly(hydroxystyrene), poly(isoprene)-b-poly(α-methyl styrene)-b-poly((4-vinyl)pyridine), poly(isoprene)-b-poly(α-methyl styrene)-b-poly((2-vinyl) pyridine), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(ethylene oxide), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(methyl methacrylate), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(acrylic acid), poly(isoprene)-b-poly(α-methyl styrene)-b-poly(dimethylethyl amino ethyl methacrylate), poly (butadiene)-

Assignees

• Univ Notre Dame Du Lac
• Purdue Res Foundation Prf
• Purdue Research Foundation

Inventors

• Phillip William A
• Boudouris Bryan W

Classifications

• C02F1/44

  by dialysis, osmosis or reverse osmosis {(general membrane separation processes B01D61/00, membrane modules B01D63/00, electrodialysis C02F1/4693, combination of membrane modules and bioreactors C02F3/1268)} · CPC title

• B01D71/80 Primary

  Block polymers · CPC title

• B01D2325/04

  Characteristic thickness · CPC title

• B01D69/02

  characterised by their properties · CPC title

• C08J9/00

  Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof (mechanical aspects of shaping of plastics or substances in a plastic state for the production of porous or cellular articles B29C) · CPC title