Polyphenylenes, methods, and uses thereof

Patent metadata

Field	Value
Publication number	US-11802187-B2
Application number	US-201816603785-A
Country	US
Kind code	B2
Filing date	Apr 10, 2018
Priority date	Apr 10, 2017
Publication date	Oct 31, 2023
Grant date	Oct 31, 2023

Abstract

Described herein are anionic phenylene oligomers and polymers, and devices including these materials. The oligomers and polymers can be prepared in a convenient and well-controlled manner, and can be used in cation exchange 5 membranes. Also described is the controlled synthesis of anionic phenylene monomers and their use in synthesizing anionic oligomers and polymers, with precise control of the position and number of anionic groups.

First claim

The invention claimed is:

1. A polymer, comprising a repeating unit of Formula (I):

wherein:
R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, S 3 − X + , P 3 2− X + 2 , and COO − X + , wherein X + is H + or a cation, and provided that at least two of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from S 3 − X + , P 3 2− X + 2 , and COO − X + ;
R 1G and R 1H are independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, S 3 − X + , P 3 2− X + 2 , and COO − X + , wherein X + is H + or a cation;
A 1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl;
A 2 is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl;
L 1 is an optionally substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
L 2 is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; and
L 3 is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
wherein the sulfonated polymer has an ion exchange capacity of about 2.49 meq g −1 to about 3.7 meq g −1 ; and
provided that the repeating unit of Formula (I) is not

2. The polymer of claim 1 , wherein R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, and SO 3 − X + , wherein X + is H + or a cation, provided that at least four of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl substituted in the para-position with SO 3 − X + .

3. The polymer of claim 1 , wherein X + is H + , or a cation selected from [N(R 5A )(R 5B )(R 5C )(R 5D )] + and alkali metal ion, wherein R 5A , R 5B , R 5C , R 5D are independently H, C 1-6 alkyl, aryl, or heteroaryl.

4. The polymer of claim 1 , wherein A 1 is arylene optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and A 2 is absent.

5. The polymer of claim 4 , wherein A 1 is phenylene optionally substituted with 1, 2, 3, or 4 halo; and A 2 is absent.

6. The polymer of claim 1 , wherein L 1 is naphthalenylene, phenylene, or C 1-6 alkyl-substituted phenylene, provided that the phenylene is not p-phenylene; L 2 is absent or arylene; and L 3 is absent or arylene, wherein said arylene is optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl and halo.

7. The polymer of claim 1 , wherein -L 3 -L 2 -L 1 - is independently selected from

8. The polymer of claim 1 , comprising a repeating unit selected from:

wherein X + is H + , a cation, an alkali metal ion, or [N(R 5A )(R 5B )(R 5C )(R 5D )] + wherein R 5A , R 5B , R 5C , R 5D are independently H, C 1-6 alkyl, aryl, or heteroaryl.

9. A method of making a polymer of claim 1 , comprising:
forming a mixture of a compound of Formula (III)

wherein
R 1A , R 1B , R 1C , R 1D , R 1E , R 1F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, S 3 − X + , P 3 2− X + 2 , and COO − X + , wherein X + is H + or a cation, and provided that at least four of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl substituted in the para-position with a substituent independently selected from S 3 − X + , P 3 2− X + 2 , and COO − X + ;
A 1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and
A 2 is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl;
provided that the compound of Formula (III) is not

with at least one compound of Formula (IV),
D 1 L 1 -L 2 -L 3 D 2   (IV)

and
wherein
L 1 is an optionally substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
L 2 is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
L 3 is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
D 1 and D 2 are independently H, R 1G , R 1H , R 3G , R 3H , or a protecting group, wherein R 1G and R 1H are independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, S 3 − X + , PO 3 2− X + 2 , and COO − X + , wherein X + is H + or a cation and wherein R 3G and R 3H are independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, and cyano; and
reacting a compound of Formula (III) or (III-A), and at least one compound of Formula (IV), Diels Alder reaction provide the polymer of claim 1 .

10. An ionic membrane or an ionomer comprising a polymer of claim 1 .

Assignees

• Univ Fraser Simon

Inventors

• Holdcroft Steven
• Skalski Thomas J G
• Adamski Michael
• Britton Benjamin
• Peckham Timothy J

Classifications

• C08J5/2256 Primary

  based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation · CPC title

• B01D69/02

  characterised by their properties · CPC title

• B01D71/82

  characterised by the presence of specified groups, e.g. introduced by chemical after-treatment · CPC title

• C07C211/63

  having quaternised nitrogen atoms bound to acyclic carbon atoms · CPC title

• C07C309/44

  containing doubly-bound oxygen atoms bound to the carbon skeleton · CPC title