Sulfonated poly(ether ether ketone)/epoxy/phenol novolac blend proton‐exchange membranes with low methanol permeability

A crosslinked epoxy [4,4′‐diglycidyl‐(3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP)], cured by phenol novolac (PN), was introduced into a sulfonated poly(ether ether ketone) (SPEEK) membrane (ion‐exchange capacity = 2.0 mequiv/g) with a casting‐solution, evaporation, and heating crosslinking method to improve the mechanical properties, dimensional stability, water retention, and methanol resistance. By Fourier transform infrared analysis, the interactions between the sulfonic acid groups and hydroxyl groups in the blend membranes were confirmed. The microstructure and morphology of the blend membranes were investigated with atomic force microscopy. As expected, the blend membranes showed excellent mechanical properties, good thermal properties (thermal stability above 200°C), lower swelling ratios (1.4% at 25°C and 7.0% at 80°C), higher water retention (water diffusion coefficient = 9.8 × 10^?6 cm²/s), and a lower methanol permeability coefficient (3.6 × 10^?8 cm²/s) than the pristine SPEEK membrane. Although the proton conductivity of the blend membranes decreased, a higher selectivity (ratio of the proton conductivity to the methanol permeability) was obtained than that of the pristine SPEEK membrane. The results showed that the SPEEK/TMBP/PN blend membranes could have potential use as proton‐exchange membranes in direct methanol fuel cells. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modified Sulfonated Poly(ether ether ketone) Based Mixed Matrix Membranes for Direct Methanol Fuel Cells

Mixed matrix membranes based on zeolite 4A‐methane sulfonic acid (MSA)‐sulfonated poly(ether ether ketone) (SPEEK) are evaluated as a potential polymer electrolyte membrane (PEM) for direct methanol fuel cells (DMFCs). Ion‐exchange capacity, sorption of water, and water–methanol mixture, proton conductivity, and methanol permeability for the mixed‐matrix membranes have been extensively investigated. The mixed‐matrix membranes are also characterized for their cross‐sectional morphology, mechanical, and thermal properties. DMFCs employing SPEEK‐MSA (20 wt.%) blend, zeolite 4A (4 wt.%)‐SPEEK‐MSA (20 wt.%) mixed matrix membranes deliver peak power densities of 130 and 159 mW cm^–2, respectively; while a peak power density of only 95 mW cm^–2 is obtained for the DMFC employing pristine SPEEK membrane at 70 °C. The results showed that these SPEEK based mixed matrix membranes exhibit higher DMFC performance and lower methanol permeability in comparison to Nafion‐117 membrane.     

Sulphonated Biphenylated Poly(aryl ether ketone)s for Fuel Cell Applications

New series of fully aromatic poly(ether ketone)s with a biphenyl pendant groups were synthesised. A direct comparison of sulphonation reaction among monophenylated poly(ether ether ketone) (Ph‐PEEK), biphenylated poly(ether ether ketone) (BiPh‐PEEK) and PEEK (Victrex) was thoroughly investigated. Several advantages of the pendant‐phenyl poly(ether ketone)s compared with commercial PEEK were identified, including ready control over the site of sulphonation and degree of sulphonation (DS), and mild and rapid sulphonation. The basic membrane physical properties comprising of thermal and mechanical properties, dimensional stability and proton conductivity were studied. One new membrane, sulphonated biphenylated poly(ether ether ketone) (BiPh‐SPEEKDK) having a good combination of membrane properties was fabricated into a membrane electrode assembly (MEA), and it showed excellent direct methanol fuel cell (DMFC) performance.     

Fluorenyl‐containing Quaternary Ammonium Poly(arylene ether sulfone)s for Anion Exchange Membrane Applications

A series of anion exchange membranes (AEM) based on block quaternary ammonium poly(arylene ether sulfone) (QA‐bPAES) were successfully synthesized from 9,9′‐bis(4‐hydroxyphenyl) fluorene, 4,4′‐(hexafluoroisopropylidene) diphenol and 4,4′‐difluorodiphenyl sulfone via block polymerization, chloromethylation, quaternization, alkalization and solution casting. Properties of the obtained QA‐bPAES membranes, including ion exchange capacity (IEC), water uptake, swelling ratios, methanol permeability and ion conductivity were investigated. The obtained QA‐bPAES membranes showed low water uptakes, high ion conductivities and good physical and chemical stability. For example, the membrane of QA‐bPAES(20/10)‐1.34 with IEC of 1.34 mmol g⁻¹ exhibited swelling ratios of 5.0% and 5.1% in in‐plane and through‐plane direction, respectively, and ion conductivity of 15.6 mS cm⁻¹ in water at 60 °C with low methanol permeability of 1.06 × 10⁻⁷ cm² s⁻¹ (25 °C). All the results indicated that this type of block membranes had good potentials for alkaline anion exchange membrane fuel cell applications.     

