Sulfonated poly- ketone

Recently, the pyrazole group containing bisphenols have been synthesized from activated aromatic dihalides and 3,5-bis (4-hydroxy phenyl)-4-phenyl pyrazole or 3,5-bis(4-hydroxy phenyl)-1,4-diphenyl pyrazole. A novel synthesis of imido aryl containing bisphenols has been reported [32]. N-substituted l,4-bis(4-hydroxy phenyl)-2,3-naphthalimides were prepared from phenolphthalein and copolymerized with aromatic sulfone or ketone difluorides to obtain the poly(imidoaryl ether) sulfones/ ketones. 

Among organic materials, poly(aryl ethers) and poly (aryl sulfides) have been known, as a class of engineering thermoplastics. The electron withdrawing sulfone and ketone groups usually activate the dihalo or dinitro compounds to facilitate the nucleophilic displacement through the transition state called Meisenheimer-Iike complex, and, thus, poly(aryl ether or sulfide) sulfones... 

Scheme 6.18 Synthesis of poly(ketone ketone sulfone) via a polyaminonitrile precursor.

Poly(ketone) (12) and poly(sulfone ketone) (14) are produced according to Scheme (9). They contain significant numbers of phenylene units substituted in p- and o-positions in addition to the m-phenylene units. 

The molecular weights of poly(ketone)s obtained from diphenyl ketone and diphenyl sulfone are lower than those from diphenyl ether and diphenyl sulfide. The former monomers possess highly electron-withdrawing carbonyl or sulfone groups, which lower the electron density of the rings. 

To date, much effort has been undertaken to develop new alternatives. For example, sulfonated aromatic polymers, i.e., polymers with the sulfonic acid groups directly attached to the main chain or carrying short pendant side chains with terminal sulfonic acid units, attract increasing interest because of their chemical and thermal stability, and the ease of the sulfonation procedure. Some of the proposed polymers are sulfonated polysulfone (SPSU) [134] sulfonated poly(phenylene oxide) (SPPO) [135] sulfonated poly-(ether ether ketone) (SPEEK) [136] poly(phenylquinoxaline) (PPQ) [137] and poly(benzeneimidazole) (PBI) [138],... 

In addition to Nafion-based catalyst layers, additional types have been developed, including CLs with different ion exchange capacities (lECs) [57,58] or with other hydrocarbon-type ionomers such as sulfonated poly(ether ether ketone) [58-60], sulfonated polysulfone [61,62], sulfonated polyether ionomers [63], and borosiloxane electrolytes [64], as well as sulfonated polyimide [65]. These nonfluorinated polymer materials have been targeted to reduce cost and/or increase operating temperature. Unfortunately, such CLs still encounter problems with low Pt utilization, flooding, and inferior performance compared wifh convenfional Nafion-based CLs. 

Easton, E. B., Astill, T. D., and Holdcroft, S. Properties of gas diffusion electrodes containing sulfonated poly (ether ether ketone). Journal of the Electrochemical Society 2005 152 A752-A758. 

Ramani, V., Swier, S., Shaw, M. T, Weiss, R. A., Kunz, H. R., and Fenton, J. M. Membranes and MEAs based on sulfonated poly(ether ketone ketone) and heteropolyacids for polymer electrolyte fuel cells. Journal of the Electrochemical Society 2008 155 B532-B537. 

Proton conductivity as a function of lEC for ETFE-g-PSSA = polyethylenetetrafluoroethylene-gra/t-polystyrene sulfonic acid, BAM membrane = substituted poly(trifluorostyrene) sulfonic acid, SPEEK = sulfonated poly(ether ether ketone) and Nafion. (From Peckham, T. J. et al. 2007. Journal of Materials Chemistry 17 3255-3268, and Dolye, M. et al. 2001. Journal of Physical Chemistry B 105 9387-9394.)... 

Studies on morphology and conclusions about observed levels of proton conductivity have also been carried out on PEMs other than Nafion and sulfonated poly(ether ketone). These include studies in which phenomenological examinations of relationships between conductivity and observed microstructure were carried out upon polymer systems where acid content was varied but the basic chemical structure was kept constant. In addition, other systems allowed... 

Of all the hydrocarbon-based PEMs, this group most likely has the largest variety of different systems. This is probably due to the wealth of prior knowledge of the nonsulfonated analogues that have been developed over the last several decades as well as the general expectation of higher thermal stability, better mechanical properties, and increased oxidative stability over polystyrene-based systems. Within the context of this section, polyarylenes are systems in which an aryl or heteroaryl ring is part of the main chain of the polymer. This section will, therefore, include polymers such as sulfonated poly (ether ether ketone) and sulfonated poly(imides) but will not include systems such as sulfonated polystyrene, which will be covered in Section 3.3.I.3. 

