Sulfonated fluorinated poly arylene

H. Ghassemi, J.E. McGrath, T.A. Zawodzinski, Jr., Multiblock sulfonated-fluorinated poly(arylene ether)s for a proton exchange membrane fuel cell. Polymer 2006, 47(11), 4132-M139. 

Scheme 2.28 Structure of sulfonated fluorinated poly(arylene ether) containing naphthalene moieties in the main chain. Taken from Ref. [137],...

Scheme 2.36 Structures of sulfonated fluorinated poly(arylene ether)s using different bisphenol units in the polymer main chain.

Table 2.12 Interesting Set of Properties Obtained for Synthesized Sulfonated Fluorinated Poly(Arylene Ether)s Including Thermal Degradation, Mechanical Properties, Oxidative Stability, Water Uptake, Swelling and Proton Conductivity for Variations of DS... 

Furthermore, Banerjee and group prepared sulfonated fluorinated poly(arylene ether sulfone) (IBQSH-XX) copolymers (where XX=20, 30, 40, 50, and 60 and DS=0.16, 0.26, 0.39, 0.47, 0.56, respectively) based on imidoaryl biphenol, namely, 3,8-few(4-hydroxyphenyl)-A -phenyl-l,2-naph-thaUmide (IB), by direct copolymerization with SDCDPS as the sulfonated monomer and QBF as the fluorinated monomer [160]. Sulfonated copolymers were obtained with M values in the range 41,200-60,200g/mol with D values in the range 0.96-1.89 the trend increased with an increase in the DS (0.16-0.56 as per H-NMR spectra). Scheme 2.36 shows a representative structure of sulfonated fluorinated poly(arylene ether sulfone) containing IB... 

Densely sulfonated fluorinated poly(arylene ether ketone) copolymers (SPAEK-xx, where xx=15, 20, 25, 30, and 35) was prepared by Pang et al. [172] and evaluated for proton conductivity. The Tg of the copolymers was in the range 193-231 °C and the T s% was in the range 364—390 °C, with a decreasing trend with an increase in the DS. The structure of the tetra-sulfonated fluorinated poly(arylene ether ketone) copolymer is shown in Fig. 2.11(a). 

Figure 2.11 (a) Structure of tetra-sulfonated fluorinated poly(arylene ether ketone) copolymer (taken from Ref. [172]) (b) TEM image of SPAEK-35. Reproduced with permission from Ref [172],... 

Scheme 2.46 Structure of comb-shaped densely sulfonated fluorinated poly(arylene ether)s with four sulfonic...

FIGURE 4.13 TGA traces of sulfonated-fluorinated poly(arylene ether sulfone)s in the salt form (a) and acid form (b) (under N2). (Reprinted after modification from Ghassemi, H. et al.. Polymer, 47(11), 4132, 2006. With permission.)... 

In 2006, McGrath and coworkers reported multiblock sulfonated-fluorinated poly(arylene ether sulfone)s (MB) for PEMs by the nucleophilic aromatic substitution of the dialkali metal salt of bisphenol-terminated poly(arylene ether sulfone) and decafluorobiphenyl-terminated poly(arylene ether) [28] (Scheme 4.10). 

Another synthetic approach has been reported by Nakabayashi et al. [36]. As described earlier, mnltiblock sulfonated-fluorinated poly(arylene ether sulfone)s were prepared by the bisphenol-terminated poly(arylene ether sulfone) and decafluorobiphenyl-terminated poly(arylene ether), which was obtained by an excess amount of DFBP and bisphenol-terminated poly(arylene ether sulfone). However, considering the high reactivity of DFBP, multiblock copolymers can be obtained by connecting hydroxy-terminated oligomers with a small amount of DFBP. That is, DFB functions as a chain extender. The synthetic procedure is depicted in Scheme 4.11. 

Rreparation and Evaluation of Sulfonated-Fluorinated Poly(arylene ether)s Membranes for Rroton Exchange Membrane Fuel Cell (REMFC). Electrochimica Acta. 49 2315-2323. 

Qi, Y. Ding, J. Day, M. Jiang, J. Callender, C. L., Cross-linkable highly fluorinated poly(arylene ether ketones/sulfones) for optical waveguiding applications, Chem. Mater. 2005,17, 676-682. 

