Poly(phenylene) and m-terphenyl as protecting groups for benzimidazolium hydroxides

Patent metadata

Field	Value
Publication number	US-2019016851-A1
Application number	US-201716068654-A
Country	US
Kind code	A1
Filing date	Jan 6, 2017
Priority date	Jan 8, 2016
Publication date	Jan 17, 2019
Grant date	—

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.

First claim

1 . A compound of Formula (I):

wherein
R 101 and R 102 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R 103 and R 104 are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, heteroaryl, and halo, wherein said alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, or heteroaryl is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo;
R 105 is selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R 106 , R 107 , R 108 , and R 109 are independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl.

2 . The compound of claim 1 , wherein R 101 and R 102 are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl.

3 - 5 . (canceled)

6 . The compound of claim 1 , wherein R 101 and R 102 are each methyl.

7 - 11 . (canceled)

12 . The compound of claim 1 , wherein R 103 and R 104 are each independently selected from methyl and phenyl, wherein said phenyl is optionally substituted with 1, 2, 3, or 4 halo.

13 . The compound of claim 1 , wherein R 105 is selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, and heteroaryl.

14 . (canceled)

15 . (canceled)

16 . The compound of claim 1 , wherein R 105 is selected from hydrogen and methyl.

17 . (canceled)

18 . The compound of claim 1 , wherein R 106 , R 107 , R 108 , and R 109 are each hydrogen.

19 . The compound of claim 1 , further comprising an anion 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 anion X − counterbalances the positive charge in the compound.

20 . The compound of claim 19 , selected from the group consisting of:

wherein X − is an anion 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.

21 . A polymer comprising a repeating unit derived from a compound of claim 1 .

22 . A polymer comprising repeating units of Formula (II-A) and (II-B)

wherein:
R 101a , R 102a , and R 102b are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R 111a , R 110a , R 111b , and R 110b are each independently selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, heteroarylene, wherein said alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, or heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo;
R 105a and R 105b are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R 106a , R 107a , R 108a , R 109a , R 106b , R 107b , R 108b , and R 109b are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl,
wherein the polymer comprises comprising r mole percentage repeating units of Formula (II-A), and s mole percentage repeating units of Formula (II-B), and
r is from 1 mole percent to 100 mole percent,
s is from 0 mole percent to 99 mole percent, and
r+s=100%.

23 . The polymer of claim 22 , wherein R 101a , R 102a , and R 102b are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl.

24 - 26 . (canceled)

27 . The polymer of claim 22 , wherein R 101a , R 102a , and R 102b are each methyl.

28 - 31 . (canceled)

32 . The polymer of claim 22 , wherein R 111a , R 110a , R 111b , and R 110b are each phenylene, wherein said phenylene is optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo.

33 . The polymer of claim 22 , wherein R 105a and R 105b are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, and heteroaryl.

34 . (canceled)

35 . (canceled)

36 . The polymer of claim 22 , wherein R 105a and R 105b are each independently selected from hydrogen and methyl.

37 . (canceled)

38 . The polymer of claim 22 , wherein R 106a , R 107a , R 108a , and R 109a , R 106b , R 107b , R 108b , and R 109b are each hydrogen.

39 . The polymer of claim 22 , 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.

40 . An ionic membrane comprising a polymer of claim 22 .

41 . A polymer of claim 22 , incorporated into a catalyst layer of a fuel cell, of an electrolyzer, or of other electrochemical devices.

Assignees

• Univ Fraser Simon

Inventors

• Holdcroft Steven
• Wright Andrew

Classifications

• C08J2365/02

  Polyphenylenes · CPC title

• C25B13/08

  based on organic materials · CPC title

• C08G2261/62

  Mechanical aspects · CPC title

• C08G61/10 Primary

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title

• C08G2261/614

  for liquids · CPC title