Regulation of micromorphology and proton conductivity of sulfonated polyimide/crosslinked PNIPAm semi‐interpenetrating networks by hydrogen bonding

A series of novel sulfonated polyimide (SPI)/crosslinked poly(N‐isopropylacrylamide) (cPNIPAm) semi‐interpenetrating polymer networks (semi‐IPNs) were synthesized as the proton exchange membranes for direct methanol fuel cells via in situ polymerization. The micromorphology and properties of the semi‐IPN membranes were characterized. The results indicated that the hydrogen bonds between cPNIPAm and SPI in the semi‐IPN structure were a crucial factor for regulating the micromorphology, proton conductivity and other properties of the semi‐IPN membranes. A more uniform sulfonic ionic cluster distribution was observed in the membrane of SPI‐20‐cPNIPAm with equimolar ratio of sulfonic acid groups and amido bonds, which could provide effective proton transport channels. The SPI‐20‐cPNIPAm exhibited a maximum proton conductivity of 0.331 S cm^?1 at 80 ^oC (relative humidity 100%), an optimal selectivity of 8.01 × 10⁵ S s cm^?3 and an improved fuel cell performance of 72 mW cm^?2 compared with both pristine SPI and other semi‐IPN membranes. The SPI‐20‐cPNIPAm semi‐IPN membranes also retained good mechanical properties and thermal stabilities on the whole. © 2014 Society of Chemical Industry     

Proton exchange membrane based on crosslinked sulfonated polyphosphazene containing pendent perfluorosulfonic acid groups with sulfonated poly(ether ether ketone)

A series of crosslinked membranes based on new sulfonated polyphosphazene bearing pendent perfluorosulfonic acid groups (PMFP‐g‐PS) and sulfonated poly (ether ether ketone) were prepared and evaluated as proton exchange membranes for direct methanol fuel cells (DMFCs). The structure of PMFP‐g‐PS was characterized by Fourier transform infrared spectroscopy, ¹H and ¹⁹F NMR spectra. In comparison with the pristine PMFP‐g‐PS membrane, the crosslinked membranes showed improved water uptakes and proton conductivities. The methanol permeability values of the membranes were in the range of 1.32 × 10^?7 to 3.85 × 10^?7 cm²/s, which were lower than Nafion 117 (12.1 × 10^?7 cm²/s). The selectivity of all the membranes was much higher compared with Nafion 117. Furthermore, transmission electron microscopy observation revealed that clear phase‐separated structures were well dispersed and connected to each other in the membranes. These membranes displayed high water uptakes and low swelling ratios, high proton conductivities, low methanol permeability values, good thermal, and oxidative stabilities. The results indicate that these membranes are potential candidate proton exchange membrane materials for DMFCs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43492.     

Cross‐linked Poly(arylene ether ketone) Proton Exchange Membranes with High Ion Exchange Capacity for Fuel Cells

Sulfonated poly(arylene ether ketone) (SPAEK) possessing the pendant carboxylic acid groups was synthesized. The carboxylic acid groups of SPAEK were reacted with a cross‐linking reagent to prepare a cross‐linked membrane with a high ion exchange capacity (IEC), a high oxidative stability, and an excellent mechanical strength. The cross‐linking hindered the mobility of the polymer chains and thus strongly affected the water uptake and the methanol permeability of the membranes. Also, as the cross‐linker used in this study bore sulfonic acid groups, cross‐linking did not lead to a noticeable loss of the proton conductivity. The cross‐linked SPAEK membrane with 20% cross‐linking density, CSPAEK‐20% membrane, exhibited a high proton conductivity of 0.045 S cm^–1 associated with a high IEC value of 1.78 mmol g^–1 but a low methanol permeability of 4.3 × 10^–7 cm² s^–1. The CSPAEK‐20% membrane also showed excellent cell performance and oxidation resistance.     

