Synthesis and characterization of partially disulfonated hydroquinone‐based poly(arylene ether sulfone)s random copolymers for application as proton exchange membranes

Partially disulfonated hydroquinone (HQ)‐based poly(arylene ether sulfone) random copolymers were synthesized and characterized for application as proton exchange membranes. The copolymer composition was varied in the degree of disulfonation. The copolymers were characterized by ¹H NMR, Differential Scanning Calorimetry (DSC), and other analytical techniques. The copolymer with a 25% degree of disulfonation showed the best balance between water uptake and proton conductivity. The copolymers showed substantially reduced methanol permeability compared with Nafion® and satisfactory direct methanol fuel cell performance. The methanol selectivity improved significantly in comparison to Nafion® 117. At a given ionic composition, the HQ‐based system showed higher water uptake and proton conductivity than the biphenol‐based (BPSH‐xx) poly(arylene ether sulfone)s copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 384–391, 2009     

Sorption and diffusion of methanol and water in PVDF‐g‐PSSA and Nafion® 117 polymer electrolyte membranes

Sorption and diffusion properties of poly(vinylidene fluoride)‐graft‐poly(styrene sulfonic acid) (PVDF‐g‐PSSA) and Nafion® 117 polymer electrolyte membranes were studied in water/methanol mixtures. The two types of membranes were found to have different sorption properties. The Nafion 117 membrane was found to have a maximum in‐solvent uptake around 0.4 to 0.6 mole fraction of methanol, while the PVDF‐g‐PSSA membranes took up less solvent with increasing methanol concentration. The proton NMR spectra were recorded for membranes immersed in deuterated water/methanol mixtures. The spectra showed that the hydroxyl protons inside the membrane exhibit resonance lines different from the resonance lines of hydroxyl protons in the external solvent. The spectral features of the lines of these internal hydroxyl groups in the membranes were different in the Nafion membrane compared with the PVDF‐g‐PSSA membranes. Diffusion measurements with the pulsed field gradient NMR (PFG‐NMR) method showed that the diffusion coefficient of the internal hydroxyl groups in the solvent immersed Nafion membrane mirrors the changes in the diffusion coefficients of hydroxyl and methyl protons in the external solvent. For the PVDF‐g‐PSSA membranes, a decrease in the diffusion coefficient of the internal hydroxyl protons was seen with increasing methanol concentration. These results indicate that the morphology and chemical structure of the membranes have an effect on their solvent sorption and diffusion characteristics. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3277–3284, 2000     

Studies on sulfonic acid functionalized hollow silica spheres/Nafion® composite proton exchange membranes

In this work, sulfonic acid functionalized hollow silica spheres (SAFHSS)/Nafion® composite membranes were prepared by a recasting procedure. The influences of temperature on water uptake, swelling degree, and proton conductivity of the composite membranes were studied. In comparison with the pure recast Nafion® membrane, it was found that water uptake of composite membranes increased with increasing SAFHSS loading at all temperature studied. The swelling degree of SAFHSS/Nafion® composite membranes with 10～15 wt % SAFHSS loading was lower than that of the pure recast Nafion® at all temperatures in the study. The proton conductivity of SAFHSS/Nafion® composite membranes was constantly higher than that of the pure recast Nafion® at all temperatures (50～130 °C). In a range from 50 to 130 °C, the highest conductivity of composite membranes was obtained when 10 wt % SAFHSS was loaded. The maximum conductivity reached 0.1 S cm^?1 at 100% relative humidity and 100 °C, even the temperature reached to 130 °C, the conductivity of the composite membranes with 10 wt % SAFHSS was still as high as 4.4 × 10^?2 S cm^?1 at 100% relative humidity, whereas the conductivity of the pure recast Nafion® was only 2.2 × 10^?3 S cm^?1. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2647–2655, 2009     

Pore‐filling electrolyte membranes based on microporous polyethylene matrices activated with plasma and sulfonated hydrogenated styrene butadiene block copolymer. Synthesis,microstructural and electrical characterization

