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US-20260125498-A1 - ION-EXCHANGE MEMBRANES AND METHODS OF MAKING SAME

US20260125498A1US 20260125498 A1US20260125498 A1US 20260125498A1US-20260125498-A1

Abstract

Ion-exchange polymers prepared from cross-linkable monomers including at least two polymerizable groups and at least one ionic functional group, copolymers including the cross-linkable monomers and optionally monofunctional monomers including one polymerizable group and at least one ionic functional group, and methods of preparing same.

Inventors

  • Jovan Kamcev
  • David Kitto

Assignees

  • REGENTS OF THE UNIVERSITY OF MICHIGAN

Dates

Publication Date
20260507
Application Date
20231115

Claims (20)

  1. 1 . An ion exchange polymer, comprising the product of polymerizing a plurality of monomers, wherein the plurality of monomers comprises monomers of Compound (I), Compound (II), Compound (III), Compound (IV), Compound (V), Compound (VI), Compound (VII), Compound (VIII), or a combination thereof: wherein each X is independently selected from C(H) and N; each A 1 is independently selected from C, N, and O, wherein when two adjacent A 1 are N, then one R 3 on at least one N is absent; n is 0, 1, 2, 3, 4, or 5; each m is independently 1 or 2; each q is independently 1 or 2; each p is 0 or 1; each R 1 is independently selected from H, OH, C 1 -C 6 alkyl, O—C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl; each R 2 is independently selected from H, OH, C 1 -C 6 alkyl, O—C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl; each R 3 is independently absent, H, OH, C 1 -C 6 alkyl, O—C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, or substituted or unsubstituted phenyl; each R 4 is independently selected from C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl or two geminal R 4 together with the N atom to which they are attached form a 5- to 8-member heterocycloalkyl, each of R 5 , R 5 ′, R 5 , R 5 ′, R 7 , and R 7 ′ are selected from CH═CH 2 , CH 2 CH═CH 2 and H, wherein at least one of R 5 , R 5 , and R 7 is CH═CH 2 or CH 2 CH═CH 2 and at least one of R 5 ′, R 5 ′, and R 7 ′ is CH═CH 2 or CH 2 CH═CH 2 ; each R 8 is independently selected from CH═CH 2 , CH 2 CH═CH 2 , C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl; and each Y is independently an inorganic anion or an organic anion.
  2. 2 . The ion-exchange polymer according to claim 1 , wherein the plurality of monomers further comprises monomers of Compound (IX), Compound (X), Compound (XI), Compound (XII), Compound X (III), Compound (XIV), Compound (XV), Compound (XVI), or a combination thereof, wherein each X is independently selected from C(H) and N; each A 1 is independently selected from C, N, and O, wherein when two adjacent A 1 are N, then one R 3 on at least one N is absent; each n is independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; each m is independently 1 or 2; each q is independently 1 or 2; each p is 0 or 1; each Y is independently an inorganic anion or an organic anion; each R 1 is independently selected from H, OH, C 1 -C 6 alkyl, O—C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl; each R 2 is independently selected from H, OH, C 1 -C 6 alkyl, O—C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl; each R 3 is independently absent, H, OH, C 1 -C 6 alkyl, O—C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, or substituted or unsubstituted phenyl; each R 4 is independently selected from C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl or two geminal R 4 together with the N atom to which they are attached form a 5- to 8-member heterocycloalkyl, each of R 5 , R 5 ′, R 6 , R 6 ′, R 7 , and R 7 ′ are selected from CH═CH 2 , CH 2 CH═CH 2 and H, wherein at least one of R 5 , R 6 , and R 7 is CH═CH 2 or CH 2 CH═CH 2 and at least one of R 5 ′, R 6 ′, and R 7 ′ is CH═CH 2 or CH 2 CH═CH 2 ; each R 8 is independently selected from CH═CH 2 , CH 2 CH═CH 2 , C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, and substituted or unsubstituted phenyl; and each Z is independently selected from H, OH, NH 2 , C(O)OH, C 1 -C 6 alkyl, C 1 -C 6 alkyl-OH, C 1 -C 6 alkyl-C(O)OH, CH═CH 2 , and CH 2 CH═CH 2 .
  3. 3 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (II), Compound (IV), both X are N, or in Compound (IX), compound (X), or Compound (XII), X is N.
