Highly sulfonated poly(phenylene sulfones): optimization of the polymerization conditions

Atanasov, Vladimir; Buerger, Matthias; Wohlfarth, Andreas; Schuster, Michael; Kreuer, Klaus‐Dieter; Maier, Joachim

doi:10.1007/s00289-011-0539-3

Cited by 13 publications

(12 citation statements)

References 14 publications

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“…Disodium-3,3′-disulfonate-4,4′-difluorodiphenylsulfone (sMSO 2 -207) was purchased from Fumatech GmbH (Germany) and ion exchanged to its protonic form using Dow cation exchange resin Marathon C. Monosulfonated poly(phenylene sulfone) (sPSO 2 -220) was synthesized according to refs − . Hypersulfonated poly(phenylene sulfone) (sPSO 2 -142) was synthesized according to ref .…”

Section: Methodsmentioning

confidence: 99%

Proton Dissociation of Sulfonated Polysulfones: Influence of Molecular Structure and Conformation

et al. 2015

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The counterion condensation behavior of proton conducting sulfonated polysulfones has been investigated by combining electrophoretic NMR, pulsed magnetic field gradient NMR, and conductivity measurements on monomeric and polymeric samples with concentrations of ionic groups in the range where dissociation is not complete (IEC = 4.55–7.04 mequiv g–1). In this regime, counterion condensation is shown to critically depend on details of the molecular structure, and all atom molecular dynamics (MD) simulations reveal the formation of well-defined ionic aggregates (e.g., triple ions). The corresponding global minima of the free energy are suggested to be the result of a delicate balance of the energetics involved in conformational changes, formation of ionic aggregates, and solvation. This goes beyond Manning’s counterion condensation theory and has important implications for the development of membranes with high ionic conductivity as needed for many electrochemical applications such as fuel cells and batteries.

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Section: Methodsmentioning

confidence: 99%

Proton Dissociation of Sulfonated Polysulfones: Influence of Molecular Structure and Conformation

et al. 2015

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“…The MW of these ionomers was varied in the range from 28 800 to 68 800 g mol À1 , which matches the lower end of the MW estimated from experiments. [18][19][20]33 Water contents of 5, 7, 9, 11, 13, and 15H 2 O/ SO 3 H were selected to study the evolution of the nanoscale phase separation as a function of hydration. The short side chain (SSC) PFSA ionomer (EW ¼ 828) and Naon (EW ¼ 1244) were also modeled and compared with sPSO 2 ionomers with EWs of 781 and 1014 in order to evaluate how the backbone and side chain chemistry affect the hydrated morphology.…”

Section: Introductionmentioning

confidence: 99%

Mesoscale modeling of hydrated morphologies of sulfonated polysulfone ionomers

Wang

Paddison

2014

Soft Matter

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The hydrated morphologies of sulfonated poly(phenylene) sulfone (sPSO2) ionomers as a function of equivalent weight (EW), molecular weight (MW), and water content were investigated by using mesoscale dissipative particle dynamics (DPD) simulations. The morphological changes were characterized by analyzing the water distribution and plotting the radial distribution functions for the water particles. The results were compared to typical PFSA ionomers (i.e., Nafion and Aquivion) to evaluate the effects of backbone and side chain chemistry. Our results show that water is more likely to be equally distributed within the hydrophilic domains of the sPSO2 ionomers particularly at low water content, which is in contrast to strong phase separation observed in PFSA ionomers at the same level of hydration. As the degree of sulfonation is increased (i.e., decreasing the EW), well-connected water clusters develop in the sPSO2 ionomers even at low water content which are less affected by changes in the MW than observed for PFSA ionomers. The size of the water clusters is estimated to be from 1.2 to 1.5 nm (compared to ∼ 3.5 nm in Nafion) at a water content of 7H2O/SO3H, which is consistent with results determined from previous experiments. This suggests that the high proton conductivity observed in the sPSO2 ionomers is due to the well-connected hydrophilic pathways.

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“…This work describes the optimized step-growth polymerization of sulfonated polysulfone sPPS-360 (IEC = 2.78 mequiv g À1 , EW = 360 g mequiv À1 ), which is a member of a family of materials that may offer a real alternative to PFSAs. [15][16][17][18][19][20][21][22][23] The pure polysulfone backbone of sPPS-360 gives rise to several advantages over commonly reported sulfonated polyarylenes due to its electronwithdrawing groups ( SO 2 ) in the "ortho" position to the sulfonic acid groups. The resulting strong backbone polarity contributes to increased thermal, thermooxidative, and hydrolytic stability which is critical when dealing with high temperature, high water activity, and formation of radicals in a fuel cell.…”

Section: Introductionmentioning

confidence: 99%

Optimized step‐growth polymerization of water‐insoluble, highly sulfonated poly(phenylene sulfone)

Katcharava

Saatkamp

Muenchinger

et al. 2022

Polymers for Advanced Techs

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Due to its potential for fuel cell applications, the synthesis of sulfonated poly(phenylene sulfone) with an ion-exchange capacity (IEC) of 2.78 mequiv g À1 (sPPS-360) is optimized and the effect of increased molecular weight on mechanical properties studied.The synthesis comprises the step-growth polymerization of sulfonated difluorodiphenylsulfone (sDFDPS) with thiobisbenzenethiol (TBBT), followed by an oxidation (via hydrogen peroxide). In the past, this procedure was marked by very low reproducibility and often limited achievable molecular weight. Sodium sulfate-a byproduct in the preparation of sDFDPS-is found to be retained throughout the monomer's established purification procedure via recrystallization from alcohol/water mixtures. The contamination is quantified by atomic absorption spectroscopy (AAS) and combustion analysis. At corrected monomer ratios, the preparation of sPPS-360 is highly reproducible and a subsequent optimization of synthetic parameters yields a significant increase in number average molecular weight (typical M n 15-30 kDa up to 154 kDa). Improved viscoelastic properties of optimized sPPS-360s are evident in tensile tests at 30 %RH, better membrane-forming properties and reduced water uptake (when submerged in water).

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Highly sulfonated poly(phenylene sulfones): optimization of the polymerization conditions

Cited by 13 publications

References 14 publications

Proton Dissociation of Sulfonated Polysulfones: Influence of Molecular Structure and Conformation

Proton Dissociation of Sulfonated Polysulfones: Influence of Molecular Structure and Conformation

Mesoscale modeling of hydrated morphologies of sulfonated polysulfone ionomers

Optimized step‐growth polymerization of water‐insoluble, highly sulfonated poly(phenylene sulfone)

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