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Poly(arylene piperidinium) hydroxide ion exchange membranes: synthesis, alkaline stability and conductivity

Olsson, Joel LU ; Pham, Thanh Huong LU and Jannasch, Patric LU (2018) In Advanced Functional Materials 28(2).
Abstract
A series of poly(arylene piperidinium)s (PAPipQs) devoid of any alkali-sensitive aryl ether bonds or benzylic sites are prepared and studied as anion exchange membranes (AEMs) for alkaline fuel cells. First, the excellent alkaline stability of the model compound 4,4-diarylpiperidinium is confirmed. Medium molecular weight poly(arylene piperidine)s are then synthesized in polycondensations of N-methyl-4-piperidone and either bi- or terphenyl via superelectrophilic... (More)
A series of poly(arylene piperidinium)s (PAPipQs) devoid of any alkali-sensitive aryl ether bonds or benzylic sites are prepared and studied as anion exchange membranes (AEMs) for alkaline fuel cells. First, the excellent alkaline stability of the model compound 4,4-diarylpiperidinium is confirmed. Medium molecular weight poly(arylene piperidine)s are then synthesized in polycondensations of N-methyl-4-piperidone and either bi- or terphenyl via superelectrophilic activation in triflic acid. Film-forming PAPipQs are subsequently prepared in Menshutkin reactions with methyl, butyl, hexyl, and octyl halides, respectively. AEMs based on poly(terphenyl dimethylpiperidinium) show the best performance with no structural degradation detectable by 1H NMR spectroscopy after storage in 2 maq. NaOH at 60 °C after 15 d, and a mere 5% ionic loss at 90 °C. In the fully hydrated state these AEMs reach an OH conductivity of 89 mS cm−1 at 80 °C. The presence of longer pendant N-alkyl chains (butyl to octyl) is found to significantly promote Hofmann ring-opening elimination reactions and the degradation rate increases with increasing alkyl chain length. The results of the present study demonstrate that PAPipQs are efficiently prepared from readily available monomers and show excellent alkaline stability and OH conductivity when devoid of pendant N-alkyl chains. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Advanced Functional Materials
volume
28
issue
2
pages
10 pages
publisher
Wiley-VCH
external identifiers
  • scopus:85035022747
ISSN
1616-3028
DOI
10.1002/adfm.201702758
language
English
LU publication?
yes
id
77801c38-564a-4e47-a459-266e76c398e3
date added to LUP
2017-09-25 14:14:53
date last changed
2018-05-20 04:37:27
@article{77801c38-564a-4e47-a459-266e76c398e3,
  abstract     = {A series of poly(arylene piperidinium)s (PAPipQs) devoid of any alkali-sensitive aryl ether bonds or benzylic sites are prepared and studied as anion exchange membranes (AEMs) for alkaline fuel cells. First, the excellent alkaline stability of the model compound 4,4-diarylpiperidinium is confirmed. Medium molecular weight poly(arylene piperidine)s are then synthesized in polycondensations of <em style="margin: 0px; padding: 0px; border: 0px; outline: 0px; font-size: 16px; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); color: rgb(51, 51, 51); font-family: &quot;Open Sans&quot;, Arial, Helvetica, &quot;Lucida Sans Unicode&quot;, sans-serif;">N</em>-methyl-4-piperidone and either bi- or terphenyl via superelectrophilic activation in triflic acid. Film-forming PAPipQs are subsequently prepared in Menshutkin reactions with methyl, butyl, hexyl, and octyl halides, respectively. AEMs based on poly(terphenyl dimethylpiperidinium) show the best performance with no structural degradation detectable by 1H NMR spectroscopy after storage in 2 maq. NaOH at 60 °C after 15 d, and a mere 5% ionic loss at 90 °C. In the fully hydrated state these AEMs reach an OH<sup>−</sup> conductivity of 89 mS cm<sup>−1</sup> at 80 °C. The presence of longer pendant <i>N</i>-alkyl chains (butyl to octyl) is found to significantly promote Hofmann ring-opening elimination reactions and the degradation rate increases with increasing alkyl chain length. The results of the present study demonstrate that PAPipQs are efficiently prepared from readily available monomers and show excellent alkaline stability and OH<sup>−</sup> conductivity when devoid of pendant <em style="margin: 0px; padding: 0px; border: 0px; outline: 0px; font-size: 16px; vertical-align: baseline; background: 0px 0px rgb(249, 249, 249); color: rgb(51, 51, 51); font-family: &quot;Open Sans&quot;, Arial, Helvetica, &quot;Lucida Sans Unicode&quot;, sans-serif;">N</em>-alkyl chains.},
  articleno    = {1702758},
  author       = {Olsson, Joel and Pham, Thanh Huong and Jannasch, Patric},
  issn         = {1616-3028},
  language     = {eng},
  number       = {2},
  pages        = {10},
  publisher    = {Wiley-VCH },
  series       = {Advanced Functional Materials},
  title        = {Poly(arylene piperidinium) hydroxide ion exchange membranes: synthesis, alkaline stability and conductivity},
  url          = {http://dx.doi.org/10.1002/adfm.201702758},
  volume       = {28},
  year         = {2018},
}