Preparation of KOH‐doped PVA/PSSA Solid Polymer Electrolyte for DMFC: The Influence of TiO2 and PVP on Performance of Membranes

The development of low cost alkaline anion solid exchange membranes requires high ionic conductivity, low liquid uptake, strong mechanical properties and chemical stability. PVA/PSSA blends cross‐linked with glutaraldehyde and decorated with titanium dioxide nanoparticles introduce advantages relative to the pristine membrane of PVA and PVA/PVP membranes due to their improved electrical response and low methanol uptake/ swelling ratio allowing their use in alkaline direct methanol fuel cells.     

Synthesis and Characterisation of Sulphonated Poly(arylene sulphone) Terpolymers with Triphenylphosphine Oxide Moieties for Proton Exchange Membrane Fuel Cells

For application in fuel cells, a series of sulphonated poly(phenylene sulphone) terpolymers with triphenylphosphine oxide moieties as constitutional units in the polymer backbone have been prepared. The synthesis of the terpolymers represents a two‐step process including: (i) an aromatic nucleophilic substitution polycondensation of three difluoro monomers with varying ratios, i.e. 3,3′‐disulphonate‐4,4′‐difluorodiphenylsulphone, 4,4′‐difluorodiphenylsulphone and bis(4‐fluorophenyl)phenyl phosphine oxide (BFPPO), with 4,4′‐thiobisbenzenethiol yielding sulphonated poly(phenylene sulphide) terpolymers (sPPSPO) and (ii) their following oxidation with hydrogen peroxide in acidic solution to yield sulphonated poly(phenylene sulphone) terpolymers (sPPSO2PO). The structures and molecular compositions were confirmed by ¹H and ¹³C NMR spectroscopy. The ion exchange capacity (IEC) was adjusted at will choosing the appropriate ratio of sulphonated and unsulphonated monomers. Terpolymers with 1.72 ≤ IEC ≤ 2.32 have been obtained. Sulphonated poly(arylene) ionomers containing only sulphone (–SO₂–) linkages and phosphine oxide (–PO–) units rather than ether or sulphide in the backbone reveal a high thermal and oxidative stability. Membranes were cast either from dimethylformamide (DMF) or from dimethyl sulphoxide (DMSO) solutions. For all terpolymers some general characteristic trends were observed, such as an increase of the proton conductivity with increasing IEC, water uptake and temperature. The series of sPPSO2PO membranes offered high conductivities at high humidification, however, their performance strongly depends on the relative humidity. The mechanical properties of sulphonated poly(phenylene sulphone)s have been considerably improved by means of terpolymerisation with phenylene oxide moieties. Even under high humidification the terpolymers form clear, flexible membranes the stress at break of some membranes exceeds that of Nafion® under the same conditions by 40%.     

EB‐crosslinked Polymer Electrolyte Membranes Based on Highly Sulfonated Poly(ether ether ketone) and Poly(vinylidene fluoride)/Triallyl Isocyanurate

In this study, crosslinked polymer electrolyte membranes for polymer electrolyte membrane fuel cell (PEMFC) applications are prepared using electron beam irradiation with a mixture of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and triallyl isocyanurate (TAIC) at a dose of 300 kGy. The gel‐fraction of the irradiated SPEEK/PVDF/TAIC (95/4.5/0.5) membrane is 87% while the unirradiated membrane completely dissolves in DMAc solvent. In addition, the water uptake of the irradiated membrane is 221% at 70 °C while that of the unirradiated membrane completely dissolves in water at above 70 °C. The ion exchange capacity and proton conductivity of the crosslinked membrane are 1.57 meq g⁻¹, and 4.0 × 10⁻² S cm⁻¹ (at 80 °C and RH 90%), respectively. Furthermore, a morphology study of the membranes is conducted using differential scanning calorimetry and X‐ray diffractometry. The cell performance study with the crosslinked membrane demonstrates that the maximum power density is 518 mW cm⁻² at 1036 mA cm⁻² and the maximum current density at applied voltage of 0.4 V is 1190 mA cm⁻².     