In this research a series of pore‐filling electrolyte membranes were prepared, based on a sulfonated and hydrogenated styrene/butadiene block copolymer (SHSBS) and plasma‐treated microporous polyethylene (PE) membranes. The pore‐filling electrolyte membranes were characterized by means of scanning electronic microscopy (SEM), infrared spectroscopy (FTIR‐ATR), and dynamic mechanical analysis (DMA). In addition, the water uptake and methanol/water uptake capacities of these membranes were determined using several methanol in water solutions, as well as the permeability coefficients, for both water and methanol, using a 2 M methanol in water solution and pure methanol. Finally, electrical behavior was recorded by means of electrochemical impedance spectroscopy (EIS) and the four probe technique (FPT). The SEM images recorded show good coating of the pore‐filling electrolyte membranes on the plasma‐treated PE matrices, and DMA shows the proper relaxations of the two components: PE and SHSBS. Furthermore, the methanol/water absorption capacity was observed to diminish with plasma treatment of the matrix. Methanol permeability of the pore‐filling electrolyte membranes is notably lower than that of the Nafion® membrane, ion conductivity moving in the order of 10⁻² S cm⁻¹. Both of these characteristics qualify the experimental membranes as candidates to be applied as proton exchangers in fuel cells (FCs). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1684–1695, 2008     

Structure–property correlations of sulfonated polyimides. I. Effect of bridging groups on membrane properties

A series of six‐membered sulfonated polyimides were synthesized using 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid as the sulfonated diamine, and various nonsulfonated diamine monomers having different bridging groups. These bulky bridging groups have the capacity to increase hydrolytic stability and proton conductivity. Polyimides with bulky bridging groups showed increased solubility but exhibited lower thermal stability. The ion exchange capacity and water uptake reduced with increase in the bulkiness of the bridging group. This was attributed to the increase in the molecular weight of the repeating unit and hence effectively reduced the sulfonic acid content. In low temperatures, the conductivity was lower than Nafion®115 and, with increase in temperature, the conductivity rapidly increased and exhibited better conductivity than Nafion®115. Polyimides with bulky bridging groups 4‐amino phenyl sulfone, and 2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane showed higher conductivity than other polyimides and Nafion®115 despite low ion exchange capacity. The hydrolytic stability of the polyimides with bulky bridging groups was higher than the polyimides with less bulky atoms because of the imparted flexibility. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3612–3620, 2004     

Comparative effect of phthalazinone units in sulfonated poly(arylene ether ether ketone ketone) copolymers as proton exchange membrane materials

A new series of aromatic poly(arylene ether ether ketone ketone) copolymers containing pendant sulfonic acid groups (SPAEEKK‐D) were synthesized from commercially available monomers 1,3‐bis(4‐fluorobenzoyl)‐benzene, sodium 6,7‐dihydroxy‐2‐naphthalenesulfonate, and 4‐(4‐hydroxyphenyl)‐2,3‐phthalazin‐1‐one (DHPZ). Structure–property relationships of the phthalazinone SPAEEKK‐D series poly(arylene ether ether ketone ketone) copolymer were compared with copolymers SPAEEKK‐B and SPAEEKK‐H containing different diols such as 4,4′‐biphenol and hydroquinone, respectively, prepared in our earlier work. Ion exchange capacity (IEC_w, weight‐based; IEC_v, volume‐based), thermal stabilities, swelling, proton and methanol transport properties of the membranes were investigated in relation to their structures and compared with those of perfluorinated ionomer (Nafion 117). The SPAEEKK‐D membrane incorporating the phthalazinone monomer DHPZ showed relatively lower water uptake and methanol permeability compared with earlier SPAEEKK‐B and SPAEEKK‐H membranes incorporating biphenol and hydroquinone monomers, respectively. Inclusion of phthalazinone in the SPAEEKK‐D copolymers led to lower water absorption, enabling increased proton exchange concentrations in the hydrated polymer matrix that resulted in more desirable membrane properties for future direct methanol fuel cell applications. The SPAEEKK‐D membranes also showed improved mechanical and thermal properties and oxidative stability compared with the earlier SPAEEKK‐B and ‐H membranes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 989–1002, 2008     

