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Sulfonated poly(arylene ether sulfone) ionomers containing di- and tetrasulfonated arylene sulfone segments

Persson Jutemar, Elin LU ; Takamuku, Shogo LU and Jannasch, Patric LU (2011) In Polymer Chemistry 2(1). p.181-191
Abstract
Poly(arylene ether sulfone) (PSU) ionomers containing disulfonated aryl-SO2-aryl and tetrasulfonated aryl-SO2-aryl-aryl-SO2-aryl segments, respectively, were synthesized and studied to establish their structure–property relationships as proton-exchange membranes. High molecular weight PSUs with different distributions of sulfone bridges in the backbone were prepared by nucleophilic aromatic substitution reactions involving 4,4′-dichlorodiphenyl sulfone (DCDPS), 4,4′-bis[(4-chlorophenyl)sulfonyl]-1,1′-biphenyl (BCPSB), 4,4′-isopropylidenediphenol (bisphenol A), and 4,4′-(1,4-phenylenediisopropylidene)bisphenol (bisphenol P). The polymers were sulfonated via metallation and reaction with sulfur dioxide, followed by oxidation of the resulting... (More)
Poly(arylene ether sulfone) (PSU) ionomers containing disulfonated aryl-SO2-aryl and tetrasulfonated aryl-SO2-aryl-aryl-SO2-aryl segments, respectively, were synthesized and studied to establish their structure–property relationships as proton-exchange membranes. High molecular weight PSUs with different distributions of sulfone bridges in the backbone were prepared by nucleophilic aromatic substitution reactions involving 4,4′-dichlorodiphenyl sulfone (DCDPS), 4,4′-bis[(4-chlorophenyl)sulfonyl]-1,1′-biphenyl (BCPSB), 4,4′-isopropylidenediphenol (bisphenol A), and 4,4′-(1,4-phenylenediisopropylidene)bisphenol (bisphenol P). The polymers were sulfonated via metallation and reaction with sulfur dioxide, followed by oxidation of the resulting sulfinates. This procedure allowed the introduction of two sulfonic acid units on electron-deficient aryl rings in ortho positions to each sulfone bridge of the PSUs. Analysis by small angle X-ray scattering of solvent cast membranes showed that ionic clustering was promoted in ionomers containing sulfonated BCPSB residues and flexible bisphenol P residues. The fully sulfonated PSUs had ion-exchange capacities (IECs) of 3.3–4.1 meq g−1 and were water soluble. However, partly sulfonated polymers with IECs of approx. 1.7 meq g−1 showed high proton conductivity at moderate water uptake and decomposed only above 240 °C during heating 1 °C min−1 under air. This work demonstrated that BCPSB residues can be conveniently and fully tetrasulfonated, which opens possibilities to prepare various aromatic copolymers and membranes with locally very high densities of hydrolytically stable sulfonic acid groups. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
sulfonation, proton conductivity, polymer electrolytes, proton exchange membrane fuel cells, SAXS
in
Polymer Chemistry
volume
2
issue
1
pages
181 - 191
publisher
Royal Society of Chemistry
external identifiers
  • wos:000285066700022
  • scopus:78650104494
ISSN
1759-9954
DOI
10.1039/C0PY00290A
language
English
LU publication?
yes
id
7edd2a6b-ed4c-4181-b4a9-b06a1486724f (old id 1712075)
alternative location
http://pubs.rsc.org/en/Content/ArticleLanding/2011/PY/C0PY00290A
date added to LUP
2010-11-04 17:07:34
date last changed
2017-01-01 03:30:37
@article{7edd2a6b-ed4c-4181-b4a9-b06a1486724f,
  abstract     = {Poly(arylene ether sulfone) (PSU) ionomers containing disulfonated aryl-SO2-aryl and tetrasulfonated aryl-SO2-aryl-aryl-SO2-aryl segments, respectively, were synthesized and studied to establish their structure–property relationships as proton-exchange membranes. High molecular weight PSUs with different distributions of sulfone bridges in the backbone were prepared by nucleophilic aromatic substitution reactions involving 4,4′-dichlorodiphenyl sulfone (DCDPS), 4,4′-bis[(4-chlorophenyl)sulfonyl]-1,1′-biphenyl (BCPSB), 4,4′-isopropylidenediphenol (bisphenol A), and 4,4′-(1,4-phenylenediisopropylidene)bisphenol (bisphenol P). The polymers were sulfonated via metallation and reaction with sulfur dioxide, followed by oxidation of the resulting sulfinates. This procedure allowed the introduction of two sulfonic acid units on electron-deficient aryl rings in ortho positions to each sulfone bridge of the PSUs. Analysis by small angle X-ray scattering of solvent cast membranes showed that ionic clustering was promoted in ionomers containing sulfonated BCPSB residues and flexible bisphenol P residues. The fully sulfonated PSUs had ion-exchange capacities (IECs) of 3.3–4.1 meq g−1 and were water soluble. However, partly sulfonated polymers with IECs of approx. 1.7 meq g−1 showed high proton conductivity at moderate water uptake and decomposed only above 240 °C during heating 1 °C min−1 under air. This work demonstrated that BCPSB residues can be conveniently and fully tetrasulfonated, which opens possibilities to prepare various aromatic copolymers and membranes with locally very high densities of hydrolytically stable sulfonic acid groups.},
  author       = {Persson Jutemar, Elin and Takamuku, Shogo and Jannasch, Patric},
  issn         = {1759-9954},
  keyword      = {sulfonation,proton conductivity,polymer electrolytes,proton exchange membrane fuel cells,SAXS},
  language     = {eng},
  number       = {1},
  pages        = {181--191},
  publisher    = {Royal Society of Chemistry},
  series       = {Polymer Chemistry},
  title        = {Sulfonated poly(arylene ether sulfone) ionomers containing di- and tetrasulfonated arylene sulfone segments},
  url          = {http://dx.doi.org/10.1039/C0PY00290A},
  volume       = {2},
  year         = {2011},
}