Sulfonated Diels-Alder poly

Sulfonated Diels-Alder poly(phenylene) (SDAPP). 

FIGURE 6.19 DMFC performance of DA-SPPs and Nafion (80°C, 200 seem of air fed to the cathode at 15 psig backpressure 1 mL min methanol fed to anode at 0 psig backpressure 1 M left, 3 M right.). (Reprinted from J. Power Sources, 195, Stanis, R. J., Yaklin, M.A., Cornelius, C.J., Takatera, T., Umemoto, A., Ambrosini, A., and Fujimoto, C.H., Evaluation of hydrogen and methanol fuel cell performance of sulfonated Diels Alder poly(phenylene) membranes, 104-110, Copyright (2010), with permission from Elsevier.)... 

FIGURE 6.20 Charge-discharge curves of the SDAPP membranes. (Reprinted from Electrochem. Commun., 20, Fujimoto, C., Kim, S., Stains, R., Wei, X., Li, L., and Yang, Z.G., Vanadium redox flow battery efficiency and durability studies of sulfonated Diels Alder poly(phenylene)s, 48-51, Copyright (2012), with permission from Elsevier.)... 

Stanis R. J., Yaklin M. A., Cornelius C. J., Takatera T., Umemoto A., Ambrosini A., Fujimoto C. H., Evaluation of hydrogen and methanol fuel cell performance of sulfonated Diels Alder poly(phenylene) membranes. Journal of Power Sources, 2010, 195, 104-110. 

Anionic and Cationic Polymerizations o Radical Polymerization Advances o Coordination Polymerizations 0 Step-Growth Polymerization Advances 0 Synthesis of Tactic Polymers o Stereoblock Copolymers o Dispersion Polymerizations o Cellulosic Graft Copolymers o Diels-Alder Polymer Forming Reactions o A New Path To Phenolic Resins o Nitrogen Heterocycle Polymerizations o Optically Active Polymers o Poly (Phenylene Sulfide) o Poly (Aryl Ethers) o (Poly (Aryl Ether Sulfones) o Epoxy and Isocyanate Resin Replacement o Azlactone Functionalized Oligomers o Epoxy Resin-Isocyanate Reactions o Chelating Polymers o Oxazoline Functionalized Polymers o Poly (Alkyl Methacrylates) o Macromers... 

Fig. 7.12 Synthesis of polysulfophenylated poly(phenylene) via Diels-Alder polymerization followed by sulfonation...

Cornelius et al. have synthesized a series of unique poly(phenylene)-based polyelectrolytes by Diels-Alder polymerization followed by post-sulfonation (Fig. 7.12) [29-32]. The ionomers are composed of sulfonated, highly phenylated poly(phenylene)s and do not carry any heteroatoms as their constituents except for the sulfonic acid groups. The complete aryl backbone resulted in a tough rigid-rod material with no Tg below the decomposition temperature. The stiffness of the ionomer backbone did not negatively affect the membrane properties such as water uptake (21-137%, in water) and proton conductivity (13-123 mS/cm, in water at 30°C) with lECs ranging from 0.98 to 2.2 meq/g. 

The Diels-Alder reaction is another straightforward way to synthesize poly (/7-phenylene)s [10-13]. Figure 6.6 shows the synthesis and sulfonation process of DA-sulfonated poly(phenylene sulfone) (DA-SPP) ionomers. However, they might be mixed with a few flexible meta-linkages due to their sterically crowded systems. 

Lim Y, Lee H., Lee S., Jang H., Hossain M. A., Cho Y, Kim T., Hong Y, Kim W., Synthesis and properties of sulfonated poly(phenylene sulfone)s without ether linkage by Diels-Alder reaction for PEMFC apphcation, Electrochimica Acta, 2014, 119, 16-23. 

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