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CA-3009698-C - POLY(PHENYLENE) AND M-TERPHENYL AS PROTECTING GROUPS FOR BENZIMIDAZOLIUM HYDROXIDES

CA3009698CCA 3009698 CCA3009698 CCA 3009698CCA-3009698-C

Abstract

The present disclosure provides alkaline-stable m-terphenyl benzimidazolium hydroxide compounds, in which the C2-position is attached to a phenyl group having various substituents at the ortho positions. Polymers incorporating m-terphenylene repeating groups derived from these alkaline-stable benzimidazolium hydroxide compounds are also presented, along with their inclusion in ionic membranes and in electrochemical devices.

Inventors

  • Steven Holdcroft
  • Andrew Wright

Assignees

  • SIMON FRASER UNIVERSITY

Dates

Publication Date
20260505
Application Date
20170106
Priority Date
20160108

Claims (10)

  1. CLAIMS The embodiments of the disclosure in which an exclusive property or privilege is claimed are defined as follows: 1. A polymer having r mole percentage of repeating units of Formula (II-A): (II-A) incorporated into the backbone of the polymer, wherein the polymer optionally has s mole percentage of repeating units of Formula 10 (II-B): (II-B) incorporated into the backbone of the polymer, 15 wherein: R111a R110a N N R101a R102a R105a R106a R107a R108a R109a R111b R110b N N R102b R105b R106b R107b R108b R109b r is from 1 mole percent to 100 mole percent, s is from 0 mole percent to 99 mole percent, and r+s=100%, and wherein: R101a, R102a, and R102b 5 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R111a andR110a and R111b and R110b are each methylene or phenylene, and wherein R111a and R110a are the same, and R111b and R110b are the same; R105a and R105b are each independently selected from hydrogen, alkyl, 10 perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; and R106a, R107a, R108a, R109a, R106b, R107b, R108b, and R109b are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl.
  2. 2. The polymer of Claim 1, wherein R101a, R102a, and R102b are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl.
  3. 3. The polymer of Claim 1, wherein R101a, R102a, and R102b 15 are each methyl.
  4. 4. The polymer of any one of Claims 1 to 3, wherein R111a, R110a, R111b, and R110b are each phenylene.
  5. 5. The polymer of any one of Claims 1 to 4, wherein R105a and R105b are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, and 20 heteroaryl.
  6. 6. The polymer of any one of Claims 1 to 5, wherein R105a and R105b are each independently selected from hydrogen and methyl.
  7. 7. The polymer of any one of Claims 1 to 6, wherein R106a, R107a, R108a, and R109a, R106b, R107b, R108b, and R109b are independently selected from hydrogen and alkyl. 25
  8. 8. The polymer of any one of Claims 1 to 7, further comprising one or more anions X-selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, cyanide, acetate, nitrate, sulfate, phosphate, triflate, tosylate, tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, wherein the one or more anions X- counterbalance the positive charges in the polymer. 5
  9. 9. An ionic membrane comprising a polymer of any one of Claims 1 to 8.
  10. 10. A polymer of any one of Claims 1 to 8, incorporated into a catalyst layer of a fuel cell, of an electrolyzer, or of other electrochemical devices.

Description

POL Y(PHENYLENE) AND M-TERPHENYL AS PROTECTING GROUPS FOR BENZIMIDAZOLIUM HYDROXIDES CROSS-REFERENCE TO RELATED APPLICATION 5 This application claims the benefit of U.S. Provisional Application No. 62/276,724, filed January 8, 2016. BACKGROUND Immobilized quaternary ammoniums are a class of cationic head groups that support the conduction of anions. They have been used in a range of technologies, such 10 as anion-exchange resins, hydrogen fuel cells, water electrolyzers, redox-:flow batteries, and reverse dialysis. However, of the numerous reported cationic groups, few show promise of long term stability under strong alkaline conditions at elevated temperatures (e.g., 80 °C). A sub-class of cationic head group that are attracting increasing attention are sterically-protected imidazoliums and benzimidazoliums. 15 There is a need for alkaline-stable cationic head groups that can be used in anionexchange resins, hydrogen fuel cells, and the like. The present disclosure seeks to fulfill these needs and provides further related advantages. SUMMARY This summary is provided to introduce a selection of concepts in a simplified 20 form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. In one aspect, the present disclosure features a compound of Formula (I): R R107*-R100 ~,1010 R1os R1os ~ 109 k Rrn3 102 25 (I) wherein Date Rer;ue/Date Received 2023-04-18 R101 and R102 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R103 and R104 are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, heteroaryl, and halo, wherein said alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, or heteroaryl is 5 each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo; R105 is selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R106, R107, R108, and R109 are independently selected from hydrogen, alkyl, 10 perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl. In another aspect, the present disclosure features a polymer including a repeating unit derived from a compound of Formula (I). In yet another aspect, the present disclosure features a polymer having r mole percentage of repeating units of Formula (II-A): R111a R110a R N N 101a R102a R105a R106a R107a R108a R109a (II-A) incorporated into the backbone of the polymer, wherein the polymer optionally has s mole percentage of repeating units of Formula (IIB): R111b R110b N N R102b R105b R106b R107b R108b R109b (II-B) incorporated into the backbone of the polymer, wherein: 5 r is from 1 mole percent to 100 mole percent, s is from 0 mole percent to 99 mole percent, and r+s=100%, and wherein: R101a, R102a, and R102b are each independently selected from alkyl, 10 perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; R111a, R110a, R111b, and R110b are each methylene or phenylene, and wherein R111a and R110a are the same, and R111b and R110b are the same; R105a and R105b are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl; and 15 R106a, R107a, R108a, R109a, R106b, R107b, R108b, and R109b are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl In yet a further aspect, the present disclosure features an ionic membrane including a polymer including repeating units of Formula (II-A) and/or (II-B). ~ ~* x In yet a further aspect, the present disclosure features a polymer including repeating units of Formula (II-A) and/or (II-B), incorporated into a catalyst layer of a fuel cell, of an electrolyzer, or of other electrochemical devices. DESCRIPTION OF THE DRAWINGS The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein: FIGURES lA-lD show X-ray crystal structures of embodiments of model 10 compounds in their iodide form with thermal ellipsoids at a 50% probability level alongside the dihedral angles measured (A represents the 2-phenyl plane and B represents the benzimidazolium plane). Only one of the two unique BrB structures is shown for clarity and PhB co-crystallized with H2O (where the hydrogens of H2O are not shown). 15 FIGURE 2 is a graphical representation of reaction profiles for two hydroxidemediated degradation pathways (de-methylation and ring-opening) for HB, MeB, and PhB. The dotted lines represent the higher energy, TS2,trans, ring-opening degradation pathway. No barrier was found between IS1 and IS2 FIGURE 3 is a Huggins-Kraemer plot of PPB in NMP calculated from the 20 measured visco