Polycondensation of structurally divergent tetraamine monomers with dicarboxylic acids to synthesize polybenzimidazole copolymers for polymer electrolyte membranes

Maity, Sudhangshu; Jana, Tushar

doi:10.1002/pi.4830

Cited by 14 publications

(8 citation statements)

References 61 publications

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“…It is widely known that polybenzimidazole is a hygroscopic polymer and it has a high affinity to form stronger intermolecular interactions with water molecules, which severely influences the dimensional stability of the membrane. − After immersing the membranes in distilled water for 3 days, we observed that the amount of water uptake (WU) of PyOPBI, Me-PyOPBI, Ph-PyOPBI, and Ph(CF 3 )-PyOPBI membranes is 13.21, 17.01, 20.55, and 16.56 wt %, respectively (Figure S9). It is quite evident from the data that the introduction of pendant type side groups in PyOPBI backbone has increased the WU; however, Ph(CF 3 )-PyOPBI displays the least WU among the pendant type polymers because of the hydrophobic nature owing to the presence of trifluoro functionality in the polymer backbone.…”

Section: Resultsmentioning

confidence: 97%

“…To address this concern, we recently synthesized pyridine-bridged PBI (PyPBI), which was obtained by poly condensing 2,6-bis (3′,4′-diaminophenyl)-4-phenylpyridine (PyTAB), a tetraamine monomer which was made readily, with varieties of dicarboxylic acids. Several PyPBIs synthesized so far showed good solubility and processability along with very good thermal, mechanical and chemical stabilities. − However, it was observed that the membranes of PyPBI get dissolved in concentrated (85%) PA and therefore needs attention. Recently, we addressed this problem by cross-linking the PyPBI chains using BrPPO, but this approach hinders the solubility .…”

Section: Resultsmentioning

confidence: 99%

“…Very recently, our research group reported a novel type of readily accessible and less-expensive nitrogen-rich heterocyclic tetraamine, a 2,6-bis(3′,4′-diaminophenyl)-4-phenylpyridine (PyTAB)-based homo and copolymer of PBI, named as PyPBI, as a PEM candidate that fulfilled most of the needs for application in HT-PEMFCs. − The good solubility, higher affinity with PA, superior mechanical and chemical properties, and readily synthesizable raw materials make PyPBI membranes a sustainable alternative to conventional PBI polymeric materials. However, questions remain regarding the structural instability in highly concentrated PA and the PEM performance.…”

Section: Introductionmentioning

confidence: 99%

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Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Harilal

Shukla

Ghosh

et al. 2021

ACS Appl. Energy Mater.

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Although pyridine bridged oxypolybenzimidazole (PyOPBI) membranes are considered to be promising hightemperature proton exchange membrane (HT-PEM) materials that have the potential to overcome many obstacles such as solubility, membrane processability, cost, etc., of the mainstream conventional polybenzimidazole (PBI)-based HT-PEM, the weak structural stability of PyOPBI in concentrated phosphoric acid (PA) and poor dimensional and mechanical stability have been the crucial issues restraining the performance. To mitigate these bottlenecks, in this work, we successfully synthesized three types of PyOPBIs with flexible aryl ether backbones and bulky substituents by polycondensation reaction of various aryl diacids and pyridine-bridged tetraamine 2,6-bis(3′,4′-diaminophenyl)-4-phenylpyridine (PyTAB) in Eaton's reagent followed by casting as HT-PEMs. Three designed bulky substitute containing PyOPBI membranes showed considerably high PA loading capacity (16−22 mol of PA/repeat unit) and proton conductivity (0.04−0.078 S/cm) at 180 °C as compared to earlier reported unsubstituted PyOPBI membranes (14 mol of PA/repeat unit and 0.007 S/cm at 180 °C). In addition, the obtained membranes showcased good chemical, mechanical, thermal, and long-term conductivity stabilities and outstanding stability in concentrated PA. The pendent groups and the bulkiness of the backbone are believed to be the cause behind better stability and facilitating proton transport that results in higher proton conductivity. The single cell made from the membrane electrode assembly of these bulky substituted PyOPBI membranes displayed a peak power density in the range of 144−240 mW cm −2 under H 2 /O 2 at 160 °C, which is considerably higher than that for unsubstituted PyOPBI membrane (90.4 mW cm −2 ). Overall, the current results provide an effective strategy to explore the benefits of structural modulation of PyOPBI using various structurally divergent diacids to enhance HT-PEM properties and suggest a scalable route for the advancement of PBI-based HT-PEM fuel cells.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Harilal

Shukla

Ghosh

et al. 2021

ACS Appl. Energy Mater.