Blend membranes based on disulfonated poly(aryl ether ether ketone)s (SPEEK) and poly(amide imide) (PAI) for direct methanol fuel cell usages

Highly disulfonated poly(aryl ether ether ketone)s (SPEEK-70) copolymer was synthesized via direct polymerization to precisely control the degree of sulfonation (D_s = 1.40), which was confirmed and estimated by ¹H NMR. As expected, the proton conductivity of SPEEK-70 membrane is 0.084 S/cm at 25 °C and increases to 0.167 S/cm at 80 °C, surpassing that of Nafion^® 117. However, the relatively high methanol crossover and excessively swelling properties limited its usage in DMFC. Poly(amide imide) was blended with SPEEK-70 to improve the methanol resistance and mechanical properties. These blend membranes were characterized as a function of weight fraction of PAI in terms of ion exchange capacity (IEC), water uptake, water desorption, proton conductivity and methanol permeability in detail. Although the proton conductivities decreased upon the addition of PAI, higher selectivity values defined as the ratio of proton conductivity to methanol permeability were found for the blend membranes. Therefore, the SPEEK/PAI blend membranes are promising for usage in DMFC.     

Surface Fluorination of Poly(fluorenyl ether ketone) Ionomers as Proton Exchange Membranes for Fuel Cell Application

A series of sulphonated poly(fluorenyl ether ketone) ionomers were successfully fluorinated by the means of direct surface fluorination. Polymer ionomer samples in two different states (membrane and powder) were treated with F₂ gas which is diluted in N₂ in a special reactor. X‐ray photoelectron spectroscopy (XPS) was used to examine the F/C ratios of the fluorinated materials. The results revealed that the fluorination only occurred on the membrane surface and the fluorination degree increased with increasing F₂ concentration in N₂. The membrane subjected to fluorination shows an obviously enhanced oxidative stability. The endurance in a Fenton's reagent of FSPFEK‐P‐28 is longer than 180 min which is two times longer than that of un‐fluorinated SPFEK. The PEM properties and single fuel cell performances were investigated by comparison of un‐ and fluorinated polymer ionomers. The fluorinated membranes demonstrated an enhanced hydrophobic surface property, increased proton conductivities and better single fuel cell performances. Surface fluorination provides a convenient and useful approach to prepare highly proton conductive membrane with long life‐time PEM fuel cell applications.     

Synthesis and characterization of a new type of sulfonated poly(ether ether ketone ketone)s for proton exchange membranes

A novel series of sulfonated poly(ether ether ketone ketone)s (SPEEKKs) were prepared by aromatic nucleophilic polycondensation with different ratios of 1,3‐bis(3‐sodium sulfonate‐4‐fluorobenzoyl)benzene to 1,3‐bis(4‐fluorobenzoyl)benzene. ¹H‐NMR spectroscopy was used to confirm the degrees of sulfonation (DS) of the polymers. Thermal stabilities of the SPEEKKs in acid form were characterized by thermogravimetric analysis (TGA), which showed that SPEEKKs were excellently thermally stable at high temperatures. SPEEKK polymers can be easily cast into tough membranes. Both of proton conductivity and methanol diffusion coefficient have been tested in this article. Other properties of the SPEEKK membranes were investigated in detail. The results show that the SPEEKK membranes are promising in proton exchange membrane fuel cells (PEMFCs) application. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Membrane Design for Direct Ethanol Fuel Cells: A Hybrid Proton‐Conducting Interpenetrating Polymer Network

A series of hybrid proton‐conducting membranes with an interpenetrating polymer network (IPN) structure was designed with the direct ethanol fuel cell (DEFC) application in mind. In these membranes, glutaraldehyde crosslinked poly(vinyl alcohol) (PVA) were interpenetrated with the copolymer of 2‐acrylamido‐2‐methyl‐propanesulphonic acid (AMPS) and 2‐hydroxyethyl methacrylate (HEMA) crosslinked by poly(ethylene glycol) dimethacrylate (PEGDMA). Silica from the in situ sol–gel hydrolysis of tetraethyl orthosilicate (TEOS) was uniformly dispersed in the polymer matrix. The membranes fabricated as such had ion exchange capacities of 0.84–1.43 meq g^–1 and proton conductivities of 0.02–0.11 S cm^–1. The membranes exhibited significantly lower fuel permeabilities than that of Nafion. In a manner totally unlike Nafion, fuel permeabilities were lower at higher fuel concentrations, and were lower in ethanol than methanol solutions. These behaviours are all relatable to the unique swelling characteristics of PVA (no swelling in ethanol, partial swelling in methanol and extensive swelling in water) and to the fuel blocking and swelling suppression properties of silica particles. The membranes are promising for DEFC applications since a high concentration of fuel may be used to reduce fuel crossover and to improve the anode kinetics for a resultant increase in both the energy and power densities of the fuel cell.     

