Perfluorosulfonate ionomers, hydration

The sensitivity to hydrolysis is a key issue in many applications. The ester bond in 4GT-PTMO copolymers is sensitive to hydrolysis however, it is fairly protected since most of the ester is contained in a crystalline structure. The addition of a small amount (1-2%) of a hindered aromatic polycarbodiimide substantially increases the lifetime of this material in the presence of hot water or steam (Brown et al., 1974). Polyurethanes are susceptible to hydrolytic attack, especially those with polyester soft segments. However, polyester soft segment polyurethanes are generally more resistant to oils, organic solvents, and thermal degradation. lonomers will swell when exposed to water in fact, a commercial hydrated perfluorosulfonic ionomer (Nation) is used as a membrane separator in chlor-alkali cells. Styrene-diene copolymers and polyolefin TPEs are insensitive to water. 

Another approach for increasing the amount of water in the anode catalyst layer is to boost the water content in the catalyst layer components. A conventional catalyst layer, for instance, may contain up to 30% by weight amount of fully hydrated perfluorosulfonic ionomer. Thus, an increase in water content can be accomplished by increasing the amount of the water-containing ionomer used in the catalyst layer or by employing a different ionomer with higher water content. Alternatively, more hygroscopic materials may be incorporated into the anode catalyst layer to retain more water therein. 

The earliest concerted effort in the research and development of Nafion perfluorosulfonate ionomers was directed toward their use as a permselective membrane separator in electrochemical cells used in the large scale industrial production of NaOH, KOH, and CI2. In short, the membrane in this application, in addition to keeping CI2 and H2 gases separated, prevents the unfavorable back migration of hydrated OH ions from the catholyte (concentrated aqueous NaOH or KOH) chamber, while allowing for the transport of hydrated Na+ ions from the anolyte chamber in which is aqueous NaCl. 

Lowry, S. R., Mauritz, K. A., An investigation of ionic hydration effects in perfluorosulfonate ionomers by Fourier transform infrared spectroscopy. J. Am. Chem. Soc. 1980, 102 (14), 4665-1667. 

I, 1980, 76, 2558-2574 L.Y. Levy, A. Jenard and H.D. Hurwitz, Hydration and ion-exchange process in carboxylic membranes. Part 1. Infrared spectroscopic investigation of the acid membranes, J. Chem. Soc. Trans. 1, 1982, 78, 29-36 M. Falk, Infrared spectra of perfluorosulfonated polymer and water in perfluorosulfonate polymer, Perfluorinated Ionomer Membranes, ed. A. Eisenberg, H.L. Yeager, ACS Symposium Series, American Chemical Society, Washington DC, 1982, p. 139 C. Heitner-Wirguin and D. Hall, An infrared study of an anion exchange membrane,... 

J.H. Han, K.W. Lee, G.W. Jeon, C.E. Lee, W.K. Park, E.H. Choi, H nuclear magnetic resonance study of hydrated water dynamics in perfluorosulfonic acid ionomer NAFION, Appl. Phys. Lett. 106 (2015) 023104. 

Yoshimiu-a and Iwasaki of Sumitomo Chemical Co. have synthesized aromatic ionomers containing pendant perfluorosulfonic acid groups (Fig. 7.29) [79]. Poly (arylene ether sulfone) was brominated and then perfluorosulfonated via Ullmann coupling reaction in the presence of copper catalyst. The lEC was controllable up to 1.58 meq/g. The obtained ionomer membranes behaved very differently from the typical sulfonated aromatic ionomer membranes. Characteristic hydrophobic/hydro-philic separation (ca. 3-4 nm) was observed in the smaU-angle X-ray scattering (SAXS) analyses of the hydrated samples. The ionic clusters were slightly smaller... 

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