Poly(phenylene)-based anion exchange polymers and methods thereof
View Patent ↗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.
1. A composition comprising a structure having the formula (III):
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;
m is an integer of from about 1 to 1000;
L′ is a sublink; and
each R L is, independently, a reactive end group,
wherein at least one R A is disposed on a pendent aryl group of formula (III).
2. The composition of claim 1 , wherein L′ comprises a covalent bond, 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, optionally substituted C 4-18 aryleneoxy, optionally substituted polyphenylene, or a structure of formula (II):
or a salt thereof or a form thereof including a counter ion.
3. The composition of claim 1 , wherein R L is optionally substituted C 5-19 aryloyl or optionally substituted C 4-18 aryl.
4. The composition of claim 1 , wherein the composition comprises a structure having the formula (IIIa) or (IIIb):
or a salt thereof or a form thereof including a counter ion.
5. A composition comprising a structure having the formula (IV):
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;
each of m and n is, independently, an integer of from about 1 to 1000;
L is a linking segment; and
Ar* is a hydrophobic segment,
wherein at least one R A is disposed on a pendent aryl group of formula (IV).
6. The composition of claim 5 , wherein the composition comprises a structure having the formula (V) or (Va);
or a salt thereof or a form thereof including a counter ion, and wherein:
each R L is, independently, a reactive end group;
each R H , if present, is, independently, H, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 heteroalkyl, halo, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, optionally substituted C 4-18 aryl-C 1-6 alkoxy, optionally substituted C 4-18 aryloxy, optionally substituted C 5-19 aryloxycarbonyl, optionally substituted C 5-19 aryloyl, optionally substituted C 4-18 arylcarbonyl-C 1-6 alkyl, optionally substituted C 4-18 arylsulfonyl, or optionally substituted C 4-18 arylsulfonyl-C 1-6 alkyl; and
each h, if present, is, independently, an integer of from 0 to 5, wherein at least one h is not 0.
7. A composition of claim 5 , wherein the composition is a polymer or a solid membrane.
8. 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.
9. 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 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 R A1 is, independently, a cationic functionality;
each q is, independently, an integer of from 1 to 5; and
each a1 is, independently, an integer of from 1 to 5.
10. The composition of claim 8 , 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 —, —(CRL R L2 ) La —SO 2 —(CR L1 R L2 ) Lb —, —(CR L1 R L2 ) La —C(O)NR L3 —(CR L1 R L2 ) Lb —, —(CRL R L2 ) La —NR L3 C(O)—(CR L1 R L2 ) Lb —, —(CR L1 R L2 ) La —SO 2 NR L3 —(CRL R L2 ) Lb —, or —(CRL R L2 ) La —NR L3 SO 2 —(CR L1 R L2 ) Lb —;
each of R L , 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.
11. The composition of claim 1 , wherein:
the cationic functionality is selected from the group consisting of:
or a salt thereof or a form thereof including a counter ion;
each of R N1 , R N2 , R N3 , R N4 , R N5 , R N6 , R N7 , R N8 , R N9 , R N10 , and R N11 is, independently, H, halo, cyano, nitro, nitroso, azido, sulfo, carboxyaldehyde, carboxyl, hydroxyl, amino, amidino, amido, thioamido, dithiocarboxyamino, optionally substituted C 1-12 alkyl, optionally substituted C 3-12 cycloalkyl, optionally substituted C 1-12 alkanoyl, optionally substituted C 1-12 alkoxy, optionally substituted heterocyclyl, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy, and wherein a combination of R N1 and R N2 , a combination of R N1 and R N3 , a combination of R N1 and R N4 , a combination of R N3 and R N4 , or a combination of R N5 and R N6 , taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group;
each of R a5 , R a6 , R a7 , R a8 , R a9 , R 10 , R a11 , and R a12 is, independently, absent, a covalent bond, H, or optionally substituted alkyl, wherein a combination of R a6 and R a7 , a combination of R a7 and R a8 , a combination of R a8 and R a9 , a combination of R a9 and R a10 , a combination of R a10 and R a11 , or a combination of R a11 and R a12 , taken together with the parent atom to which each are attached, can form a heterocyclyl group or an aryl group;
each of a 5 , a 6 , a 7 , a 8 , a 9 , and a 10 is, independently, C, N, O, or S, in which at least one of a 5 , a 6 , a 7 , a 8 , and a 9 within a five-membered ring is N, O, or S and at least one of a 5 , a 6 , a 7 , a 8 , a 9 , and a 10 within a six-membered ring is N, O, or S; and
each B is, independently, an anionic moiety.
12. The composition of claim 1 , wherein at least one R A is an optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, optionally substituted C 4-18 aryl-C 1-6 alkoxy, optionally substituted C 4-18 aryloxy, optionally substituted C 5-19 aryloxycarbonyl, optionally substituted C 7-11 aryloyl, optionally substituted C 4-18 arylcarbonyl-C 1-6 alkyl, optionally substituted C 4-18 arylsulfonyl, or optionally substituted C 4-18 arylsulfonyl-C 1-6 alkyl.