Sulfonated poly(phenylene ether ether sulfone) membrane tailored with layer-by-layer self-assembly of poly(diallyldimethylammonium chloride) and phosphotungstic acid for DMFC applications

Poly(diallyldimethylammonium chloride) (PDDA) and phosphotungstic acid (PTA) were used as cationic and anionic polyelectrolyte layers, respectively, in an alternating fashion to enhance the methanol barrier property and oxidative stability of sulfonated poly (phenylene ether ether sulfone) (SPEES) proton exchange membranes (PEMs). The multilayer PEMs were characterized by AFM, FTIR, and AC impedance spectroscopy. Methanol permeability of the multilayered membranes was found to be much lower than the bare SPEES membrane. The multilayered membranes displayed significantly improved oxidative stability and dimensional stability compared to pristine SPEES membrane. Conversely, the water uptake (%) and proton conductivity (S cm⁻¹) of the prepared membranes decrease to some extent with increasing the PDDA/PTA bilayers in comparison to the pristine SPEES membrane. The maximum relative selectivity (2.23 × 10⁴ S cm⁻³ s) and retained weight (88.9%) were observed for SPEES-[PDDA/PTA]₅ multilayered membrane. The obtained results exposed the possibility of SPEES-[PDDA/PTA]₅ multilayered membrane to serve as high-performance PEMs in direct methanol fuel cells. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47344.     

Relationship Between Methanol Permeability and Structure of Different Radiation‐Grafted Membranes

Styrene grafted and sulfonated poly(vinylidene fluoride) and poly(vinylidene fluoride‐co‐hexafluoropropylene) films are candidates as electrolytes in direct methanol fuel cells. Their behaviour in water, 1 and 3 mol dm^–3 aqueous methanol, and pure methanol were studied. According to SAXS results, water and methanol‐water solutions have similar effects on the membranes, i.e., the lamellar period increases and the ionic domains enlarge. Furthermore, differences in the ionic domain structures in pure methanol and water were observed. These structural changes together with dissimilar liquid uptakes in water and in methanol are reflected as changes in the conductivities. An increase in the SAXS intensity and changes in the Bragg distance of the ionic peak were observed in methanol compared to aqueous solutions. This may be related to the hydrophobicity of the CH₃ group on methanol. Dissimilarities in methanol permeability through the radiation‐grafted membrane can be related to structural differences in membranes observed with SAXS. Permeabilities were observed to be lower for the radiation‐grafted membranes compared to Nafion® 115, which compensates for the higher area resistance of the experimental membranes and thus improves their performance in a fuel cell.     

Preparation and Characterization of Semi‐IPN Fluorine Containing Polybenzimidazole/Nafion Composite Membrane for Fuel Cells

A facile way to prepare semi‐interpenetrating polymer network (semi‐IPN) membrane which adopted 1,3‐benzenedisulfonyl azide (1,3‐BDSA) to crosslink with fluorine containing polybenzimidazole (Aliphatic‐16F‐PBI) in the Aliphatic‐16F‐PBI/Nafion composite membranes was proposed. By means of Fourier transformed infrared (FTIR) spectra analysis, the possible crosslinking reaction mechanism was investigated. Results suggested that 1,3‐BDSA molecule loses a nitrogen and forms nitrene upon heating. Then this nitrene reacts with C–H bond of Aliphatic‐16F‐PBI. Scanning electron microscope (SEM) images showed that the compatibility of PBI and Nafion improved while hexadecafluoro‐octyl groups were implanted into Aliphatic‐16F‐PBI molecule. The properties of Aliphatic‐16F‐PBI/Nafion composite membranes for fuel cell applications were determined through tests of gel fraction, thermogravimetry (TG), dimensional stability, mechanical property and proton conductivity. The gel fraction could reach 27.9% when 7.4% 1,3‐BDSA was added into the composite membranes. The proton conductivity of the semi‐IPN Aliphatic‐16F‐PBI/Nafion composite membranes could reach 0.69 × 10^–2 S cm^–1 at 120 °C at 100% relative humidity. Such high crosslink degree resulted in the improvement of the tensile strength, dimensional stability and chemical oxidative stability of semi‐IPN Aliphatic‐16F‐PBI/Nafion composite membranes. Nonetheless, it had little effect on the thermal stability.     

