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US 11,970,590 B2Granted
Polyphenylenes, methods, and uses thereof
AssigneeSimon Fraser University
InventorsSteven Holdcroft, Thomas J. G. Skalski, Michael Adamski, Benjamin Britton, Timothy J. Peckham
Life of this patent
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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.
Claims18
A polymer, comprising a first repeating unit of Formula (I):
- and
- a second repeating unit of Formula (II):
- wherein:
- R1A, R1B, R1C, R1D, R1E, and R1F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6 alkyl, halo, nitro, cyano, SO3−X+, PO32−X+2, and COO−X+, wherein X+ is H+ or a cation, and provided that at least two of R1A, R1B, R1C, R1D, R1E, and R1F are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3−X+, PO32−X+2, and COO−X+, wherein X+ is H+ or a cation;
- R1G and R1H 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 C1-6 alkyl, halo, nitro, cyano, SO3−X+, PO32−X+2, and COO−X+, wherein X+ is H+ or a cation;
- R3A, R3B, R3C, R3D, R3E, and R3F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6 alkyl;
- halo, nitro, and cyano;
- R3G and R3H 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 C1-6 alkyl, halo, nitro, and cyano;
- A1 and B1 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;
- A2 and B2 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;
- L1 and K1 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 C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
- L2 and K2 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 C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
- and
- L3 and K3 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 C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl;
- provided that the repeating unit of Formula (I) is not
12 more elements
A random block copolymer, comprising:
- a first block selected from
- and
- any combination thereof, wherein X+ is H+, a cation, an alkali metal ion, or [N(R5A)(R5B)(R5C)(R5D)]+ wherein R5A, R5B, R5C, R5D are independently H, C1-6alkyl, aryl, or heteroaryl;
- and
- a second block selected from
- and
- any combination thereof;
- wherein
- n is an integer of from 3 to 100,
- m is an integer of from 3 to 100;
- and
- wherein a mole ratio of the first block to the second block ranges from 1:99 to 99:1.
9 more elements
A method of making a random block copolymer, comprising
- forming a mixture of a first polymer of Formula (VI)
- wherein
- R1A, R1B, R1C, R1D, R1E, and R1F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6 alkyl, halo, nitro, cyano, SO3−X+, PO32−X+2, and COO−X+, wherein X+ is H+ or a cation, and provided that at least two of R1A, R1B, R1C, R1D, R1E, and R1F are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3−X+, PO32−X+2, and COO−X+, wherein X+ is H+ or a cation,
- R1G and R1H 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 C1-6 alkyl, halo, nitro, cyano, SO3−X+, PO32−X+2, and COO−X+, wherein X+ is H+ or a cation,
- A1 is 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,
- A2 is 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,
- L1 is 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 C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl,
- L2 is independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl,
- L3 is independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl,
- n is an integer of from 3 to 100, and
- A is a reactive first terminal group;
- and
- a second polymer of Formula (VII)
- wherein
- R3A, R3B, R3C, R3D, R3E, and R3F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6 alkyl;
- halo, nitro, and cyano,
- R3G and R3H 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 C1-6 alkyl, halo, nitro, and cyano,
- B1 is 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,
- B2 is 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,
- K1 is 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 C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl,
- K2 is independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl,
- K3 is independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl,
- m is an integer of from 3 to 100, and
- B is a second reactive terminal group configured to react with A;
- and
- reacting A and B to provide a random block copolymer of Formula (VIII)
- wherein a mole ratio of the first block to the second block ranges from 1:99 to 99:1.
24 more elements
Dependencies are inferred from the claim text.