New organic–inorganic hybrid membranes based on sulfonated polyimide/aminopropyltriethoxysilane doping with sulfonated mesoporous silica for direct methanol fuel cells

A series of novel composite methanol‐blocking polymer electrolyte membranes based on sulfonated polyimide (SPI) and aminopropyltriethoxysilane (APTES) doping with sulfonated mesoporous silica (S‐mSiO₂) were prepared by the casting procedure. The microstructure and properties of the resulting hybrid membranes were extensively characterized. The crosslinking networks of amino silica phase together with sulfonated mesoporous silica improved the thermal stability of the hybrid membranes to a certain extent in the second decomposition temperature (250–400°C). The composite membranes doping with sulfonated mesoporous silica (SPI/APTES/S‐mSiO₂) displayed superior comprehensive performance to the SPI and SPI/APTES membranes, in which the homogeneously embedded S‐mSiO₂ provided new pathways for proton conduction, rendered more tortuous pathways as well as greater resistance for methanol crossover. The hybrid membrane with 3 wt % S‐mSiO₂ into SPI/APTES‐4 (SPI/A‐4) exhibited the methanol permeability of 4.68 × 10^?6 cm² s^?1at 25°C and proton conductivity of 0.184 S cm^?1 at 80°C and 100%RH, while SPI/A‐4 membrane had the methanol permeability of 5.16 × 10^?6 cm² s^?1 at 25°C and proton conductivity of 0.172 S cm^?1 at 80°C and 100%RH and Nafion 117 exhibited the values of 8.80 × 10^?6 cm² s^?1 and 0.176 S cm^?1 in the same test conditions, respectively. The hybrid membranes were stable up to about 80°C and demonstrated a higher ratio of proton conductivity to methanol permeability than that of Nafion117. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

In situ sol–gel route to novel sulfonated polyimide?SiO2 hybrid proton‐exchange membranes for direct methanol fuel cells

Polyimides (PIs) as high‐performance organic matrices are used in the preparation of PI composites because of their excellent mechanical, thermal and dielectric properties. The sol–gel method is a promising technique for preparing these PI composites due to the mild reaction conditions and the process being controllable. Although sulfonated polyimide (SPI) proton‐exchange membranes have attracted much attention recently, studies on preparing SPI‐based hybrid proton‐exchange membranes for fuel cells have been rare. A series of SPI? SiO₂ hybrid proton‐exchange membranes were prepared from amino‐terminated SPI pre‐polymers, 3‐glycidoxypropyltrimethoxysilane (KH‐560) and tetraethylorthosilicate through a co‐hydrolysis and condensation process using an in situ sol–gel method. The reactive silane KH‐560 was used to react with amino‐terminated SPI to form silane‐capped SPI in order to improve the compatibility between the polymer matrix and the inorganic SiO₂ phase. The microstructure and mechanical, thermal and proton conduction properties were studied in detail. The hybrid membranes were highly uniform without phase separation up to 30 wt% SiO₂. The storage modulus and tensile strength of the hybrid membranes increased with increasing SiO₂ content. The introduction of SiO₂ improved the methanol resistance while retaining good proton conductivity. The hybrid membrane with 30 wt% SiO₂ exhibited a proton conductivity of 10.57 mS cm^?1 at 80 °C and methanol permeability of 2.3 × 10^?6 cm² s^?1 possibly because the crosslinking structure and SiO₂ phases formed in the hybrids could retain water and were helpful to proton transport. Copyright © 2010 Society of Chemical Industry     

一种新型磺化聚酰亚胺质子交换膜的合成与表征

质子交换膜是质子交换膜燃料电池膜电极的核心部件之一,它的性能好坏对整个系统的运行起着至关重要的作用．目前在质子交换膜燃料电池中普遍采用的质子交换膜材料是全氟磺酸系列薄膜,这类材料具有较高的质子传导率、化学及机械稳定性,但用于直接甲醇燃料电池（DMFC）时则存在甲醇渗透、导致燃料电池输出性能大大降低的问题     

Montmorillonite‐reinforced sulfonated poly(phthalazinone ether sulfone ketone) nanocomposite proton exchange membranes for direct methanol fuel cells

