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Multiblock copolymers containing highly sulfonated poly(arylene sulfone) blocks for proton conducting electrolyte membranes

Takamuku, Shogo LU and Jannasch, Patric LU (2012) In Macromolecules 45(16). p.6538-6546
Abstract
We report on multiblock copolymers consisting of highly sulfonated hydrophilic poly(arylene sulfone) (SPAS) blocks combined with hydrophobic poly(arylene ether sulfone) (PAES) blocks. Dithiol-terminated precursor blocks of sulfonated poly(arylene thioether sulfone) (SPATS) were first prepared via polycondensations involving a novel tetrasulfonated dichlorotetraphenyldisulfone monomer, followed by coupling with pentafluorophenyl end capped PAES precursor blocks under mild conditions to form SPATS-PAES block copolymers. The thioether bridges of the SPATS blocks were then selectively oxidized to obtain the SPAS-PAES copolymers with hydrophilic blocks containing exclusively sulfone bridges. Thus, the SPAS blocks were designed for high chain... (More)
We report on multiblock copolymers consisting of highly sulfonated hydrophilic poly(arylene sulfone) (SPAS) blocks combined with hydrophobic poly(arylene ether sulfone) (PAES) blocks. Dithiol-terminated precursor blocks of sulfonated poly(arylene thioether sulfone) (SPATS) were first prepared via polycondensations involving a novel tetrasulfonated dichlorotetraphenyldisulfone monomer, followed by coupling with pentafluorophenyl end capped PAES precursor blocks under mild conditions to form SPATS-PAES block copolymers. The thioether bridges of the SPATS blocks were then selectively oxidized to obtain the SPAS-PAES copolymers with hydrophilic blocks containing exclusively sulfone bridges. Thus, the SPAS blocks were designed for high chain stiffness, stability towards desulfonation and had an ion exchange capacity (IEC) of 4.2 mequiv. g-1. Membranes of the SPAS-PAES copolymers were phase separated on the nano scale and showed an increased thermal stability and decreased water uptake in relation to the corresponding SPATS-PAES membranes. meta-Connectivity in the sulfonated blocks gave slightly higher water uptake than pure para-connectivity. At 80 ˚C and 30% relative humidity, the proton conductivity of a SPAS-PAES membrane with an IEC of 1.8 mequiv. g-1 reached 5.1 mS cm-1, which was comparable to that of Nafion® and far exceeded that of a sulfonated statistical copolymer membrane with a similar IEC. This class of block copolymers possesses very attractive properties and has great prospective to meet the demands of various electrochemical applications. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
fuel cells, polymer electrolyte membranes, aromatic block copolymers, ionomer, poly(phenyl sulfone)s
in
Macromolecules
volume
45
issue
16
pages
6538 - 6546
publisher
The American Chemical Society
external identifiers
  • wos:000307988500024
  • scopus:84865611233
ISSN
0024-9297
DOI
10.1021/ma301245u
language
English
LU publication?
yes
id
d8114fe0-21d9-4477-b2ec-a32e5c4a1f20 (old id 2968082)
alternative location
http://pubs.acs.org/doi/abs/10.1021/ma301245u?prevSearch=jannasch&searchHistoryKey=
date added to LUP
2012-09-11 16:07:44
date last changed
2017-11-19 03:02:15
@article{d8114fe0-21d9-4477-b2ec-a32e5c4a1f20,
  abstract     = {We report on multiblock copolymers consisting of highly sulfonated hydrophilic poly(arylene sulfone) (SPAS) blocks combined with hydrophobic poly(arylene ether sulfone) (PAES) blocks. Dithiol-terminated precursor blocks of sulfonated poly(arylene thioether sulfone) (SPATS) were first prepared via polycondensations involving a novel tetrasulfonated dichlorotetraphenyldisulfone monomer, followed by coupling with pentafluorophenyl end capped PAES precursor blocks under mild conditions to form SPATS-PAES block copolymers. The thioether bridges of the SPATS blocks were then selectively oxidized to obtain the SPAS-PAES copolymers with hydrophilic blocks containing exclusively sulfone bridges. Thus, the SPAS blocks were designed for high chain stiffness, stability towards desulfonation and had an ion exchange capacity (IEC) of 4.2 mequiv. g-1. Membranes of the SPAS-PAES copolymers were phase separated on the nano scale and showed an increased thermal stability and decreased water uptake in relation to the corresponding SPATS-PAES membranes. meta-Connectivity in the sulfonated blocks gave slightly higher water uptake than pure para-connectivity. At 80 ˚C and 30% relative humidity, the proton conductivity of a SPAS-PAES membrane with an IEC of 1.8 mequiv. g-1 reached 5.1 mS cm-1, which was comparable to that of Nafion® and far exceeded that of a sulfonated statistical copolymer membrane with a similar IEC. This class of block copolymers possesses very attractive properties and has great prospective to meet the demands of various electrochemical applications.},
  author       = {Takamuku, Shogo and Jannasch, Patric},
  issn         = {0024-9297},
  keyword      = {fuel cells,polymer electrolyte membranes,aromatic block copolymers,ionomer,poly(phenyl sulfone)s},
  language     = {eng},
  number       = {16},
  pages        = {6538--6546},
  publisher    = {The American Chemical Society},
  series       = {Macromolecules},
  title        = {Multiblock copolymers containing highly sulfonated poly(arylene sulfone) blocks for proton conducting electrolyte membranes},
  url          = {http://dx.doi.org/10.1021/ma301245u},
  volume       = {45},
  year         = {2012},
}