  4. 4 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (II), Compound (III), Compound (IV), Compound (V), Compound (VI), Compound (VII), Compound (IX), Compound (X), Compound (XI), Compound (XII), Compound (XIII), Compound (XIV), or Compound (XV), n is 0, 1, 2, or 3.
  5. 5 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (IV), Compound (V), Compound (VI), and Compound (VII), both m are 0 or both m are 1, or wherein in Compound (IX), Compound (XII), Compound (XIII), Compound (XIV), Compound (XV), m is 0 or 1.
  6. 6 . The ion-exchange polymer according to claim 1 , wherein in Compound (II) or Compound (VI), both q are 0, both q are 1, or both q are 2, or wherein in Compound (X) or Compound (XIV) q is 0, 1, or 2.
  7. 7 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (II), Compound (III), Compound (IV), Compound (V), Compound (VI), Compound (VII), Compound (IX), Compound (X), Compound (XI), Compound (XII), Compound (XIII), Compound (XIV), or Compound (XV), at least one A 1 is C, at least one A 1 is O, or at least one A 1 is N.
  8. 8 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (II), Compound (III), Compound (IV), Compound (V), Compound (VI), Compound (VII), Compound (VIII), Compound (V), Compound (VI), or Compound (VII), Compound (IX), Compound (X), Compound (XI), Compound (XII), Compound (XIII), Compound (XIV), or Compound (XV), at least one Y is an inorganic anion.
  9. 9 . (canceled)
  10. 10 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (II), Compound (III), Compound (IV), Compound (V), Compound (VI), Compound (VII), Compound (VIII), Compound (V), Compound (VI), or Compound (VII), Compound (IX), Compound (X), Compound (XI), Compound (XII), Compound (XIII), Compound (XIV), or Compound (XV), at least one Y is an organic anion.
  11. 11 . (canceled)
  12. 12 . The ion-exchange polymer according to claim 1 , wherein in Compound (I) or Compound (II), both R 1 are H, both R 1 are C 1 alkyl, or both R 1 are phenyl, or wherein in Compound (IX) or Compound (X), R 1 is H, C 1 alkyl, or phenyl.
  13. 13 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (II), Compound (IV), Compound (IX), Compound (X), or Compound (XII), at least one R 2 is H, C 1 alkyl, or phenyl.
  14. 14 . The ion-exchange polymer according to claim 1 , wherein in Compound (I), Compound (II), Compounds (III), Compound (IV), Compound (V), Compound (VI), Compound (VII), Compound (V), Compound (VI), or Compound (VII), Compound (IX), Compound (X), Compound (XI), Compound (XII), Compound (XIII), Compound (XIV), or Compound (XV), all R 3 are H or at least one R 3 is OH.
  15. 15 . The ion-exchange polymer according to claim 1 , wherein in Compound (III), Compound (VII), Compound (XI), or Compound (XV), all R 4 are C 1 alkyl.
  16. 16 . The ion-exchange polymer according to claim 1 , wherein in Compound (III) or Compound (XI), two geminal R 4 together with the N atom to which they are attached form a 5- or 6-member heterocycloalkyl.
  17. 17 . The ion-exchange polymer according to claim 1 , wherein in Compound (VIII), R 5 and R 5 ′, R 6 and R 6 ′, or R 7 and R 7 ′ are CH═CH 2 , or R 5 and R 5 ′, R 6 and R 6 ′, or R 7 and R 7 ′ are CH 2 CH═CH 2 , or wherein in Compound (XV), R 5 , R 6 , or R 7 is CH═CH 2 or CH 2 CH═CH 2 .
  18. 18 . The ion-exchange polymer according to claim 1 , wherein in Compound (V), Compound (VII), Compound (VIII), Compound (XIII), Compound (XIV), or Compound (XVI), each R 8 is C 1 alkyl or C 2 alkyl.
  19. 19 . (canceled)
  20. 20 . The ion-exchange polymer according to claim 1 , wherein the monomers comprise one or more of: wherein the monomers further include counteranions such that the monomers have electroneutrality.