Influence of temperature and humidity on the mechanical properties of Nafion® 117 polymer electrolyte membrane

The dynamic mechanical properties of Nafion® 117 have been measured in‐plane parallel and perpendicular to the lamination direction in a specially designed humidity cell, which allows measurement of the stiffness and mechanic loss under fuel cell relevant temperature and humidity conditions (50–100% relative humidity, 30–120 °C). The results obtained at different temperature–humidity conditions are compared with the mechanical behavior of the dry as well as the membrane saturated with liquid water. Different regimes of change in mechanical properties were found, although in general water acts as a plasticizer in Nafion®. At elevated temperatures it stiffens the membrane by stabilizing the network of hydrophilic clusters. An intermediate increase of mechanical strength at very low humidity levels is attributed to an enforcement by formation of hydrates and hydrogen bridge bonds between vicinal sulfonic acid groups. This increase is significant for the protonated state of the membrane and disappears after ion exchange. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 786–795, 2005     

Synthesis of proton‐conducting block copolymer membranes composed of a fluorinated segment and a sulfonic acid segment

Diblock copolymer membranes having a fluorinated segment and a sulfonic acid segment were prepared by living radical polymerization, solution casting, and crosslinking, followed by heat treatment. Diblock copolymers of 2,3,4,5,6‐pentafluorostyrene (PFS)/4‐(1‐methylsilacyclobutyl)styrene (SBS) and neopentyl styrenesulfonate (SSPen) (poly(PFS‐co‐SBS)‐b‐polySSPen)s were synthesized by nitoroxy‐mediated living radical polymerization. Self‐standing crosslinked membranes were obtained by casting a THF solution of the block copolymer with Pt catalyst. Heat treatment of the membrane at 230 °C induced decomposition of the neopentyl sulfonate esters to provide block copolymer membranes having a fluorinated segment and a free sulfonic acid segment. It was confirmed that the block copolymer with a high sulfonic acid content exhibited high ion exchange capacity and high proton conductivity as well as high thermal stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4479–4485, 2008     

Dependence of methanol permeability on the nature of water and the morphology of graft copolymer proton exchange membranes

Novel polymers with controlled microstructures were prepared and studied to further advance the understanding of structure–property relationships of proton conducting membranes. PAN‐g‐macPSSA membranes, which contained poly(styrenesulfonic acid) (PSSA) grafts of defined graft length, are compared with PVDF‐g‐PSSA membranes, prepared by radiation‐grafting, and Nafion® 117. The intrinsic properties of PAN‐g‐macPSSA membranes are insensitive to the macromonomer graft length but are highly dependent on the ion exchange capacities (IEC). Increasing the IEC increases the content of free water absorbed by the membrane. Self‐diffusion coefficients of water in water‐swollen PAN‐g‐macPSSA were found to be similar to that of N117, despite PAN‐g‐macPSSA's higher water content. Of the polymers studied, PAN‐g‐macPSSA exhibited the lowest methanol permeability, which is explained on the basis of it containing a more tortuous ionic network. Methanol permeability decreased with decreasing volume of free water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2240–2252, 2006     

Effect of acidification treatment and morphological stability of sulfonated poly(arylene ether sulfone) copolymer proton‐exchange membranes for fuel‐cell use above 100 °C

