Polymer Electrolyte Membranes Based on Multiblock Poly(phenylene ether ketone)s with Pendant Alkylsulfonic Acids: Effects on the Isomeric Configuration and Ion Transport Mechanism

Two structural variations of multiblock poly(phenylene ether ketone)s (bSPPEKs) with pendant alkylsulfonic acids were prepared by a polycondensation reaction between oligomeric difluoro and diphenoxide precursors, followed by successive demethylation and sulfonation processes. Two isomers, bis[4-fluoro-3-(4′-methoxylbenzoyl)]biphenyl (p-BFMBP) and bis[5-fluoro-2-(4′-methoxylbenzoyl)]biphenyl (m-BFMBP), were prepared as the difluoro starting monomers. The corresponding polymer membranes were obtained with good mechanical stability to facilitate the further characterizations. The morphology of bSPPEKs was confirmed by atomic force microscopy, from which the distinct phase separation could be identified with the average hydrophilic domain size of ca. 15–20 nm for the m-bSPPEKs. It is worth noting that both m- and p-bSPPEKs show quite comparable, or even better, ion conduction capacities than commercially available Nafion membrane, especially under low relative humidity conditions (30–50%), suggesting their p...

[1]  Yunqi Li,et al.  Enhanced proton conductivity of sulfonated poly(p-phenylene-co-aryl ether ketone) proton exchange membranes with controlled microblock structure , 2015 .

[2]  Tomoya Higashihara,et al.  Polyphenylenes and the related copolymer membranes for electrochemical device applications , 2014 .

[3]  N. Mack,et al.  Controlled disulfonated poly(arylene ether sulfone) multiblock copolymers for direct methanol fuel cells. , 2014, ACS applied materials & interfaces.

[4]  Nanwen Li,et al.  Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers , 2014 .

[5]  Zhenhua Jiang,et al.  Poly(aryl ether ketone) containing flexible tetra-sulfonated side chains as proton exchange membranes , 2014 .

[6]  K. Kreuer.  Ion Conducting Membranes for Fuel Cells and Other Electrochemical Devices , 2014 .

[7]  D. Yan,et al.  Sulfonated poly(arylene ether phosphine oxide)s with various distributions and contents of pendant sulfonic acid groups synthesized by direct polycondensation , 2014 .

[8]  T. Hayakawa,et al.  Polymer electrolyte membranes based on poly(phenylene ether)s with sulfonic acid via long alkyl side chains , 2013 .

[9]  K. Miyatake,et al.  Sulfonated poly(arylene ether phosphine oxide ketone) block copolymers as oxidatively stable proton conductive membranes. , 2013, ACS applied materials & interfaces.

[10]  G. Voth,et al.  Molecular Dynamics Simulations of Proton Transport in 3M and Nafion Perfluorosulfonic Acid Membranes , 2013 .

[11]  Tomoya Higashihara,et al.  Polymer electrolyte membranes based on poly(m-phenylene)s with sulfonic acid via long alkyl side chains , 2013 .

[12]  S. Jang,et al.  Polymer electrolyte membranes based on poly(arylene ether sulfone) with pendant perfluorosulfonic acid , 2013 .

[13]  G. Giffin,et al.  Interplay between structure and relaxations in perfluorosulfonic acid proton conducting membranes. , 2013, Journal of the American Chemical Society.

[14]  Dong Won Shin,et al.  A clustered sulfonated poly(ether sulfone) based on a new fluorene-based bisphenol monomer , 2012 .

[15]  Lianjun Wang,et al.  Preparation and properties of novel sulfonated poly(p-phenylene-co-aryl ether ketone)s for polymer electrolyte fuel cell applications , 2012 .

[16]  Ryszard Wycisk,et al.  Synthesis and characterization of poly(para-phenylene disulfonic acid), its copolymers and their n-alkylbenzene grafts as proton exchange membranes: high conductivity at low relative humidity , 2012 .

[17]  K. Miyatake,et al.  Block poly(arylene ether sulfone ketone)s containing densely sulfonated linear hydrophilic segments as proton conductive membranes , 2012 .

[18]  Y. Takeoka,et al.  Synthesis of Hydrophilic-Hydrophobic Block Copolymer Ionomers Based on Polyphenylenes. , 2012, ACS macro letters.

[19]  Ying‐Ling Liu.  Developments of highly proton-conductive sulfonated polymers for proton exchange membrane fuel cells , 2012 .

[20]  G. Voth,et al.  Mesoscale Simulation of Proton Transport in Proton Exchange Membranes , 2012 .

[21]  Hongwei Zhang,et al.  Recent development of polymer electrolyte membranes for fuel cells. , 2012, Chemical reviews.

[22]  P. Jannasch,et al.  Multiblock Copolymers with Highly Sulfonated Blocks Containing Di‐ and Tetrasulfonated Arylene Sulfone Segments for Proton Exchange Membrane Fuel Cell Applications , 2012 .

[23]  M. Guiver,et al.  A new class of highly-conducting polymer electrolyte membranes: Aromatic ABA triblock copolymers , 2012 .

[24]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[25]  Lianjun Wang,et al.  Graft-crosslinked copolymers based on poly(arylene ether ketone)-gc-sulfonated poly(arylene ether sulfone) for PEMFC applications. , 2011, Macromolecular rapid communications.

[26]  B. Freeman,et al.  Effect of Free Volume on Water and Salt Transport Properties in Directly Copolymerized Disulfonated Poly(arylene ether sulfone) Random Copolymers , 2011 .

[27]  Lianjun Wang,et al.  Preparation and properties of sulfonated poly(phenylene arylene)/sulfonated polyimide (SPA/SPI) blend membranes for polymer electrolyte membrane fuel cell applications , 2011 .

[28]  Michihisa Koyama,et al.  Chemical Degradation Mechanism of Model Compound, CF3 ( CF2 ) 3O ( CF2 ) 2OCF2SO3H , of PFSA Polymer by Attack of Hydroxyl Radical in PEMFCs , 2010 .

[29]  S. Paddison,et al.  Mesoscale modeling of hydrated morphologies of 3M perfluorosulfonic acid-based fuel cell electrolytes. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[30]  S. Paddison,et al.  A comparative study of the hydrated morphologies of perfluorosulfonic acid fuel cell membranes with mesoscopic simulations , 2008 .

[31]  B. Freeman,et al.  Gas separation properties of aromatic polyimides , 2003 .

[32]  Michael A. Hickner,et al.  Direct polymerization of sulfonated poly(arylene ether sulfone) random (statistical) copolymers: candidates for new proton exchange membranes , 2002 .