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Highly proton conducting electrolyte membranes based on poly(arylene sulfone)s with tetrasulfonated segments

Weiber, Annika LU ; Takamuku, Shogo LU and Jannasch, Patric LU (2013) In Macromolecules 46(9). p.3476-3485
Abstract
A series of fully aromatic polymers having only sulfone bridges linking the aromatic rings has been synthesized via polycondensations and studied as proton-exchange membranes. Mixtures of tetrasulfonated 4,4’-bis[(4-chlorophenyl)sulfonyl]-1,1’-biphenyl (BCPSBP), non-sulfonated BCPSBP and 4,4’-thiobisbenzenethiol were copolymerized by nucleophilic aromatic substitution reactions to obtain sulfonated poly(arylene thioether sulfone)s (SPATSs) with ion exchange capacities (IECs) between 2.0 and 4.0 meq. g-1. The thioether bridges of the SPATSs were quantitatively oxidized to sulfone bridges to obtain the corresponding sulfonated poly(arylene sulfone)s (SPASs). Small angle X-ray scattering of dry SPATS and SPAS membranes showed that the... (More)
A series of fully aromatic polymers having only sulfone bridges linking the aromatic rings has been synthesized via polycondensations and studied as proton-exchange membranes. Mixtures of tetrasulfonated 4,4’-bis[(4-chlorophenyl)sulfonyl]-1,1’-biphenyl (BCPSBP), non-sulfonated BCPSBP and 4,4’-thiobisbenzenethiol were copolymerized by nucleophilic aromatic substitution reactions to obtain sulfonated poly(arylene thioether sulfone)s (SPATSs) with ion exchange capacities (IECs) between 2.0 and 4.0 meq. g-1. The thioether bridges of the SPATSs were quantitatively oxidized to sulfone bridges to obtain the corresponding sulfonated poly(arylene sulfone)s (SPASs). Small angle X-ray scattering of dry SPATS and SPAS membranes showed that the tetrasulfonated segments promoted a distinct phase separation of the ionic groups already at quite low ionic contents. The SPAS polymers degraded between 300 and 340 ºC in air which was significantly above the degradation temperature of the corresponding SPATSs polymers. Moreover, SPAS membranes showed a significantly lower water uptake than the corresponding SPATS membranes. SPATS and SPAS membranes with IEC values of 2.4 and 2.2 meq. g-1, respectively, maintained high proton conductivity at low relative humidity (RH). At 30% RH and 80 ºC, these membranes reached 8 and 10 mS cm-1, respectively. The latter value coincided with that recorded for the state-of-the-art perfluorinated NRE212 membrane under the same conditions. Thus, the SPAS materials combine a straight-forward synthetic pathway with a very robust polymer structure giving high proton conductivity at reduced RH. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
block copolymers, ionomers, polyelectrolytes, proton-exchange membranes, transport properties
in
Macromolecules
volume
46
issue
9
pages
3476 - 3485
publisher
The American Chemical Society
external identifiers
  • wos:000319185000032
  • scopus:84877785497
ISSN
0024-9297
DOI
10.1021/ma4002929
language
English
LU publication?
yes
id
6a0e8dd5-1a5a-4bd8-9e4a-56e870b84a3c (old id 3561028)
date added to LUP
2013-04-10 17:10:52
date last changed
2019-08-14 01:17:45
@article{6a0e8dd5-1a5a-4bd8-9e4a-56e870b84a3c,
  abstract     = {A series of fully aromatic polymers having only sulfone bridges linking the aromatic rings has been synthesized via polycondensations and studied as proton-exchange membranes. Mixtures of tetrasulfonated 4,4’-bis[(4-chlorophenyl)sulfonyl]-1,1’-biphenyl (BCPSBP), non-sulfonated BCPSBP and 4,4’-thiobisbenzenethiol were copolymerized by nucleophilic aromatic substitution reactions to obtain sulfonated poly(arylene thioether sulfone)s (SPATSs) with ion exchange capacities (IECs) between 2.0 and 4.0 meq. g-1. The thioether bridges of the SPATSs were quantitatively oxidized to sulfone bridges to obtain the corresponding sulfonated poly(arylene sulfone)s (SPASs). Small angle X-ray scattering of dry SPATS and SPAS membranes showed that the tetrasulfonated segments promoted a distinct phase separation of the ionic groups already at quite low ionic contents. The SPAS polymers degraded between 300 and 340 ºC in air which was significantly above the degradation temperature of the corresponding SPATSs polymers. Moreover, SPAS membranes showed a significantly lower water uptake than the corresponding SPATS membranes. SPATS and SPAS membranes with IEC values of 2.4 and 2.2 meq. g-1, respectively, maintained high proton conductivity at low relative humidity (RH). At 30% RH and 80 ºC, these membranes reached 8 and 10 mS cm-1, respectively. The latter value coincided with that recorded for the state-of-the-art perfluorinated NRE212 membrane under the same conditions. Thus, the SPAS materials combine a straight-forward synthetic pathway with a very robust polymer structure giving high proton conductivity at reduced RH.},
  author       = {Weiber, Annika and Takamuku, Shogo and Jannasch, Patric},
  issn         = {0024-9297},
  keyword      = {block copolymers,ionomers,polyelectrolytes,proton-exchange membranes,transport properties},
  language     = {eng},
  number       = {9},
  pages        = {3476--3485},
  publisher    = {The American Chemical Society},
  series       = {Macromolecules},
  title        = {Highly proton conducting electrolyte membranes based on poly(arylene sulfone)s with tetrasulfonated segments},
  url          = {http://dx.doi.org/10.1021/ma4002929},
  volume       = {46},
  year         = {2013},
}