Directly copolymerized wholly aromatic sulfonated poly(arylene ether sulfone) copolymers derived from 4,4′‐biphenol, 4,4′‐dichlorodiphenyl sulfone, 3,3′‐disulfonated, and 4,4′‐dichlorodiphenyl sulfone (BPSH) were evaluated as proton‐exchange membranes for elevated temperature operation (100–140 °C). Acidification of the copolymer from the sulfonated form after the nucleophilic step (condensation) copolymerization involved either immersing the solvent‐cast membrane in sulfuric acid at 30 °C for 24 h and washing with water at 30 °C for 24 h (method 1) or immersion in sulfuric acid at 100 °C for 2 h followed by similar water treatment at 100 °C for 2 h (method 2). The fully hydrated BPSH membranes treated by method 2 exhibited higher proton conductivity, greater water absorption, and less temperature dependence on proton conductivity as compared with the membranes acidified at 30 °C. In contrast, the conductivity and water absorption of a control perfluorosulfonic acid copolymer (Nafion 1135) were invariant with treatment temperature; however, the conductivity of the Nafion membranes at elevated temperature was strongly dependent on heating rate or temperature. Tapping‐mode atomic force microscope results demonstrated that all of the membranes exposed to high‐temperature conditions underwent an irreversible change of the ionic domain microstructure, the extent of which depended on the concentration of sulfonic acid sites in the BPSH system. The effect of aging membranes based on BPSH and Nafion at elevated temperature on proton conductivity is also discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2816–2828, 2003     

Nafion®/(organically modified silicate) nanocomposites via polymer in situ sol–gel reactions: Mechanical tensile properties

A series of Nafion®/[organically modified silicate (ORMOSIL)] hybrid materials have been created by in situ sol–gel copolymerizations of tetraethylorthosilicate and semiorganic silicon alkoxide monomers. The trends in the mechanical tensile properties of these hybrid materials were largely rationalized in terms of the entrapment of the long sulfonic acid side chains in silicate or ORMOSIL structures. There is a significant increase in the mechanical strength relative to that of unfilled Nafion®, except in one case. Young's modulus is enhanced relative to that of unfilled acid form Nafion® in a number of cases, although the degree of ductility is reduced relative to that of unfilled Nafion®. The filler fractions are beneath a critical value that would reflect percolation of a glassy, direct load‐bearing silicate phase. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2237–2247, 2002     

Sulfonated polybenzimidazoles: Proton conduction and acid–base crosslinking

A series of soluble, benzimidazole‐based polymers containing sulfonic acid groups (SuPBI) has been synthesized. SuPBI membranes resist extensive swelling in water but are poor proton conductors. When blended with high ion exchange capacity (IEC) sulfonated poly(ether ether ketone) (SPEEK), a polymer that has high proton conductivity but poor mechanical integrity, ionic crosslinks form reducing the extent of swelling. The effect of sulfonation of PBI on crosslinking in these blends was gauged through comparison with nonsulfonated analogs. Sulfonic acid groups present in SuPBI compensate for acid groups involved in crosslinking, thereby increasing IEC and proton conductivity of the membrane. When water uptake and proton conductivity were compared to the IEC of blends containing either sulfonated or nonsulfonated PBI, no noticeable distinction between PBI types could be made. Comparisons were also made between these blends and pure SPEEK membranes of similar IEC. Blend membranes exhibit slightly lower maximum proton conductivity than pure SPEEK membranes (60 vs. 75 mS cm^?1) but had significantly enhanced dimensional stability upon immersion in water, especially at elevated temperature (80 °C). Elevated temperature measurements in humid environments show increased proton conductivity of the SuPBI membranes when compared with SPEEK‐only membranes of similar IEC (c.f. 55 for the blend vs. 42 mS cm^?1 for SPEEK at 80 °C, 90% relative humidity). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3640–3650, 2010     

Synthesis and properties of sulfonated poly(arylene ether) containing tetraphenylmethane moieties for proton‐exchange membrane

