Poly(phenylene)-based anion exchange polymers and methods thereof

Patent metadata

Field	Value
Publication number	US-10053535-B2
Application number	US-201715398547-A
Country	US
Kind code	B2
Filing date	Jan 4, 2017
Priority date	Jan 4, 2016
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

The present invention relates to anionic exchange polymers including a poly(phenylene) structure. The structure can include any useful cationic moiety. Methods and uses of such structures and polymers are also described herein. In one instance, such polymers are employed to form a solid membrane.

First claim

The invention claimed is:

1. A composition comprising a structure having the formula (II):

or a salt thereof or a form thereof including a counter ion, wherein:
each R A comprises an aryl group and a cationic functionality, wherein the aryl group is selected from the consisting of an optionally substituted aryl, optionally substituted alkaryl, optionally substituted arylalkoxy, optionally substituted aryloxy, optionally substituted aryloxycarbonyl, optionally substituted aryloyl, optionally substituted arylcarbonylalkyl, optionally substituted arylsulfonyl, and optionally substituted arylsulfonylalkyl;
each R 1 and R 3 is, independently, H, halo, cyano, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 1-12 heteroalkyl, R S , R P , R C , or R F , wherein R S is an acidic moiety comprising a sulfonyl group, R P is an acidic moiety comprising a phosphoryl group, R C is an acidic moiety comprising a carbonyl group, and R F is an electron-withdrawing moiety;
each Ar L is, independently, a bivalent linker comprising optionally substituted arylene;
each Ar M is, independently, a bivalent linker comprising optionally substituted arylene;
each q is, independently, an integer of from 0 to 5, in which each q for R 1 is, independently, 0 or 1;
each a is, independently, an integer of from 0 to 5, wherein at least one a is not 0; and
m is an integer of from about 1 to 1000,
wherein at least one R A is disposed on a pendent aryl group of formula (II).

2. The composition of claim 1 , wherein:
at least one R A is L A -Ar A or a salt thereof or a form thereof including a counter ion;
L A is a covalent bond, carbonyl, oxy, thio, azo, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, or optionally substituted C 4-18 aryleneoxy; and
Ar A is an optionally substituted aryl comprising one or more cationic functionalities.

3. The composition of claim 1 , wherein:
at least one R A is

 or a salt thereof or a form thereof including a counter ion;
each L A and L A1 is, independently, a covalent bond, carbonyl, oxy, thio, azo, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, or optionally substituted C 4-18 aryleneoxy;
each R 4 is, independently, H, halo, cyano, nitro, nitroso, azido, sulfo, carboxyaldehyde, carboxyl, hydroxyl, amino, amidino, amido, thioamido, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 1-12 alkoxy, R S , R P , R C , or R P , wherein R S is an acidic moiety comprising a sulfonyl group, R P is an acidic moiety comprising a phosphoryl group, R C is an acidic moiety comprising a carbonyl group, and R F is an electron-withdrawing moiety;
each R A1 is, independently, a cationic functionality;
each q is, independently, an integer of from 0 to 5; and
each a1 is, independently, an integer of from 1 to 5.

4. The composition of claim 2 , wherein:
L A is a covalent bond, carbonyl, sulfonyl, —NR L3 —, —CR L1 ═N—, —(CR L1 R L2 ) La —, —C(O)NR L3 —, —NR L3 C(O)—, —PR L3 —, —SO 2 NR L3 —, —NR L3 SO 2 —, —(CR L1 R L2 ) La —C(O)—(CR L1 R L2 ) Lb —, —(CR L1 R L2 ) La —SO 2 —(CR L1 R L2 ) Lb —, —(CR L1 R L2 ) La —C(O)NR L3 —(CR L1 R L2 ) Lb —, —(CR L1 R L2 ) La —NR L3 C(O)—(CR L1 R L2 ) Lb —, —(CR L1 R L2 ) La —SO 2 NR L3 —(CR L1 R L2 ) Lb —, or —(CR L1 R L2 ) La —NR L3 SO 2 —(CR L1 R L2 ) Lb —;
each of R L1 , R L2 , and R L3 is, independently, H, halo, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 alkoxy, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl; and
each of La and Lb is, independently, an integer of from 0 to 10, wherein at least one of La or Lb is not 0.

5. The composition of claim 1 , wherein:
the composition comprises a structure having the formula (IIA):

or a salt thereof or a form thereof including a counter ion;
each Ar A is, independently, an optionally substituted aryl group comprising one or more cationic functionalities; and
each L A is, independently, a covalent bond, carbonyl, oxy, thio, azo, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, or optionally substituted C 4-18 aryleneoxy.

6. The composition of claim 2 , wherein Ar A is substituted with one or more substituents selected from the group consisting of halo, cyano, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted nitroalkyl, and optionally substituted alkyl.

7. The composition of claim 1 , wherein:
the composition comprises a structure having any one of formulas (IIq) to (IIx):

or a salt thereof or a form thereof including a counter ion;
each R A1 is, independently, a cationic functionality;
each L A and L A1 is, independently, a covalent bond, carbonyl, oxy, thio, azo, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, or optionally substituted C 4-18 aryleneoxy;
each R 4 and R M1 , if present, is, independently, H, halo, cyano, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 1-12 heteroalkyl, R S , R P , R C , or R F ; and
each a1 is, independently, an integer of from 0 to 5, wherein at least one a1 is not 0.

8. The composition of claim 1 , wherein:
the composition comprises a structure having any one of formulas (II-11) to (II-13):

or a salt thereof or a form thereof including a counter ion;
Ar A is an optionally substituted aryl comprising one or more cationic functionalities;
each R 7 is, independently, H, halo, cyano, nitro, nitroso, azido, sulfo, carboxyaldehyde, carboxyl, hydroxyl, amino, amidino, amido, thioamido, dithiocarboxyamino, optionally subst

Assignees

• Nat Tech & Eng Solutions Sandia Llc
• Los Alamos Nat Security Llc

Inventors

• Kim Yu Seung
• Lee Kwan-Soo
• Fujimoto Cy

Classifications

• C08J5/2256

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

• C08G2261/312

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

• C08J2365/02

  Polyphenylenes · CPC title

• C08G2261/516

  ion-conductive · CPC title

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title