Novel proton conducting sulfonated poly(arylene ether) copolymers containing aromatic nitriles

Sumner, Michael J.; Harrison, William; Weyers, R.M; Kim, Yu Seung; McGrath, James E.; Riffle, Judy S.; Brink, A. E.; Brink, M.

doi:10.1016/j.memsci.2004.03.031

Cited by 183 publications

(106 citation statements)

References 23 publications

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“…A disulfonated poly(arylene ether benzonitrile) copolymer containing 6F-BPA (6FCN, see Fig. 20(b)) had much less water uptake than both the copolymer without benzonitrile groups and the copolymer without fluorine and nitrile groups at equivalent IECs; the proton conductivities of the structures were all comparable [102]. In particular, Kim et al reported that the 6FCN copolymer displayed the highest fuel cell performance [103].…”

Section: Introduction Of Functional Groupsmentioning

confidence: 99%

Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs)

Park

Lee

Guiver

2011

Progress in Polymer Science

618

229

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Section: Introduction Of Functional Groupsmentioning

confidence: 99%

Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs)

Park

Lee

Guiver

2011

Progress in Polymer Science

618

229

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“…[4][5][6] Consequently, much progress has been made to develop novel hydrocarbon PEMs based on sulfonated aromatic polymers, which have good physical properties and are inexpensive. The most widely investigated PEMs include sulfonated derivatives of poly(arylene ether sulfone)s (SPAES), 7,8 poly-(arylene ether ether ketone)s (SPEEK), [9][10][11] poly(arylene sulfide sulfone)s (SPSS), 12,13 poly(arylene ether nitrile)s (SPAEEN), [14][15][16] polyimides (SPI), [17][18][19][20][21] and polyphenylenes (PP). [22][23][24] Many hydrocarbon polymers show sufficiently high conductivities only at high ion-exchange capacities (IEC)s, which causes extensive water uptake above a critical temperature (percolation threshold), or a dramatic loss of mechanical properties due to dimensional swelling that render them unsuitable for practical PEM applications.…”

Section: Introductionmentioning

confidence: 99%

Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups

et al. 2010

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New monomers containing two or four pendent phenyl groups were synthesized by bromination of bis(4-fluorophenyl) sulfone, followed by Suzuki coupling with benzeneboronic acid. The resulting monomers were converted to the corresponding sulfonated monomers having two or four pendent sulfonic acid groups, predominately at the p-phenyl position. Aromatic nucleophilic substitution (SNAr) polycondensation using the di- and tetrasulfonated monomers provided sulfonated poly(arylene ether sulfone) copolymers S2-PAES-xx and S4-PAES-xx, respectively, where xx refers to the molar ratio of the sulfonated to non-sulfonated pendent phenyl monomer. Copoly(arylene ether sulfone)s based on the corresponding non-sulfonated monomers were also synthesized for a parallel study on postpolymerization sulfonation of these copolymers. Postsulfonation occurred predominately at the para-pendent phenyl site, and the reactions were complete within a short time (about 30 min), without evidence of chain degradation. Flexible and tough membranes having high mechanical strength were obtained by solution casting of all four series of copolymers. The copolymers with two or four pendent sulfonic acid groups had high proton conductivities in the range of 44−142 mS/cm for S2-PAES-xx and 51−158 mS/cm for S4-PAES-xx at room temperature, respectively. The methanol permeabilities of these copolymers were in the range of 0.8 × 10−8−15.0 × 10−7 cm2/s, which is lower than Nafion (16.7 × 10−7 cm2/s). The S4-PAES-xx membranes displayed better properties (lower water uptake and higher proton conductivities) than the S2-PAES-xx membranes, which can be attributed to the more blocky architecture of the sulfonic acid groups in the S4 membranes. A combination of high proton conductivities, low water uptake, and low methanol permeabilities for some of the obtained copolymers indicated that they are good candidate materials for proton exchange membrane in fuel cell applications.

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“…Their good mechanical properties, high chemical and thermal resistance, and strongly polar pendant nitrile groups, make poly(aryl ether nitrile)s good candidates for matrices in advanced composites in aerospace industries. It is also found that the introduction of nitrile groups into proton conductive sulfonated thermoplastics decreased their moisture absorption [41,42]. In addition, it is also believed that the presence of nitriles have the potential to promote adhesion of the polymers to heteropolyacids in composite membranes or to electrodes in the preparation of MEAs.…”

Section: Introductionmentioning

confidence: 99%

Low-swelling proton-conducting copoly(aryl ether nitrile)s containing naphthalene structure with sulfonic acid groups meta to the ether linkage

Gao

Robertson²,

Guiver³

et al. 2006

Polymer

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Wholly aromatic poly(aryl ether ether nitrile)s containing naphthalene structure with sulfonic acid groups meta to ether linkage (m-SPAEEN), intended for fuel cells applications as proton conducting membrane materials, were prepared via nucleophilic substitution polycondensation reactions. The incorporation of rigid naphthalene structure with meta-sulfonic acid groups was with the intent of improving the aggregation of hydrophilic and hydrophobic domains and to increase the acidity and conductivities. m-SPAEEN copolymers were readily synthesized by potassium carbonate mediated nucleophilic polycondensation reactions of commercially available monomers: 2,6-difluorobenzonitrile (2,6-DFBN), 2,8-dihydroxynaphthalene-6-sulfonate sodium salt (2,8-DHNS-6), and 4,4 0 -biphenol (4,4 0 -BP) in dimethylsulfoxide (DMSO) at 160-170 8C. The sulfonic acid group content (SC), expressed as a number per repeat unit of polymer, ranged from 0 to 0.6 and was readily controlled by changing the feed ratio of 2,8-DHNS-6 to 2,6-DFBN. High thermal stability of m-SPAEEN copolymers was indicated by observed glass transition temperatures (T g s) ranging from 223 to 335 8C in sodium salt form and from 230 to 260 8C in acid form (m-SPAEENH) and decomposition temperatures (T d )s over 250 8C in acid form and over 350 8C in sodium form in both nitrogen and air. All m-SPAEENH copolymers exhibited reasonable flexibility and tensile strength in the range of 39-78 MPa, indicating they were mechanically stronger than Nafion w 117, which had an approximate value of 10 MPa under the same test conditions. As expected, m-SPAEENH copolymers showed considerably reduced moisture absorption compared to previously prepared sulfonated hydroquinone based poly(aryl ether nitrile). m-SPAEENH copolymers also showed improved proton conductivities. Proton conductivity curves parallel to that of Nafion 117 were obtained with proton conductivity of 10 K1 S/cm at equivalent ion exchange capacities (IEC) of 1.6 and 1.9, comparable to Nafion w 117. The best compromise combining PEM mechanical strength, water swelling and proton conductivity, was achieved at SC of 0.5 and 0.6. Crown

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Novel proton conducting sulfonated poly(arylene ether) copolymers containing aromatic nitriles

Cited by 183 publications

References 23 publications

Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs)

Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs)

Polymer Electrolyte Membranes Derived from New Sulfone Monomers with Pendent Sulfonic Acid Groups

Low-swelling proton-conducting copoly(aryl ether nitrile)s containing naphthalene structure with sulfonic acid groups meta to the ether linkage

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