A novel sulfonated poly(arylene ether) containing tetraphenylmethane moieties was successfully synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place only at the para position on the pendant phenyl rings because of the specially designed parent polymer. The sulfonation degree can be easily controlled by using different ratios of sulfonation agent to polymer repeating unit. The position and degree of sulfonation were characterized by ¹H NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N′‐dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton's reagent test revealed that the membrane exhibited superior stability to oxidation. The proton conductivities of the films were determined to be equivalent with Nafion® 117 under same conditions. The new polymer with sulfonic acid function on pendent phenyl rings can be potentially used as a proton‐exchange membrane for polymer electrolyte membrane fuel cell. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6411–6418, 2005     

Synthesis of sulfonated aromatic poly(ether amide)s and their application to proton exchange membrane fuel cells

A series of wholly aromatic sulfonated poly(ether amide)s (SPEAs) containing a sulfonic acid group on the dicarbonyl aromatic ring were prepared via a polycondensation reaction of sulfonated terephthalic acid (STA), terephthalic acid (TA), and aromatic diamine monomers. The degree of sulfonation was readily controlled by adjusting the monomer feed ratio of STA and TA in the polymerization process, and randomly sulfonated polymers with an ion exchange capacity (IEC) of 1.0–1.8 mequiv/g were prepared using this protocol. The chemical structures of randomly sulfonated polymers were characterized using NMR and FT‐IR spectroscopies. Gel permeation chromatography analysis of SPEAs indicated the formation of high‐molecular‐weight sulfonated polymer. Tough and flexible SPEA membranes were obtained from solution of N,N‐dimethylacetamide, and thermogravimetric analysis of these membranes showed a high degree of thermal stability. Compared with previously reported sulfonated aromatic polyamides, these new SPEAs showed a significantly lower water uptake of 10–30%. In proton conductivity measurements, ODA‐SPEA‐70 (IEC = 1.80 mequiv/g), which was obtained from polycondensation of 4,4′‐oxydianiline and 70 mol % STA, showed a comparable proton conductivity (105 mS/cm) to that of Nafion 117 at 80 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 485–496, 2009     

Highly proton conducting proton‐exchange membranes based on fluorinated poly(arylene ether ketone)s with octasulfonated segments

A new bisphenol monomer containing a pair of electron‐rich tetra‐arylmethane units was designed and synthesized. Based on this monomer, along with commercial 4,4′‐(hexafluoroisopropylidene)diphenol A and 4,4′‐difluorobenzophenone, a series of novel poly(arylene ether ketone)s containing octasulfonated segments of varying molar percentage (x) (6F‐SPAEK‐x) were successfully synthesized by polycondensation reactions, followed by sulfonation. Tough, flexible, and transparent membranes, exhibiting excellent thermal stabilities and mechanical properties were obtained by casting. 6F‐SPAEK‐x samples exhibited appropriate water uptake and swelling ratios at moderate ion exchange capacities (IECs) and excellent proton conductivities. The highest proton conductivity (215 mS cm⁻¹) is observed for hydrated 6F‐SPAEK‐15 (IEC = 1.68 meq g⁻¹) at 100 °C, which is more than 1.5 times that of Nafion 117. Furthermore, the 6F‐SPAEK‐10 membrane exhibited comparable proton conductivity (102 mS cm⁻¹) to that of Nafion 117 at 80 °C, with a relatively low IEC value (1.26 meq g⁻¹). Even under 30% relative humidity, the 6F‐SPAEK‐20 membrane (2.06 meq g⁻¹) showed adequate conductivity (2.1 mS cm⁻¹) compared with Nafion 117 (3.4 mS cm⁻¹). The excellent comprehensive properties of these membranes are attributed to well‐defined nanophase‐separated structures promoted by strong polarity differences between highly ionized and fluorinated hydrophobic segments. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 25–37     

Copoly(arylene ether nitrile) and copoly(arylene ether sulfone) ionomers with pendant sulfobenzoyl groups for proton conducting fuel cell membranes

