IP Library › Granted Patent US 11,891,481
Granted Patent B2
US 11,891,481 · App. 17/357,252 · Granted Feb 6, 2024

Poly(aryl ether) based polymers and associated gas separation membranes

Inventors: Timothy Manning Swager (Newton, MA); Zachary Smith (Belmont, MA); Francesco Maria Benedetti (Urbania, IT); Sheng Guo (Brookline, MA)
Assignee: Massachusetts Institute of Technology
C08G65/4075B01D53/228B01D67/0006B01D67/0093B01D69/02B01D71/52C08G65/4087C08G65/485C08J5/18B01D2325/20B01D2325/34C08G2650/36C08J2371/12
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Quick Facts
Patent No.
US 11,891,481
App. No.
17/357,252
Granted
Feb 6, 2024
Kind
B2
Abstract

Compositions and methods related to the synthesis and application of poly(aryl ether)s are generally described.

Claims (24)

1. A method of making a gas separation membrane comprising a poly(aryl ether), comprising:

providing a first prepolymer comprising a monomer of a formula (X) x —Ar—(OH) y , wherein Ar comprises at least one aryl or heteroaryl group, X is a halogen or a halogen equivalent, each X is the same or different, and x+y is at least two;

providing a second prepolymer comprising a comonomer of a formula (X) x —Ar′—(OH) y wherein Ar′ comprises at least one aryl or heteroaryl group, X is a halogen or a halogen equivalent, each X is the same or different, and x+y is at least two;

providing a catalyst;

providing a base;

reacting the first prepolymer with the second prepolymer in the presence of the catalyst and the base to provide the poly(aryl ether); and

forming the gas separation membrane.

2. The method of claim 1 , wherein the poly(aryl ether) is of a formula [(—Ar—O—Ar′—O—) n ] or [(—Ar′—O—Ar—O—) n ], wherein n is greater than 1.

3. The method of claim 1 , wherein the halogen is bromide, chloride, and/or iodide.

4. The method of claim 1 , wherein the catalyst comprises a metal.

5. The method of claim 4 , wherein the metal is palladium, nickel, or iron.

6. The method of claim 1 , further comprising:

providing a third prepolymer comprising a second comonomer of a formula (X) x —Ar″−(OH) y , wherein Ar″ comprises at least one aryl or heteroaryl group, X is a halogen or a halogen equivalent, each X is the same or different, and x+y is at least two, and

reacting the first prepolymer with the second prepolymer and the third prepolymer in the presence of the catalyst and the base to provide the poly(aryl ether).

7. The method of claim 6 , wherein the poly(aryl ether) is of a formula [(—Ar′—O—Ar—O—Ar″—O—) n ] or [(—Ar″—O—Ar—O—Ar′—O—) n ], wherein n is greater than 1.

8. The method of claim 1 , further comprising:

providing an endcapping agent; and

reacting the first prepolymer with the second prepolymer and the endcapping agent in the presence of the catalyst and the base to provide the poly(aryl ether).

9. The method of claim 8 , wherein the poly(aryl ether) is of a formula [(—Ar—O—Ar′—O—) n EC], [EC(—Ar—O—Ar′—O—) n ], [EC—O—Ar′(—Ar—O—Ar′—O—) n EC], [(—Ar′—O—Ar—O—) n EC], [EC(—Ar′—O—Ar—O—) n ], [EC(—Ar′—O—Ar—O) n —Ar′—EC], [EC(—Ar—O—Ar′—O—) n Ar—EC], or [EC(—Ar′—O—Ar—O—) n EC], wherein n is greater than 1 and EC is the endcapping agent.

10. The method of claim 8 , wherein the endcapping agent comprises an alkyne, a polymer, a cyclic group, a heterocyclic group, and/or a nanoparticle.

11. The method of claim 8 , wherein the endcapping agent comprises norbornene.

12. The method of claim 1 , further comprising functionalizing the poly(aryl ether).

13. The method of claim 12 , wherein the poly(aryl ether) is functionalized by halogenation, sulfonation, nitration, acylation, nitrene addition, carbene addition, radical addition, and/or chloromethylation.

14. The method of claim 1 , wherein Ar and/or Ar′ comprises a benzene group, a phenanthrene group, an iptycene group, a spirobi(indene) group, a fluorene group, a spirobifluorene group, a pyridine group, a bipyridine group, a phenanthroline group, a cyclopentane group, and/or a bicyclic ring structure, any of which may be optionally substituted.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 14, 2022
From: SWAGER, TIMOTHY MANNING; SMITH, ZACHARY; BENEDETTI, FRANCESCO MARIA; GUO, SHENG
To: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
Reel/Frame 058738/0157 →
Continuity (2)
Provisional Application 63155697 · Mar 2, 2021
Related Publication 20220282041A1 · Sep 8, 2022
Cited By (2)
US 12,252,584 US 12,297,322