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“…This can be accomplished by using different aromatic/aliphatic dialdehyde and tetraamine precursors (monomers) prior to the condensation polymerization. [27][28][29][30][31][32] Another synthetic method is N-substitution of PBI, which others have attempted with varying success. [33][34][35][36] Other PBI materials have been derived from synthetic techniques by crosslinking with other functionalized compounds, such as halogenated alkyl/phenyl compounds, aldehydes and alcohols.…”

Section: Introductionmentioning

confidence: 99%

Blended polybenzimidazole and melamine-co-formaldehyde thermosets

Klaehn

Orme

Peterson

2016

Journal of Membrane Science

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Polybenzimidazole [PBI; poly-2,2'(m-phenylene)-5,5'-bibenzimidazole] is known to have excellent high temperature stability (up to 450 ºC) and superb H 2 /CO 2 selectivity compared to most high performance (HP) polymers. New blended thermosets were made with PBI and poly(melamine co-formaldehyde) [PMF] to produce stable thin-films after thermal processing at 220-250 ºC. PBI film formation is difficult, because of challenging processing techniques. As a result, the film tends to fracture and fissure due to processing aids and stabilizers (salt/acid additives) that are found in PBI solutions above 10 weight percent. Therefore, PBI dense thinfilms are fragile and prone to fracturing during film processing. The reported PBI-PMF blended thermosets do not have stabilizers, and can be made into dense thin-films. The PBI-PMF films were analyzed using pure and mixed gas permeability measurement techniques. At 250 °C, the © 2016. This manuscript version is made available under the Elsevier user license http://www.elsevier.com/open-access/userlicense/1.0/ data show H 2 /CO 2 gas selectivities greater than 13. Also from the gas permeation data, the energy of activation (Ep) of a mixed gas stream for PBI-PMF shows that hydrogen permeates more easily than the other gases, while the permeabilities for the larger kinetic diameter gases are greatly diminished. In addition, the FT-IR spectra show that the PBI-PMF films have changed from parent PBI after thermal processing, and PMF dominates the spectra even in minor percent compositions. Overall, the reported PBI-PMF thermoset films show good stability which can be used for high temperature gas separation.

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“…Several modified PBI based membranes are reported in the literature. Pyridine based PBI membranes with improved proton conductivity and oxidative stability; membranes of PBI segmented block copolymers and random block copolymers of PBI by using tetra-amine and dicarboxylic acid combinations have also been synthesized and examined as their applicability in PEMFCs [20][21][22]. However, among the promising candidates, sulfonated poly (arylene ether sulfone)s (SPAES)s are well-known engineering thermoplastics and these are reasonably good choice for high temperature operating PEMFCs.…”

Section: Introductionmentioning

confidence: 99%

Hydroquinone based sulfonated poly (arylene ether sulfone) copolymer as proton exchange membrane for fuel cell applications

Kiran¹,

Awasthi²,

Gaur³

2015

Express Polym. Lett.

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Abstract. Synthesis of sulfonated poly (arylene ether sulfone) copolymer by direct copolymerization of 4,4!-bis(4-hydroxyphenyl)valeric acid, benzene 1,4-diol and synthesized sulfonated 4,4!-difluorodiphenylsulfone and its characterization by using FTIR (Fourier Transform Infrared) and NMR (Nuclear Magnetic Resonance) spectroscopic techniques have been performed. The copolymer was subsequently cross-linked with 4, 4!(hexafluoroisopropylidene)diphenol epoxy resin by thermal curing reaction to synthesize crosslinked membranes. The evaluation of properties showed reduction in water and methanol uptake, ion exchange capacity, proton conductivity with simultaneous enhancement in oxidative stability of the crosslinked membranes as compared to pristine membrane. The performance of the membranes has also been evaluated in terms of thermal stability, morphology, mechanical strength and methanol permeability by using Thermo gravimetric analyzer, Differential scanning calorimetery, Atomic force microscopy, XPERT-PRO diffractometer, universal testing machine and diffusion cell, respectively. The results demonstrated that the crosslinked membranes exhibited high thermal stability with phase separation, restrained crystallinity, acceptable mechanical properties and methanol permeability. Therefore, these can serve as promising proton exchange membranes for fuel cell applications.

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Polycondensation of structurally divergent tetraamine monomers with dicarboxylic acids to synthesize polybenzimidazole copolymers for polymer electrolyte membranes

Abstract: Polybenzimidazole copolymers were synthesized by varying compositions of tetraamines monomers in polymerization feed with a single dicarboxylic acid instead of conventional method where two acids were used.

Cited by 14 publications

References 61 publications

Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Pyridine-Bridged Polybenzimidazole for Use in High-Temperature PEM Fuel Cells

Blended polybenzimidazole and melamine-co-formaldehyde thermosets

Hydroquinone based sulfonated poly (arylene ether sulfone) copolymer as proton exchange membrane for fuel cell applications

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