Polyphenylenes, methods, and uses thereof

Patent metadata

Field	Value
Publication number	US-12084554-B2
Application number	US-202318464836-A
Country	US
Kind code	B2
Filing date	Sep 11, 2023
Priority date	Apr 10, 2017
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

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 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 embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An ionic membrane comprising a copolymer having a first repeating unit of Formula (I):

and
a second repeating unit of Formula (II):

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, SO 3 − X + , PO 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 SO 3 − X + , PO 3 2− X 2 + , and COO − X + , wherein X is H + or a cation;
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, SO 3 − X + , PO 3 2− X 2 + , and COO − X + , wherein X + H + or a cation;
R 3A , R 3B , R 3C , R 3D , R 3E , and R 3F 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, and cyano;
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;
A 1 and B 1 are independently 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 and B 2 are independently 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 and K 1 are independently 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 and K 2 are independently 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 and K 3 are independently 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;
provided that the repeating unit of Formula (I) is not

2. The ionic membrane of claim 1 , wherein the first repeating unit of Formula (I) is a repeating unit of Formula (I-A):

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, SO 3 − X + , PO 3 2− X 2 + , and COO − X + , wherein X + 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 SO 3 − X + , PO 3 2− X 2 + , and COO − X + , wherein X + H + or a cation;
R 2A , R 2B , R 2C , and R 2D are independently H, halo, nitro, cyano, aryl, or 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.

3. The ionic membrane of claim 1 , wherein the second repeating unit of Formula (II) is a repeating unit of Formula (II-A)

wherein:
R 3A , R 3B , R 3C , R 3D , R 3E , and R 3F 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, and cyano;
R 4A , R 4B , R 4C , and R 4D ) are independently H, halo, nitro, cyano, aryl, or heteroaryl;
K 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;
K 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
K 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.

4. The ionic membrane 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 + H + or a cation, provided that at least two of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl substituted with 1, 2, 3, 4, or 5 SO 3 − X + .

5. The ionic membrane 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.

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

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

8. The ionic me

Assignees

• Univ Fraser Simon

Inventors

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

Classifications

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• H01M8/1023

  having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes · CPC title

• C08J2365/02

  Polyphenylenes · CPC title

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title

• C08G2261/228

  Polymers, i.e. more than 10 repeat units · CPC title