Enhanced Proton Conductivity of Sulfonated Poly(ether ether ketone) Membrane Embedded by Dopamine‐Modified Nanotubes for Proton Exchange Membrane Fuel Cell

Design and fabrication of alternative proton exchange membrane (PEM) with high proton conductivity is crucial to the commercial application of PEM fuel cell. Inspired by the bioadhesion principle, dopamine‐modified halloysite nanotubes (DHNTs) bearing –NH₂ and –NH– groups are facilely synthesized by directly immersing natural halloysite nanotubes (HNTs) into dopamine aqueous solution under mild conditions. DHNTs are then embedded into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare hybrid membranes. HNTs‐filled hybrid membranes are prepared for comparison. The microstructure and physicochemical properties of the membranes are extensively investigated. Fourier transform infrared analysis implies that ordered acid–base pairs (e.g., –S–O^–…⁺H–HN–, –S–O^–…⁺H–N–) are formed at SPEEK–DHNT interface through strong electrostatic interaction. In such a way, continuous surface‐induced ion‐channels emerge along DHNTs. Although the incorporation of DHNTs reduces the channel size, water uptake, and area swelling of the hybrid membranes, which in turn would reduce the vehicle‐type proton transfer, the acid–base pairs create continuous pathways for fast proton transfer with low energy barrier via Grotthuss mechanism. Consequently, DHNT‐filled hybrid membrane with 15% DHNTs achieves a 30% increase in proton conductivity and a 52% increase in peak power density of single cell when compared with SPEEK control membrane, particularly.     

Sulphonated Poly(ether ether ketone) Proton Exchange Membranes for Fuel Cell Applications

Polymer electrolyte membrane fuel cells (PEMFCs) are promising new power sources for automotive and portable devices. Nafion® is the currently used membrane in PEMFCs. Although these membranes show high proton conductivity and excellent chemical stability, their high cost makes them unpractical for commercial purposes. Sulphonated poly(ether ether ketone) (SPEEK) ionomers were synthesized using chlorosulphonic acid as the sulphonating agent in dichloromethane medium. Homogeneous proton-conducting membranes were developed from the obtained SPEEK by solvent casting method. Membranes were assessed for their suitability in fuel cell applications. The extent of sulphonation was controlled by varying the reaction time, concentration of polymer, and concentration of sulphonating agent. The SPEEK membranes exhibit degree of sulphonation from 10 to 66%, ion exchange capacity from 0.29 to 1.92 meq/g and maximum water and methanol uptake up to 54 and 22%, respectively, at 25°C. The membranes were characterized by FTIR to confirm sulphonation, and DSC and TGA to investigate the thermal stability. The proton conductivities of such membranes were found to be excellent in the order of 10^?2 S/cm in the fully hydrated condition at room temperature as measured by impedance spectroscopy. The durability of the membranes was also tested. The study revealed the possibility of a cheaper alternative membrane for use in PEMFC.     

Preparation and properties of bisphenol A‐based sulfonated poly(arylene ether sulfone) proton exchange membranes for direct methanol fuel cell

Novel bisphenol A‐based sulfonated poly(arylene ether sulfone) (bi A‐SPAES) copolymers were successfully synthesized via direct copolymerization of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone, 4,4′‐dichlorodiphenylsulfone, and bisphenol A. The copolymer structure was confirmed by Fourier transform infrared spectra and ¹H NMR analysis. The series of sulfonated copolymers based membranes were prepared and evaluated for proton exchange membranes (PEM). The membranes showed good thermal stability and mechanical property. Transmission electron microscopy was used to obtain the microstructures of the synthesized polymers. The membranes exhibit increased water uptake from 8% to 66%, ion exchange capacities from 0.41 to 2.18 meq/g and proton conductivities (25°C) from 0.012 to 0.102 S/cm with the degree of sulfonation increasing. The proton conductivities of bi A‐SPAES‐6 membrane (0.10–0.15 S/cm) with high‐sulfonated degree are higher than that of Nafion 117 membrane (0.095–0.117 S/cm) at all temperatures (20–100°C). Especially, the methanol diffusion coefficients of membranes (1.7 × 10^?8 cm²/s–8.5 × 10^?7 cm²/s) are much lower than that of Nafion 117 membrane (2.1 × 10^?6 cm²/s). The new synthesized copolymer was therefore proposed as a candidate of material for PEM in direct methanol fuel cell. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009