Three series of fully aromatic ionomers with naphthalene moieties and pendant sulfobenzoyl side chains were prepared via K₂CO₃ mediated nucleophilic aromatic substitution reactions. The first series consisted of poly(arylene ether)s prepared by polycondensations of 2,6‐difluoro‐2′‐sulfobenzophenone (DFSBP) and 2,6‐dihydroxynaphthalene or 2,7‐dihydroxynaphthalene (2,7‐DHN). In the second series, copoly(arylene ether nitrile)s with different ion‐exchange capacities (IECs) were prepared by polycondensations of DFSBP, 2,6‐difluorobenzonitrile (DFBN), and 2,7‐DHN. In the third series, bis(4‐fluorophenyl)sulfone was used instead of DFBN to prepare copoly(arylene ether sulfone)s. Thus, all the ionomers had sulfonic acid units placed in stable positions close to the electron withdrawing ketone link of the side chains. Mechanically strong proton‐exchange membranes with IECs between 1.1 and 2.3 meq g⁻¹ were cast from dimethylsulfoxide solutions. High thermal stability was indicted by high degradation temperatures between 266 and 287 °C (1 °C min⁻¹ under air) and high glass transition temperatures between 245 and 306 °C, depending on the IEC. The copolymer membranes reached proton conductivities of 0.3 S cm⁻¹ under fully humidified conditions. At IECs above ∼1.6 meq g⁻¹, the copolymer membranes reached higher proton conductivities than Nafion^® in the range between −20 and 120 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Viscosity behavior of polyelectrolyte copolymers containing sulfonate groups in mixed organic solvents

Copolymerization of 2-acrylamido-2-methylpropane sulfonic acid (AMPS, monomer 1) with 2-hydropropyl methacrylate (HPM, monomer 2) was conducted in ethylene glycol/water (1 : 1 in weight) at 70°C. The reactivity ratios estimated from the copolymer composition at low conversion are r₁ = 2.31 ± 0.25 and r₂ = 11.70 ± 1.05. The azeotropic composition was found at the monomer mole ratio AMPS/HPM equal to 8/2. Viscosity of these copolymers was measured in dimethyl sulfoxide (DMSO) and DMSO/tetrahydrofuran (THF) mixed solvent at 25 ± 0.05°C. Polyelectrolyte behavior was observed for all the copolymers, even in the mixed solvent containing 65 wt % of THF. The reduced viscosity at constant polymer concentration decreased with increasing THF content in the mixed solvent. The copolymers having AMPS repeat units more than 42 mol % precipitated in the mixed solvent when the THF was beyond 68 wt %. The viscosity reduction and precipitation in the copolymer solutions with increasing THF can be attributed to the dipole–dipole attraction between ion-pairs formed in less-polar medium. This is helpful in understanding the volume phase transition in highly charged hydrogels caused by mixing solvents. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1433–1438, 1997     

Investigation of sulfonated poly(ether ether ketone sulfone)/heteropolyacid composite membranes for high temperature fuel cell applications

The sulfonated poly(ether ether ketone sulfone) (SPEEKS)/heteropolyacid (HPA) composite membranes with different HPA content in SPEEKS copolymers matrix with different degree of sulfonation (DS) were investigated for high temperature proton exchange membrane fuel cells. Composite membranes were characterized by Fourier transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR band shifts suggested that the sulfonic acid groups on the copolymer backbone strongly interact with HPA particles. SEM pictures showed that the HPA particles were uniformly distributed throughout the SPEEKS membranes matrix and particle sizes decreased with the increment of copolymers' DS. The holes were not found in SPEEKS‐4/HPA30 (consisting of 70% SPEEKS copolymers with DS = 0.8 and 30% HPA) composite membrane after composite membranes were treated with boiling water for 24 h. Thermal stabilities of the composite membranes were better than those of pure sulfonated copolymers membranes. Although the composite membranes possessed lower water uptake, it exhibited higher proton conductivity for SPEEKS‐4/HPA30 especially at high temperature (above 100 °C). Its proton conductivity linearly increased from 0.068 S/cm at 25 °C to 0.095 S/cm at 120 °C, which was higher than 0.06 S/cm of Nafion 117. In contrast, proton conductivity of pure SPEEKS‐4 membrane only increased from 0.062 S/cm at 25 °C to 0.078 S/cm at 80 °C. At 120 °C, proton conductivity decreased to poor 0.073 S/cm. The result indicated that composite membranes exhibited high proton conductivity at high temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1967–1978, 2006     