To produce a composite membrane with high conductivity and low permeability, SPPESK with a degree of sulfonation of 101% was carefully selected for the preparation of montmorillonite (MMT)‐reinforced SPPESK using solution intercalation. The fundamental characteristics such as water uptake, swelling ratio, proton conductivity, methanol permeability, and mechanical properties of the composite membranes were studied. Water uptake is improved when organic MMT (OMMT) loading increase. The composite membranes with CTAB‐MMT loading of 4–0.5% show 0.143–0.150 S cm^?1 proton conductivity at 80°C, which approaches the value of Nafion112. In addition, methanol permeability was decreased to 6.29 × 10^?8 cm² s^?1 by the addition of 6 wt % OMMT. As a result, the SPPESK‐MMT composite membrane is a good candidate for use in direct methanol fuel cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39852.     

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     

Preparation and proton conductivity of phosphoric acid‐doped blend membranes composed of sulfonated block copolyimides and polybenzimidazole

A series of phosphoric acid (PA)‐doped blend membranes composed of block or random sulfonated polyimides (SPIs) and polybenzimidazole (PBI) were prepared with similar PA contents to investigate the influence of chemical structures of SPIs on proton conductivity. The proton conductivity of a PA‐doped blend membrane containing block‐type SPI, PA‐bSPI(80/20)/oPBI, was higher than that of the corresponding pristine block‐type SPI, PA‐SPI/PBI containing random‐type SPI and Nafion membranes over a wide temperature range, and reached 0.37 S cm^?1 at 90 °C and 98% relative humidity. The PA‐bSPI(80/20)/oPBI membrane also showed distinct proton conductivity even at low humidity due to a new proton transport pathway among PA and sulfonic acid groups. Also, the novel PA‐doped blend membrane showed higher proton conductivity than Nafion at both above 100 °C and below 0 °C under low relative humidity conditions. © 2013 Society of Chemical Industry     

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     

Preparation and characterization of novel grafted cellophane‐phosphoric acid‐doped membranes for proton exchange membrane fuel‐cell applications

This work concerns preparation of acid‐base polyelectrolyte membranes for fuel‐cell applications from cellulosic backbones for the first time. Grafted cellophane‐phosphoric acid‐doped membranes for direct oxidation methanol fuel cells (DMFC) were prepared following three steps. The first two steps were conducted to have the basic polymers. The first step was introducing of epoxy groups to its chemical structure through grafting process with poly(glycidylmethacrylate) (PGMA). The second step was converting the introduced epoxy groups to imides groups followed by phosphoric acid (? PO₃H) doping as the last step. This step significantly contributes to induce ion exchange capacity (IEC) and ionic conductivity (IC). Chemical changes of the cellophane composition and morphology characters were followed using FTIR, TGA, and SEM analysis. Different factors affecting the membranes characters especially IEC, methanol permeability, and thermal stability were investigated and optimized to have the best preparation conditions. Compared to Nafion 117 membrane, cellophane‐modified membranes show a better IEC, less methanol permeability, and better mechanical and thermal stability. IEC in the range of 1–2.3 meq/g compared to 0.9 meq/g per Nafion was obtained, and methanol permeability has been reduced by one‐order magnitude. However, the maximum obtained IC for cellophane‐PGMA‐grafted membrane doped with phosphoric acid was found 2.33 × 10^?3 (S cm^?1) compared to 3.88 × 10^?2 (S cm^?1) for Nafion 117. The obtained results are very promising for conducting further investigations taking into consideration the very low price of cellophane compared to Nafion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Sorption and transport properties of the semi‐interpenetrating network based on crosslinked poly(vinyl alcohol) and poly(styrene sulfonic acid‐co‐maleic anhydride) as proton‐conducting membranes

