IP Library Granted Patent US 10,022,679
Granted Patent B2
US 10,022,679 · App. 14/774,936 · Granted Jul 17, 2018

Multiblock copolymers and methods of use

Inventors: William A. Phillip (Granger, IN); Bryan W. Boudouris (Lafayette, IN)
Assignees: University of Notre Dame du Lac; Purdue Research Foundation
B01D71/80B01D61/02B01D67/0011B01D67/0093B01D69/02C02F1/44C08F293/005C08J9/00B01D67/0016B01D71/28B01D71/40B01D2325/02B01D2325/021B01D2325/04C08J2353/02
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 10,022,679
App. No.
14/774,936
Granted
Jul 17, 2018
Kind
B2
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.

Claims (22)

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)-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), or poly(butadiene)-b-poly(α-methyl styrene)-b-poly(dimethylethyl amino ethyl methacrylate).

17. The nanostructured membrane of claim 16 , wherein the terpolymer comprises polyisoprene-b-polystyrene-b-poly(N,N-di methyl acrylamide) [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), or poly(butadiene)-b-poly(α-methyl styrene)-b-poly(acrylic acid).

18. The method of claim 12 wherein the multiblock copolymer comprises a terpolymer that comprises polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) [PI-PS-PDMA] or polyisoprene-b-polystyrene-b-poly(tert-butylmethacrylate) [PI-PS-PtBMA].

Assignments (3)
CONFIRMATORY LICENSE Recorded Mar 16, 2017
From: UNIVERSITY OF NOTRE DAME
To: NATIONAL INSTITUTES OF HEALTH (NIH), U.S. DEPT. OF HEALTH AND HUMAN SERVICES (DHHS), U.S. GOVERNMENT
Reel/Frame 041589/0916 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 7, 2015
From: BOUDOURIS, BRYAN
To: PURDUE RESEARCH FOUNDATION
Reel/Frame 036749/0520 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 7, 2015
From: PHILLIP, WILLIAM A.
To: UNIVERSITY OF NOTRE DAME DU LAC
Reel/Frame 036749/0527 →
Continuity (3)
Provisional Application 61851615 · Mar 11, 2013
Provisional Application 61874776 · Sep 6, 2013
Related Publication 20160023171A1 · Jan 28, 2016
Cited By (1)
US 12,398,243