Synthesis and Proton Conductivity of Highly Sulfonated Poly(thiophenylene)

Miyatake, Kenji; Shouji, Eiichi; Yamamoto, Kimihisa; Tsuchida, Eishun

doi:10.1021/ma961830t

Cited by 76 publications

(49 citation statements)

References 31 publications

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“…Sulfonation can be performed in several ways, as follows: (1) by direct sulfonation in concentrated sulfuric acid, chlorosulfonic acid, 182-185 sulfur trioxide, or its complex with tri-ethyl-phosphate [186][187][188] ; (2) by lithiation-sulfonation-oxidation 189 ; (3) by chemically grafting a group containing a sulfonic acid onto a polymer 190 ; (4) by graft copolymerization using highenergy radiation followed by sulfonation of the aromatic component 151,152 ; or (5) by synthesis from monomers bearing sulfonic acid groups. 191 For developing polymer electrolytes for fuel cells, the most widely investigated systems include sulfonation of polysulfones (PSF) or polyethersulfone (PES), 189,[192][193][194][195][196] polyetheretherketone (PEEK) 41,182,[197][198][199][200] or polyetheretherketoneketone (PEEKK), 11 polybenzimidazoles (PBI), 41,43,190,201 polyimides (PI), 191,[202][203][204][205] polyphenylenes (PP), poly(4-phenoxybenzoyl-1,4-phenylene) (PPBP), 41,200,206 andrigidrodpoly(p-phenylenes)(PP) 179,180 ), and other polymers 207 (such as polyphenylenesulfide (PPS), 208,209 polyphenylene oxide (PPO), 210 polythiophenylene, 211 polyphenylquinoxaline, 212 and polyphosphazene 213…”

Section: Reviewsis Normally Crystalline Having a Melting Point Of 285°cmentioning

confidence: 99%

Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C

et al. 2003

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The state-of-the-art of polymer electrolyte membrane fuel cell (PEMFC) technology is based on perfluorosulfonic acid (PFSA) polymer membranes operating at a typical temperature of 80°C. Some of the key issues and shortcomings of the PFSA-based PEMFC technology are briefly discussed. These include water management, CO poisoning, hydrogen, reformate and methanol as fuels, cooling, and heat recovery. As a means to solve these shortcomings, hightemperature polymer electrolyte membranes for operation above 100°C are under active development. This treatise is devoted to a review of the area encompassing modified PFSA membranes, alternative sulfonated polymer and their composite membranes, and acidbase complex membranes. PFSA membranes have been modified by swelling with nonvolatile solvents and preparing composites with hydrophilic oxides and solid proton conductors. DMFC and H 2 /O 2 (air) cells based on modified PFSA membranes have been successfully operated at temperatures up to 120°C under ambient pressure and up to 150°C under 3-5 atm. Alternative polymers are selected from silicon-and fluorine-containing inorganic polymers or aromatic hydrocarbon polymers and functionalized by sulfonation. The sulfonated hydrocarbons and their inorganic composites are potentially promising for high-temperature operation. High conductivities have been obtained at temperatures up to 180°C. Acid-base complex membranes constitute another class of electrolyte membranes. A high-temperature PEMFC based on H 3 PO 4 -doped PBI has been demonstrated for operation at temperatures up to 200°C under ambient pressure. The advanced features include high CO tolerance, simple thermal and water management, and possible integration with the fuel processing unit.

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Section: Reviewsis Normally Crystalline Having a Melting Point Of 285°cmentioning

confidence: 99%

Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C

et al. 2003

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“…The substitution of sulfonic acid groups on the phenyl ring, which attached to the electron withdrawing imide units, might contribute to the high thermal stability of the C-S bonds. 17,19 Since the high thermal stability of sulfonic acid groups is the desired property of sulfonated polymers for practical applications as polymer electrolytes, 17, 18 the arenesulfonated HBPI might be a promising candidate to be used in polymer electrolyte fuel cell systems. The bulk degradation of polyimide backbone began at around 480 • C for both polymers.…”