This study investigates the sorption and transport properties of hydrocarbon membranes based on poly(vinyl alcohol) network and poly(styrene sulfonic acid‐co‐maleic acid) (PSSA‐MA). The water and methanol self‐diffusion coefficients through an 80 wt % PSSA‐MA interpenetrating SIPN‐80 membrane measured 3.75 × 10^?6 and 5.47 × 10^?7 cm²/s, respectively. These results are lower than the corresponding values of Nafion® 115 (8.89 × 10^?6 cm²/s for water and 8.63 × 10^?6 cm²/s for methanol). The methanol permeability of SIPN‐80 membrane is 4.1 × 10^?7 cm²/s, or about one‐fourth that of Nafion® 115. The difference in self‐diffusion behaviors of Nafion® 115 and SIPN‐80 membranes is well correlated with their sorption characteristics. The solvent uptake of Nafion® 115 increased as the methanol concentration increased up to a methanol mole fraction of 0.63, and then decreased. However, the solvent uptake of the SIPN‐80 membranes decreased sluggishly as the methanol concentration increased. The λ values of water and methanol (i.e., λ and λ) in Nafion® 115 are quite close, indicating no sorption preference between water and methanol. In contrast, the λ value is only one‐third λ for a SIPN‐80 membrane. Accordingly, the SIPN membranes are regarded as candidates for direct methanol fuel cell applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Hybrid Network Sulfonated Polynorbornene/Silica Membranes with Enhanced Proton Conductivity by Doped Phosphotungstic Acid

A series of novel hybrid sulfonated polynorbornene‐silica (PBN–SiO₂) proton conducting membranes doped with different weight ratio of phosphotungstic acid (PWA) were prepared by the casting procedure. The proton conductivity of the composite membranes containing 40 wt.% PWA reached the maximum of 6.1 × 10^–2 S cm^–1 and increased gradually with PWA content and temperature elevating, while the methanol permeabilities (3.52–9.39 × 10^–7 cm² s^–1) of these membranes were much lower than that of Nafion 117 (2.36 × 10^–6 cm² s^–1). The membranes also exhibited excellent thermally stable and mechanical properties, which imply that the PBN–SiO₂–PWA membranes are promising materials in the direct methanol fuel cells (DMFC) applications.     

Fluorinated naphthalene-based poly(arylene ether ketone)s containing pendant groups for direct methanol fuel cells

A novel series of naphthalene-based poly(arylene ether ketone) copolymers containing methoxy groups and hexafluoroisopropylidene diphenyl moieties (6F-MNPAEKs) were successfully synthesized by aromatic nucleophilic polycondensation. Chain-type fluorinated and sulfonated naphthalene-based poly(arylene ether ketone) copolymers (6F-SNPAEKs) were subsequently synthesized by demethylation and sulfobutylation. The chemical structures of 6F-SNPAEKs were confirmed by ¹H NMR. The 6F-SNPAEKs in acid form showed excellent thermal stability at elevated temperatures. The 6F-SNPAEK membranes were easily obtained by solution casting and properties for fuel cells were investigated in detail. The water uptake, swelling ratio and proton conductivity increased with degree of sulfonation (DS) and temperature. 6F-SNPAEK-90 showed the highest conductivity of 0.181 S cm^?1 at 80 °C. The methanol permeability of the membranes was in the range of 0.238–6.49 × 10^?7 cm² s^?1, compared to 1.55 × 10^?6 cm² s^?1 for Nafion 117. The membranes also showed excellent mechanical properties: the elongation at break was greater than 15%. These results indicate that the 6F-SNPAEK membranes are a promising candidate for use in direct methanol fuel cell (DMFC) applications.     

Sulfonated polyimide and poly (ethylene glycol) diacrylate based semi‐interpenetrating polymer network membranes for fuel cells

Semi‐interpenetrating polymer network (semi‐IPN) membranes based on novel sulfonated polyimide (SPI) and poly (ethylene glycol) diacrylate (PEGDA) have been prepared for the fuel cell applications. SPI was synthesized from 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid, and 2‐bis [4‐(4‐aminophenoxy) phenyl] hexafluoropropane. PEGDA was polymerized in the presence of SPI to synthesize semi‐IPN membranes of different ionic contents. These membranes were characterized by determining, ion exchange capacity, water uptake, water stability, proton conductivity, and thermal stability. The proton conductivity of the membranes increased with increasing PEGDA content in the order of 10^?1 S cm^?1 at 90°C. These interpenetrating network membranes showed higher water stability than the pure acid polyimide membrane. This study shows that semi‐IPN SPI membranes based on PEGDA which gives hydrophilic group and structural stability can be available candidates comparable to Nafion® 117 over 70°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Crosslinked hydroxyl‐conductive copolymer/silica composite membranes based on addition‐type polynorbornene for alkaline anion exchange membrane fuel cell applications