Crosslinking effects on hybrid organic–inorganic proton conducting membranes based on sulfonated polystyrene and polysiloxane

New hybrid semi‐interpenetrating proton‐conducting membranes were obtained using sulfonated polystyrene (SPS) and inorganic–organic polysiloxane phases with the aim of improving the mechanical and thermal characteristics of the pristine polymer and to study the effects of crosslinking in the latter phase in several of their properties, mainly proton conductivity. Siloxane phases were prepared using poly(dimethylsiloxane) (PDMS) and PDMS with tetraethoxysilane (TEOS) or phenyltrimethoxysilane (PTMS) as crosslinking agents. To study the crosslinking effect, membranes were prepared with different TEOS:PDMS and PTMS:PDMS mole ratios. The films obtained were characterized by FTIR, ²⁹Si‐HPDEC MAS‐NMR, ¹³C‐CP‐MAS NMR, elemental and thermal analyses. Certain properties, such as water uptake (WU), ion exchange capacity (IEC) and the state of the water, were determined. The proton conductivity was measured at different temperatures (30°C and 80°C) and relative humidities (50–95%). The water content of the hybrid membranes declined significantly, compared with the SPS membranes, depending on the nature and amount of siloxane phase added. Nonetheless, the conductivity values remained relatively high (>100 mS cm^?1 at 80°C and 95% RH) when compared to Nafion®117 presumably because of the formation of well developed proton channels, which makes them potentially promising as proton exchange membranes for fuel cells. These membranes proved to be thermally stable up to 350°C. Scanning electron microscopy (SEM) and scanning electrochemical microscopy (SECM) were used to characterize the hybrid membranes microstructures; the latter provided contrast for the conductive domains. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of sulfonated homo‐ and co‐polyimides based on 2,4 and 2,5‐diaminobenzenesulfonic acid for proton exchange membranes

A series of sulfonated homo‐ and random co‐polyimides (co‐SPI) based on 2,4‐diaminobenzenesulfonic acid (2,4‐DABS) and 2,5‐diaminobenzenesulfonic acid (2,5‐DABS) has been synthesized via conventional two‐step polyimidization method. 2,4‐DABS and 2,5‐DABS were used as sulfonated diamine compounds, 4,4′‐oxydianiline (ODA) and 4,4′‐diaminodiphenyl sulfone (DDS) were used as non‐sulfonated diamine compounds. Mixtures of sulfonated and non‐sulfonated diamine compounds were reacted with benzophenonetetracarboxylic dianhydride (BTDA) to obtain co‐SPI membranes. Molar ratios of sulfonated to non‐sulfonated diamine were systematically varied to produce copolymers of controlled compositions. The co‐SPIs were evaluated for thermal oxidative stability, ion exchange capacity (IEC), water uptake, proton conductivity, solubility, and hydrolytic stability. Proton conductivity and hydrolytic stability of the co‐SPIs were compared with the fully aromatic polyimide, homo‐SPIs (BTDA/2,4‐DABS and BTDA/2,5‐DABS). Regarding thermogravimetric analysis (TGA) analysis, it is concluded that desulfonation temperature in the range of 200–350°C suggests high stability of sulfonic acid groups. co‐SPIs with 40 mol% of 2,4‐DABS showed similar or higher proton conductivity than Nafion® 117 in water. Proton conductivity values of the co‐SPIs were mainly a function of IEC and water uptake. Consequently, the optimum concentration of 2,4‐DABS was found to be in the range of 30–40 mol% from the viewpoint of proton conductivity, IEC, and hydrolytic stability. Copyright © 2008 John Wiley & Sons, Ltd.