The vast catalogue of polymeric materials reviewed here included Nafion composite with inorganic and organic fillers, and non-fluorinated proton conducting membranes such as sulfonated polyimides, poly(arylene ether)s, polysulfones, poly (vinyl alcohol), polystyrenes, and acid-doped polybenzimidazoles. Anion-exchange membranes are also discussed because of the facile electro-oxidation of alcohols in alkaline media and because of the minimizatirHi of alcohol crossover in alkaline direct alcohol fuel cells. 

Chen Y, Guo R, Lee CH, Lee M, McGrath JE. Partly fluorinated poly(arylene ether ketone sulfone) hydrophihc-hydrophobic multiblock copolymers for fuel cell membranes. Int J Hydrogen Energy 2012 37(7) 6132-9. 

Lee HS, Roy A, Lane O, Lee M, McGrath JE. Synthesis and characterization of multiblock copolymers based on hydrophilic disulfonated poly(arylene ether sulfone) and hydrophobic partially fluorinated poly(arylene ether ketone) for fuel cell applications. J Polym Sci Part A Polym Chem 2010 48(l) 214-22. 

Scheme 2.23 Structure of fluorinated poly(arylene ether ketone) with sulfone moiety containing 1,4 naphthalene...

Mercer et al. [62] synthesized a fluorinated poly(arylene ether ketone) with sulfone moiety containing 1,4 naphthalene units (Scheme 2.23) and studied their properties. The polymer was soluble in polar aprotic solvents and in chloroform with an Mw 34,300g/mol. The Tg of the polymer was high as 205 °C and onset thermal degradation temperature was 502 °C in an air atmosphere. 

Kim et al. prepared highly fluorinated poly(arylene ether sulfone) [88] containing an ethynyl end group as thermal cross-linkable groups (Scheme 2.24) via nucleophilic aromatic substitution from 6F-BPA or 4,4 -(trifluoromethylphenylisopropylidene) diphenol (3FBPA) with an excess of pentafluorophenyl sulfone, followed by reaction with 3-ethylnylphenol, studied the effect of reaction temperature and time. 

Scheme 2.24 Structure of fluorinated poly(arylene ether sulfone) containing an ethynyl end group as thermal cross-linkable groups. Taken from Ref [88],...

Wang et al. reported clustered fluorene-based sul-fonated fluorinated poly(arylene ether sulfone) copolymers (SPAEs-xx where xx=25,30,33,36, and 39) containing four flexible pendant butylsulfonic acid (2PM-5) (Scheme 2.42) [176], All of the copolymers had good oxidative stability and retained weight... 

For PV application, fluorinated poly(arylene ether sulfone)s containing bulky cardo moiety and -CF3 groups have shown improvement in flux and separation factor owing to the increase in FFV and micro-phase-separated morphology allowing penetration of solvents into the membranes. However, fluorinated PAEs with various architectures need to be further explored for PV application. 

A. Sannigrahi, S. Takamuku, P. Jannasch, Block copolymers combining semi-fluorinated poly(arylene ether) and sulfonated poly(arylene ether sulfone) segments for proton exchange membranes, Int. J. Hydrogen Energy 39 (28) (2014) 15718-15727. 

A.K. Mohanty, E.A. Mistri, A. Ghosh, S. Banerjee, Synthesis and characterization of novel fluorinated poly(arylene ether sulfone) s containing pendant sulfonic acid groups for proton exchange membrane materials, J. Memb. Sci. 409 10 (2012) 145-155. 

Schonberger, R, Hein, M. and Kerres, J. 2007. Preparation and characterization of sulfonated partially fluorinated statistical poly(arylene ether sulfone)s and their blends with PBl. Solid State Ionics 178 547-554. 

Wholly aromatic polymers are thought to be one of the more promising routes to high performance PEMs because of their availability, processability, wide variety of chemical compositions, and anticipated stability in the fuel cell environment. Specifically, poly(arylene ether) materials such as poly-(arylene ether ether ketone) (PEEK), poly(arylene ether sulfone), and their derivatives are the focus of many investigations, and the synthesis of these materials has been widely reported.This family of copolymers is attractive for use in PEMs because of their well-known oxidative and hydrolytic stability under harsh conditions and because many different chemical structures, including partially fluorinated materials, are possible, as shown in Figure 8. Introduction of active proton exchange sites to poly-(arylene ether) s has been accomplished by both a polymer postmodification approach and direct co-... 

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