Section: Polymer Propertiesmentioning

confidence: 99%

Synthesis of Arenesulfonated Hyperbranched Polyimide from A2 + B3 Monomers

Chen

Yin

2003

Polym J

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KEY WORDSSynthesis / Hyperbranched / Dendritic / Polyimide / Arenesulfonated Polymer / Hyperbanched polymers have drawn considerable attentions in recent years for their unique physical and chemical properties due to their dendritic structure. [1][2][3][4][5] The dendritic polymers were thought to have similar properties as the perfectly branched dendrimers, such as low viscosity, good solubility, thermal property, and chemical reactivity. Therefore, hyperbranched polymers might be an alternative and cost-effective substitute for dendrimers under certain conditions, and would be promising candidates for industrial applications, because one-step polymerizations are suitable for mass production. 4 Up to now, some attempts have been reported on their applications as novel functional polymers, such as encapsulation micelles for dye molecules, 6, 7 crosslinking agents, 8,9 and nonlinear optical materials. [10][11][12] The large number of reactive groups at the periphery of hyperbranched polymers offers an easy way for further modification and special applications. [1][2][3][4] Functionalization can be performed by the reaction of the end groups with materials containing certain functional groups. The resulting functional polymers were thought to have high functionality because of the decreased chain entanglement and the peripheral location of the functional groups. 3,4 In previous work, 13 we reported the synthesis and characterization of a series of hyperbranched polyimides (HBPIs) based on a new tramine (B 3 ), 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), and conventional dianhydrides (A 2 ). Different monomer addition methods and monomer molar ratios resulted in HBPIs with amino-or anhydride-terminated groups. The amino-terminated HBPIs had degrees of branching (DB) in the range of 0.62-0.67, while the anhydrideterminated and chemically modified HBPIs gave a DB value of 1 according to 1 H NMR analysis with the help of model compounds. In present paper, we describe our initial results on the synthesis of arenesulfonated HBPI (S-HBPI) from 4, 4 -(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and TAPOB, which may be potentially applied as proton conducting polymer. Sulfonation of the polymer was directly fulfilled during the course of polymerization of poly(amic acid) precursor, by modification of the terminal anhydride groups with sulfanilic acid, and then the precursor was chemically imidized in the presence of acetic anhydride and triethylamine. EXPERIMENTAL ChemicalsN-Methyl-2-pyrrolidone (NMP) was distilled from calcium hydride under reduced pressure. 4, 4 -(Hexafluoroisopropylidene)diphthalic anhydride (6FDA) was obtained commercially, and purified by recrystallization from acetic anhydride before use. 1,3,5-Tris(4-aminophenoxy)benzene (TAPOB) was synthesized in our lab. 13 Other solvents and reagents were used as received. MeasurementsInfrared spectroscopic (IR), differential scanning calorimetric (DSC, at a heating rate of 10 • C min −1 in nitrogen) and thermogravimetric (TGA, at a heating rate of 10 • C...

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“…Proton conducting polymers have been recently developed, [1][2][3] and many polymers with sulfuric and/ or phosphonic acid groups onto thermal stable aromatic polymers that include poly(ether ether ketone), 4,5 polysulfone, 6,7 poly(aryl ether sulfone), 8 poly (aryl ether phthalazines), 9 and poly(phenylene sulfide) 10,11 have been reported. Although the polymers have a higher thermal stability and glass transition temperature (T g ) than those of Nafion (T g ¼ 115 C), most of them failed to be used as proton conducting membranes with enough lifetime.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of sulfonated aromatic fluoro‐polymers

Endo

Yamade

2010

J of Applied Polymer Sci

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Polycondensation of perfluorobiphenyl with a,a-bis(4-hydroxyphenyl)ethylbenzene and/or 9,9-bis(4-hydroxyphenyl)fluorene was investigated. The polycondensation of perfluorobiphenyl with a,a-bis(4-hydroxyphenyl) ethylbenzene and/or 9,9-bis(4-hydroxyphenyl)fluorene proceeded at low-temperature to a give high-molecular weight and thermal stable polymers. The 19 F-NMR spectra of the polymers indicate that the polymers consists of predominantly 1,4-phenylene structure with respect to the perfluoroaromatic compound. The sulfonation of the polymers obtained from the polycondensation occurred at the phenyl groups and fluorenyl side chain. A tough and smooth film was prepared by a casting method from DMF solution of the sulfonated polymer. The films showed hydrolytic and oxidative stabilities, and a high-proton conductivity.

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Synthesis and Proton Conductivity of Highly Sulfonated Poly(thiophenylene)

Cited by 76 publications

References 31 publications

Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C

Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C

Synthesis of Arenesulfonated Hyperbranched Polyimide from A2 + B3 Monomers

Synthesis and properties of sulfonated aromatic fluoro‐polymers

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