Crosslinked hydroxyl‐conductive copolymer/silica composite membranes based on addition‐type polynorbornene, poly(dodoxymethylene norbornene‐co‐norbornene‐3‐(trimethylpropyl ammonium)‐functionalized silica (QP(DNB/NB‐SiO₂), were prepared by a sol–gel method. Copolymer composite membranes with different degree of quaternary ammonium functional silica, designated as QP(DNB/NB‐SiO₂‐X) (X = 5, 10, 15 and 25 wt%, respectively), displayed good dimensional stabilities with low in‐plane swelling rate of 1.32–3.7%, good mechanical properties with high elastic modulus of 605.4–756.8 MPa and high tensile strength of 13.2–20 Mpa. The achieved copolymer composite membranes could self‐assemble into a microphase‐separated morphology with randomly oriented long‐range aliphatic chain/cylinder ionic channels that were imbedded in the hydrophobic PNB matrix. Among these membranes, the QP(DNB/NB‐SiO₂‐25) showed the parameter with ionic conductivity of 9.33 × 10^?3S cm^?1, methanol permeability of 2.89 × 10^?7cm² s^?1, and ion‐exchange capacity(IEC) of 1.19 × 10^?3 mol g^?1. A current density of 82.3mA cm^?2, the open circuit voltage of 0.65 V and a peek power density of 32 mW cm^?2 were obtained. POLYM. ENG. SCI., 58:13–21, 2018. © 2017 Society of Plastics Engineers     

Phthalonitrile end-capped sulfonated polyarylene ether nitriles for low-swelling proton exchange membranes

A series of phthalonitrile end-capped sulfonated polyarylene ether nitriles are synthesized via K₂CO₃ mediated nucleophilic aromatic substitution reaction at various molar ratios. The as-prepared polymer structures are confirmed by ¹H NMR and FTIR spectroscopy. The properties of membranes cast from the corresponding polymers are investigated with respect to their structures. The membranes exhibit good thermal and mechanical properties, low methanol permeability (0.01?×?10^?6–0.58?×?10^?6 cm²·s^?1 at 20 °C), and high proton conductivity (0.021–0.088 S·cm^?1 at 20 °C). The introduction of phthalonitrile is proved to increase intermolecular interaction, mainly contributing to the reduction in water uptake, swelling ratio, and methanol permeability. More importantly, its introduction does not decrease the proton conductivity, but there is a slight increase. Furthermore, the selectivity of SPEN-CN-50 can reach 4.11?×?10⁵ S·s·cm^?3, which is about nine times higher than that of Nafion 117. All the data show that the as-prepared membranes may be potential proton exchange membrane for DMFCs applications.     

Sulfonated poly(bis‐A)‐sulfones as proton exchange membranes for direct methanol fuel cell application

Sulfonated poly(bis‐A)‐sulfone (SPSF) samples were prepared by a mild postsulfonation method using trimethylsilyl chlorosulfonate as sulfonation agent, and their thermal and mechanical properties were evaluated. The serials of SPSF membranes are thermally stable up to 450°C in air. When compared with the poly(bis‐A)‐sulfone membrane, the hydrophilicity and water uptake of the SPSF membranes are enhanced. A microphase‐separated structure comprised of hydrophilic and hydrophobic polymer backbone was observed from atomic force microscopy phase images. The hydrophilic ionic clusters become continuous to form channels when ion exchange capacity (IEC) reached 1.47 mequiv/g. Moreover, the membranes showed very good proton conductivities (20°C, 0.01–0.11 S/cm) and low‐methanol permeability (0.09–3.06 × 10^?6 cm²/s), and the methanol diffusion coefficients were lower than that of Nafion112 (1.35 × 10^?6 cm²/s) with IEC values from 0.70 to 1.47 mequiv/g. However, the Fenton's reagent test revealed that the membranes exhibited very poor oxidation stability, which is the main defect limiting the application of SPSF for proton exchange membranes. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Gas permeation through water‐swollen polysaccharide/poly(vinyl alcohol) membranes

