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separation that forms the primary hydrophilic channels and the hydrophobic dom m e h a i f k h z d ( - e t h n c Materials 2021, 14, 1617 which the hydrophilic covalent crosslinks are intercalated in the hydrophobic do constitute the secondary hydrophilic channel. This crosslinking strategy is more p to strengthen the membrane matrix against swelling and high liquid fuel diffusion ticular feature of this design is that the crosslink is capable of maintaini2nogf 2p0roton as well as dimensional stability. In addition, the secondary hydrophilic channels sidered as “waterways canals” distributed in the integrated hydrophobic doma siintuthaetPioEnMi.sOthertehfaonrethcesaeteagpporoiaccahlelys, mdiftifgearteionntoffrothme ptrhoteoncocnonvdeunctivointya–lmcercohsasn-ilcianlking o property trade-off in aliphatic-based PEMs is few and far between in the literature. drophobic blocks which inevitably eliminates part of the proton transport networ This study extends a ternary statistical copolymer of poly(acrylonitrile-co-glycidyl spreading local isolations, and proton conduction through the membrane has t methacrylate-co-sulfopropyl methacrylate), P(AN-co-GMA-co-SPM) to a block copolymer over a longer path. The schematic diagram (Figure 1) illustrates the roles of the chain structure, P[(AN-co-GMA)-b-SPM], which is an ionomer in functionality. The ternary wioanyomsecranchaalisn”sianrertehseonlvtiiendgwtihtheeraecdhuoctehderpbryoatohnydcronphnielicticvoivtayleintctrhoesshlinykdrthoapthilicc is proton conducting in nature. The design first and foremost leverages on the ordered The expected outcome is therefore some relief of the conductivity–mechanical p structure of a block copolymer to synchronize the hydrophobicity–hydrophilicity difference conundrum. in the membrane matrix. This is done to drive a more pronounced microscale phase The actual synthesis of a series of the SPM-based diblock ionomers was reali separation that forms the primary hydrophilic channels and the hydrophobic domains, in one-pot atom transfer radical polymerization (ATRP) technique conducted in which the hydrophilic covalent crosslinks are intercalated in the hydrophobic domains to constitute the secondary hydrophilic channel. This crosslinking strategy is more pertinent aprotic solvent. The selection of AN and methacrylates (SPM and GMA) aime to strengthen the membrane matrix against swelling and high liquid fuel diffusion. A structural stability and the inherent alcohol resistance [10]. The GMA in the poly particular feature of this design is that the crosslink is capable of maintaining proton GMA) block offers the in-situ cross-linking anchors to carry out hydrophilic cross hopping as well as dimensional stability. In addition, the secondary hydrophilic channels In addition to the structural reinforcement effects generally expected from cross are considered as “waterways canals” distributed in the integrated hydrophobic domains. [T1h1e],stithueathioyndirsotphehrielfiocre–OcaHtegaonridca–llNy Hdif–fegrernotufprosmwtehreecfoonrvmenetidonfarol cmrotshs-elinckrionsgsloifnking r the hydrophobic blocks which inevitably eliminates part of the proton transport network which could be used to transport protons and water molecules through the “wa due to spreading local isolations, and proton conduction through the membrane has canals”; therefore leading to an overall improvement in proton conduction wit to occur over a longer path. The schematic diagram (Figure 1) illustrates the roles of compensatory effect between conductivity and mechanical properties. A higher the “waterways canals” in resolving the reduced proton connectivity in the hydrophilic dcheannsniteyls.oTuhtepeuxtpfercotemdoDuitrceocmteMisetthhearenforleFsuomeleCrellielf(DofMthFeCco)n,deuscpteivciitayl–lmyeacthahnigichalmetha property conundrum. concentrations, was therefore made possible. Figure 1. Schematic illustration showing the secondary hydrophilic channels (“waterway canals”) Figure 1. Schematic illustration showing the secondary hydrophilic channels (“waterway made possible by the hydrophilic covalent cross-linking of the diblock ionomers. made possible by the hydrophilic covalent cross-linking of the diblock ionomers. The actual synthesis of a series of the SPM-based diblock ionomers was realized by a one-pot atom transfer radical polymerization (ATRP) technique conducted in a polar apro- tic solvent. The selection of AN and methacrylates (SPM and GMA) aimed to the structural stability and the inherent alcohol resistance [10]. The GMA in the poly(AN-co-GMA) block offers the in-situ cross-linking anchors to carry out hydrophilic crosslinking. In addition to the structural reinforcement effects generally expected from cross-linking [11], the hy- drophilic –OH and –NH– groups were formed from the crosslinking reaction, which could be used to transport protons and water molecules through the “waterways canals”; there- fore leading to an overall improvement in proton conduction without the compensatory effect between conductivity and mechanical properties. A higher energy density output from Direct Methanol Fuel Cell (DMFC), especially at high methanol feed concentrations, was therefore made possible.PDF Image | Hydrophilic Cross-Linked Aliphatic Hydrocarbon Diblock Copolymer
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