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Ion distribution in quaternary ammonium functionalized aromatic polymers: effects on the ionic clustering and conductivity of anion exchange membranes

Weiber, Annika LU and Jannasch, Patric LU (2014) In ChemSusChem 7(9). p.2621-2630
Abstract
A series of copoly(arylene ether sulfone)s having precisely two, three or four quaternary ammonium (QA) groups clustered directly on single phenylene rings along the backbone are studied as anion exchange membranes. The copolymers are synthesized via condensation polymerizations involving either di-, tri- or tetramethylhydroquinone, followed by virtually complete benzylic bromination using N-bromosuccinimide and quaternization with trimethylamine. This synthetic strategy allows an excellent control and systematic variation of the local density and distribution of QA groups along the backbone. Small angle X-ray scattering of these copolymers shows extensive ionic clustering, promoted by an increasing density of QA on the single phenylene... (More)
A series of copoly(arylene ether sulfone)s having precisely two, three or four quaternary ammonium (QA) groups clustered directly on single phenylene rings along the backbone are studied as anion exchange membranes. The copolymers are synthesized via condensation polymerizations involving either di-, tri- or tetramethylhydroquinone, followed by virtually complete benzylic bromination using N-bromosuccinimide and quaternization with trimethylamine. This synthetic strategy allows an excellent control and systematic variation of the local density and distribution of QA groups along the backbone. Small angle X-ray scattering of these copolymers shows extensive ionic clustering, promoted by an increasing density of QA on the single phenylene rings. At an ionexchangecapacity (IEC) of 2.1 meq. g-1, the water uptake decrease with an increasing local density of QA groups. Moreover, at moderate IECs at 20 °C the Br- conductivity of the densely functionalized copolymers is higher than a corresponding randomly functionalized polymer, despite the significantly higher water uptake of the latter. Thus, placing multiple cations on single aromatic rings in the polymers facilitates the formation of a distinct percolating hydrophilic phase domain with high ionic concentration to promote efficient anion transport, despite probable limitations by reduced ion dissociation. These findings imply a viable strategy to improve the performance of alkaline membrane fuel cells. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
polyelectrolytes, cationic polymers, polysulfones, anion-exchange membranes, alkaline membrane fuel cells
in
ChemSusChem
volume
7
issue
9
pages
2621 - 2630
publisher
John Wiley & Sons
external identifiers
  • pmid:25044778
  • wos:000342813300034
  • scopus:84923904072
ISSN
1864-564X
DOI
10.1002/cssc.201402223
language
English
LU publication?
yes
id
c757151f-5015-43c4-98b5-4a2586be2058 (old id 4451312)
alternative location
http://onlinelibrary.wiley.com/doi/10.1002/cssc.201402223/abstract;jsessionid=4394113A0EF4E60E9CEE4AEF00C4E2EF.f01t01
date added to LUP
2014-07-03 12:27:04
date last changed
2016-11-20 03:19:00
@article{c757151f-5015-43c4-98b5-4a2586be2058,
  abstract     = {A series of copoly(arylene ether sulfone)s having precisely two, three or four quaternary ammonium (QA) groups clustered directly on single phenylene rings along the backbone are studied as anion exchange membranes. The copolymers are synthesized via condensation polymerizations involving either di-, tri- or tetramethylhydroquinone, followed by virtually complete benzylic bromination using N-bromosuccinimide and quaternization with trimethylamine. This synthetic strategy allows an excellent control and systematic variation of the local density and distribution of QA groups along the backbone. Small angle X-ray scattering of these copolymers shows extensive ionic clustering, promoted by an increasing density of QA on the single phenylene rings. At an ionexchangecapacity (IEC) of 2.1 meq. g-1, the water uptake decrease with an increasing local density of QA groups. Moreover, at moderate IECs at 20 °C the Br- conductivity of the densely functionalized copolymers is higher than a corresponding randomly functionalized polymer, despite the significantly higher water uptake of the latter. Thus, placing multiple cations on single aromatic rings in the polymers facilitates the formation of a distinct percolating hydrophilic phase domain with high ionic concentration to promote efficient anion transport, despite probable limitations by reduced ion dissociation. These findings imply a viable strategy to improve the performance of alkaline membrane fuel cells.},
  author       = {Weiber, Annika and Jannasch, Patric},
  issn         = {1864-564X},
  keyword      = {polyelectrolytes,cationic polymers,polysulfones,anion-exchange membranes,alkaline membrane fuel cells},
  language     = {eng},
  number       = {9},
  pages        = {2621--2630},
  publisher    = {John Wiley & Sons},
  series       = {ChemSusChem},
  title        = {Ion distribution in quaternary ammonium functionalized aromatic polymers: effects on the ionic clustering and conductivity of anion exchange membranes},
  url          = {http://dx.doi.org/10.1002/cssc.201402223},
  volume       = {7},
  year         = {2014},
}