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. § 119 (e) of U.S. Provisional Application No. 63/383,907, filed Nov. 15, 2023, the entire disclosure of which is incorporated herein by reference in its entirety. STATEMENT OF GOVERNMENT INTEREST This invention was made with government support under grant number DE-SC0022040, awarded by the Department of Energy. The government has certain rights in the invention. FIELD The disclosure relates generally to an ion-exchange polymer and methods of making same, and ion-exchange membranes comprising the ion-exchange polymer of the disclosure. More specifically, the disclosure relates to an ion-exchange polymer prepared from a plurality of polymerizable monomers including monomers including two polymerizable units and at least one ionic functional group. BACKGROUND Ion-exchange membranes (IEMs) are an important class of polymeric materials which primarily see industrial use in water purification and energy storage/generation applications, such as electrodialysis (ED), reverse electrodialysis (RED), redox flow batteries (RFBs), and fuel cells. IEMs have also been implemented in more diverse areas including drug delivery devices, food processing lines, and (bio) chemical reactors. In all of these applications, IEMs are valued for their ability to enhance or impede the transport of species based not only on their size, but also on their ionic state. IEMs feature polymer backbones with ionized or ionizable functional groups, which serve to expedite the transport of ions with opposing charge (counter-ions) while impeding that of those with similar charge (co-ions). Ion-exchange membranes have two main performance metrics, selectivity and throughput. These performance metrics are primarily derived from charge density, water content, and charge concentration (the ratio of charge density to water content). In general, selectivity increases with charge concentration of the membrane and throughput increases with charge density and water content. Thus, there is a trade-off relationship between the selectivity and throughput, based on their opposing dependence on water content. Ion-exchange membranes are often prepared from linear polymers. For linear polymers, increasing the ion-exchange capacity (IEC) of a given backbone increases the water content. Charge density initially increases with ion-exchange capacity but reaches a plateau and ultimately decreases due to a “dilution” effect which is a result of the charges being hydrophilic. The swelling of membranes can be reduced by including cross-links which trap the chains in specific configurations and prevent expansion/swelling of the polymer chains. However, commercially employed cross-linkers are neutral and, because of this, the inclusion of the cross-linkers fails to break the co-dependency of water content and IEC. Recently, charged cross-linkers have been incorporated to improve the properties of traditional ion-exchange membranes. Diamines, for example, have been reacted with some polymers to cross-link the polymer chains and introduce additional charge to the polymer. The usefulness of a single IEM is not universal. The various applications mentioned above have different performance needs. Thus, there is a need in the art for an IEM that can be tuned to have improved performance and efficiency for any given application. SUMMARY One aspect of the disclosure provides an ion-exchange polymer having a structure represented by Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), Formula (VI), Formula (VII), Formula (VIII), or Formula (IX): wherein each X is independently selected from C(H) and N; each A1 is independently selected from C, N, and O, wherein when two adjacent A1 are N, then one R3 on at least one N is absent; each n is independently an integer 0 to 10, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; each m is independently 1 or 2; each q is independently 1 or 2; each p is independently 0 or 1; each Y is independently an inorganic anion or an organic anion; each Z is independently selected from H, OH, NH2, C(O)OH, C1-C6alkyl, C1-C6alkyl-OH, C1-C6alkyl-C(O)OH, CH═CH2, and CH2CH═CH2; each R1 is independently selected from H, OH, C1-C6alkyl, O—C1-C6alkyl, C5-C6cycloalkyl, and substituted or unsubstituted phenyl; each R2 is independently selected from H, OH, C1-C6alkyl, O—C1-C6alkyl, C5-C6cycloalkyl, and substituted or unsubstituted phenyl; each R3 is independently absent, H, OH, C1-C6alkyl, O—C1-C6alkyl, C5-C6cycloalkyl, or substituted or unsubstituted phenyl; each R4 is independently selected from C1-C6alkyl, C5-C6cycloalkyl, and substituted or unsubstituted phenyl or two geminal R4 together with the N atom to which they are attached form a 5- to 8-member heterocycloalkyl; each of R5, R5′, R6, R6′, R7, and R7′ are independently selected from CH═CH2, CH2CH═CH2, and H; each Re is independently selected from CH═CH2, CH2CH═CH2, C1-C6alkyl, C5-C6cycloalkyl, a