The effect of Na‐alginate content on the gas permeation properties of water‐swollen membranes prepared by varying Na‐alginate and poly(vinyl alcohol) (PVA) content in membranes was investigated. The influences of water content and crystallinity of the membranes on the gas permeation performance of the water‐swollen membranes were studied. The gas permeation rate and selectivity of Na‐alginate/PVA water‐swollen membranes were compared with those of the dry membranes. The permeation rates of nitrogen and carbon dioxide through water‐swollen membranes were in the range of 0.4–7.6 × 10^?7 to 3.7–8.5 × 10^?6 cm³ (STP)/cm² s^?1 cmHg^?1, which were 10,000 times higher than those of dry‐state membranes. The permeation rates of mixture gases through water‐swollen Na‐alginate/PVA membranes were found to increase exponentially with the increase of Na‐alginate content, whereas carbon dioxide concentration in permeates was decreased linearly. It was found that the gas permeance of the water‐swollen membranes increased with increasing the Na‐alginate content in the membrane. Gas permeation rates of the water‐swollen Na‐alginate/PVA membranes increased with increasing the water content in the membrane and decreasing the crystallinity of the membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3225–3232, 2004     

A novel heteropolyacid-doped carbon nanotubes/Nafion nanocomposite membrane for high performance proton-exchange methanol fuel cell applications

A novel proton-exchange polymer composite membrane was synthesized using Nafion^®, tetraethoxysilane-modified carbon nanotubes (CNTs) and phosphotungstic acid-modified carbon nanotubes with the aim of using direct methanol fuel cells (DMFCs). Physicochemical properties of the modified CNTs and fabricated composite membranes were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, water uptake, thermogravimetric analysis, ion exchange capacity, proton conductivity and methanol permeability tests. It was demonstrated that chemical surface modification of CNTs and introduction of the phosphotungstic acid (PWA) groups effectively improved the performance of DMFC. It was found that the presence of PWA groups on the surface of CNTs led to the formation of strong electrostatic interactions between the PWA groups and clusters of sulfonic acid in Nafion^® macromolecules. Hence, the incorporation of inorganic phosphotungstic super-acid-doped silicon oxide-covered carbon nanotubes (CNT@SiO₂-PWA) into Nafion^® matrices enhanced the proton conductivity of the prepared membranes. Moreover, the methanol permeability was reduced to 2.63 × 10^?7 cm² s^?1 in comparison with the recast Nafion^® membrane (2.25 × 10^?6 cm² s^?1). Enhancing the proton conductivity and reducing the methanol permeability, the selectivity of the prepared nanocomposite membranes was enhanced to a greater value of 330,700 S s cm^?3 as compared to the value of 38,222 S s cm^?3 for recast Nafion^®.     

Novel sulfonated polyimide ionomers by incorporating pyridine functional group in the polymer backbone

A series of sulfonated polyimides (SPIs) containing pyridine ring in the polymer backbone were synthesized by the polycondensation of 1,4,5,8‐naphthalene‐tetracarboxylic dianhydride (NTDA), 5‐(2,6‐bis(4‐aminophenyl)pyridin‐4‐yl)‐2‐methoxy benzene sulfonic acid (SDAM), and 4,4′‐diaminodiphenyl ether (ODA). Flexible, transparent, and tough membranes were obtained. Property study revealed that all the membranes displayed high thermal stability with the desulfonation and decomposition temperature higher than 290 and 540°C, respectively, as well as good mechanical property with Young's modulus larger than 1.0 GPa, maximum strength (MS) on a scale of 60–80 MPa, and elongation at break (EB) ranged from 41.79 to 75.17%. More importantly, the new materials exhibited small water uptake and excellent dimensional stability with the highest sulfonated SPI‐80 showing the maximum water uptake of 36.1%, and maximum swollen ratio of Δt = 0.038 and Δl = 0.026, respectively (Δt and Δl stands for the thickness and diameter change of the film, respectively). The high water stability exhibited by the SPI films is attributed to the formation of inner salts and/or ionic crosslinking between the sulfonic acid and pyridine functional groups, which suppresses the water uptake ability of sulfonic acid and strengthened the interpolymer chain interactions. Thus, the excellent water stability, good thermal and mechanical properties, and the technologically applicable conductivity of SPI‐80 render this material attractive for proton exchange membrane (PEM) application. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009