13. The composition of claim 1 , wherein:
R S is —SO 2 —R S1 or —SO 2 —NR N1 —R S2 or —SO 2 —NR N1 —SO 2 —R S3 , wherein each R S1 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl; each R N1 is, independently, H, optionally substituted C 1-12 alkyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl; each R S2 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 alkylsulfonyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl; and
each R S3 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl;
R P is —P(O)(OH) 2 or —O—PO(OH) 2 or —P(O)<R P1 R P2 or —P(O)<R Ar R P2 or —P(O)<R Ar R Ar wherein each of R P1 and R P2 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 alkoxy, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy; and each R Ar is, independently, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy;
R C is —CO 2 H or —C(O)—R C1 or —R CA —C(O)—R C1 , wherein each R C1 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 alkoxy, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy; and each R CA is, independently, oxy, optionally substituted C 1-12 alkylene, or optionally substituted C 1-12 heteroalkylene; and
R F is carboxyaldehyde, optionally substituted C 1-12 alkyl, optionally substituted C 2-13 alkanoyl, or optionally substituted C 5-19 aryloyl.
14. The composition of claim 1 , wherein Ar L and/or Ar M is optionally substituted phenylene, optionally substituted naphthylene, or optionally substituted phenanthrylene; wherein the optional substitution for Ar L is R A , R S , R P , R C , or R F ; and wherein the optional substitution for Ar M is R A , R S , R P , R C , R F , or a label.
15. The composition of claim 5 , 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.
16. The composition of claim 15 , 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.
17. The composition of claim 5 , wherein:
the cationic functionality is selected from the group consisting of:
or a salt thereof or a form thereof including a counter ion;
each of R N1 , R N2 , R N3 , R N4 , R N5 , R N6 , R N7 , R N8 , R N9 , R N10 , and R N11 is, independently, H, halo, cyano, nitro, nitroso, azido, sulfo, carboxyaldehyde, carboxyl, hydroxyl, amino, amidino, amido, thioamido, dithiocarboxyamino, optionally substituted C 1-12 alkyl, optionally substituted C 3-12 cycloalkyl, optionally substituted C 1-12 alkanoyl, optionally substituted C 1-12 alkoxy, optionally substituted heterocyclyl, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy, and wherein a combination of R N1 and R N2 , a combination of R N1 and R N3 , a combination of R N1 and R N4 , a combination of R N3 and R N4 , or a combination of R N5 and R N6 , taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group;
each of R a5 , R a6 , R a7 , R a8 , R a9 , R a10 , R a11 , and R a12 is, independently, absent, a covalent bond, H, or optionally substituted alkyl, wherein a combination of R a6 and R a7 , a combination of R a7 and R a8 , a combination of R a8 and R a9 , a combination of R a9 and R a10 , a combination of R a10 and R a11 , or a combination of R a11 and R a12 , taken together with the parent atom to which each are attached, can form a heterocyclyl group or an aryl group;
each of a 5 , a 6 , a 7 , a 8 , a 9 , and a 10 is, independently, C, N, O, or S, in which at least one of a 5 , a 6 , a 7 , a 8 , and a 9 within a five-membered ring is N, O, or S and at least one of a 5 , a 6 , a 7 , a 8 , a 9 , and a 10 within a six-membered ring is N, O, or S; and
each B is, independently, an anionic moiety.
18. The composition of claim 5 , wherein:
R S is —SO 2 —R S1 or —SO 2 —NR N1 —R S2 or —SO 2 —NR N1 —SO 2 —R S3 , wherein each R S1 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl; each R N1 is, independently, H, optionally substituted C 1-12 alkyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl; each R S2 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 alkylsulfonyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl; and
each R S3 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, optionally substituted C 4-18 aryl, or optionally substituted C 1-6 alk-C 4-18 aryl;
R P is —P(O)(OH) 2 or —O—PO(OH) 2 or —P(O)<R P1 R P2 or —P(O)<R Ar R P2 or —P(O)<R A R Ar , wherein each of R 1 and R P2 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 alkoxy, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy; and each R Ar is, independently, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy;
R C is —CO 2 H or —C(O)—R C1 or —R CA —C(O)—R C1 , wherein each R C1 is, independently, H, hydroxyl, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 alkoxy, optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, or optionally substituted C 4-18 aryloxy; and each R CA is, independently, oxy, optionally substituted C 1-12 alkylene, or optionally substituted C 1-12 heteroalkylene; and
R F is carboxyaldehyde, optionally substituted C 1-12 alkyl, optionally substituted C 2-13 alkanoyl, or optionally substituted C 5-19 aryloyl.
19. The composition of claim 5 , wherein L comprises a covalent bond, an optionally substituted alkylene, an optionally substituted heteroalkylene, an optionally substituted alkyleneoxy, an optionally substituted heteroalkyleneoxy, an optionally substituted arylene, an optionally substituted aryleneoxy, an Ar* unit, or a structure of formula (II):
or a salt thereof or a form thereof including a counter ion.
20. The composition of claim 5 , wherein Ar L , Ar M , and/or Ar* is optionally substituted phenylene, optionally substituted naphthylene, or optionally substituted phenanthrylene; wherein the optional substitution for Ar′ is R A , R S , R P , R C , or R F ; wherein the optional substitution for Ar M is R A , R S , R P , R C , R F , or a label; and wherein the optional substitution for Ar* is R F .