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

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Sulfonated poly(arylene ether sulfone) ionomers containing di- and tetrasulfonated arylene sulfone segments. / Persson Jutemar, Elin; Takamuku, Shogo; Jannasch, Patric.

In: Polymer Chemistry, Vol. 2, No. 1, 2011, p. 181-191.

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T1 - Sulfonated poly(arylene ether sulfone) ionomers containing di- and tetrasulfonated arylene sulfone segments

AU - Persson Jutemar, Elin

AU - Takamuku, Shogo

AU - Jannasch, Patric

N1 - published on the web 2nd November 2010 The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Polymer and Materials Chemistry (LTH) (011001041)

PY - 2011

Y1 - 2011

N2 - 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.

AB - 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.

KW - sulfonation

KW - proton conductivity

KW - polymer electrolytes

KW - proton exchange membrane fuel cells

KW - SAXS

U2 - 10.1039/C0PY00290A

DO - 10.1039/C0PY00290A

M3 - Article

VL - 2

SP - 181

EP - 191

JO - Polymer Chemistry

JF - Polymer Chemistry

SN - 1759-9954

IS - 1

ER -