Sulfonated poly(arylene ether)s (SPAEKs) have also been developed for application in PEMs, with sulfonated poly(ether ether ketone) (SPEEK) (9a) as the archetypical example of this group. The base polymer of SPEEK is commercially available and relatively cheap, and sulfonation is a straightforward procedure using concentrated sulfuric acid. At sufficient levels of sulfonation, proton conductivity values for SPEEK are comparable to or higher than those of Nafion. However, this does lead to random copolymers where there... 

Direct copolymerization techniques have also been employed in the s)m-thesis of sulfonated poly(aryl ether ketones),i i polyimides, i 5 and poly(benzoimidazoles). The synthesis of random disulfonated biphenol poly(arylene ether sulfone) copolymers (BPSH x where x represents the percentage of disulfonated diphenylsulfone moieties in the polymer versus unsulfonated diphenylsulfone moities) (14) is shown in Scheme 3.5. 

In the sulfonated poly(arylene) systems described so far, the sulfonic acid groups have been statistically distributed along the polymer main chain. Poly(arylenes) in which the sulfonic acid sites are separated from the main chain by means of a spacer group have also been developed. Examples of systems in which this has been attempted include poly(p-phenylenes) (17),i isr poly(p-phenylene)-poly(aryl ether ketone) copolymers (18), and polyimides (19,20). These are shown in Eigure 3.24. 

One of the first examples of this type of blend was composed of SPEEK or SPES as the acidic component and diaminated PES, poly(4-vinylpyridine) (P4VP), poly(benzimidazole) (PBl), or poly(ethyleneimine) (PEI) as the basic component. " For blend lEC values of 1.0 meq/g, conductivity values were reported to be good, as was H2/O2 EC performance. Thermal stabilities for these blends was also demonstrated to be high (>270°C). Other examples of acid-base PEMs include blends of SPPO and PBI, sulfonated poly(phthalazinone ether ketone) and aminated SPES, SPIs and aminated Pls, and SPEEK with PES bearing benzimidazole side groups, ° as well as an unusual example in which the blend is composed of sulfonated, hyper-branched polyether and pyridine-functionalized polysulfone. ... 

Xing, P., Robertson, G. R, Guiver, M. D., Mikhailenko, S. D. and Kaliaguine, S. 2004. Sulfonated poly(aryl ether ketone)s containing the hexafluoroisopro-pylidene diphenyl moiety prepared by direct copolymerization, as proton exchange membranes for fuel cell application. Macromolecules 37 7960-7967. 

Fu, Y. Z., Manthiram, A. and Guiver, M. D. 2006. Blend membranes based on sulfonated poly(ether ether ketone) and polysulfone bearing benzimidazole side groups for proton exchange membrane fuel cells. Electrochemistry... 

Xing, D. M., Yi, B. L., Liu, F. Q., Fu, Y. Z. and Zhang, H. M. 2005. Characterization of sulfonated poly (ether ether ketone)/polytetrafluoroethylene composite membranes for fuel cell applications. Fuel Cells 5 406M11. 

Alberti et al. investigated the influence of relative humidity on proton conductivity and the thermal stability of Nafion 117 and compared their results with data they obtained for sulfonated poly(ether ether ketone) membranes over the broad, high temperature range 80—160 °C and RHs from 35 to 100%. The authors constructed a special cell used in conjunction with an impedance analyzer for this purpose. Data were collected at high temperatures within the context of reducing Pt catalyst CO poison-... 

The highest level, at structural scales >10 nm, is that over which long-range transport takes place and diffusion depends on the degree of connectivity of the water pockets, which involves the concept of percolation. The observed decrease in water permeation with decreasing water volume fraction is more pronounced in sulfonated poly(ether ketone) than in Nafion, owing to differences in the state of percolation. Proton conductivity decreases in the same order, as well. 

Directly copolymerized sulfonated poly(arylene ether ketone) PEMs are also possible by employing a sulfonated dihalide ketone monomer (sodium 5,5 -carbonylbis(2-fluorobenzenesulfonate)), as first reported by Wang. ° The sulfonated monomer chemical structure is shown in Figure 20. 

Sulfonated poly(arylene ether)s have shown promise for durability in fuel cell systems, while poly-(styrene)- and poly(imide)-based systems serve as model systems for studying structure-relationship properties in PEMs because their questionable oxidative or hydrolytic stability limits their potential application in real fuel cell systems. Sulfonated high performance polymer backbones, such as poly(phe-nylquinoxaline), poly(phthalazinone ether ketone)s, polybenzimidazole, and other aromatic or heteroaromatic systems, have many of the advantages of poly-(imides) and poly(arylene ether sulfone)s and may offer another route to advanced PEMs. These high performance backbones would increase the hydrated Tg of PEMs while not being as hydrolytically sensitive as poly(imides). The synthetic schemes for these more exotic macromolecules are not as well-known, but the interest in novel PEMs will surely spur developments in this area. 

Figure 13. A few microstructural parameters for Nafion and sulfonated poly(arylene ether ketone)s,i as a function of the solvent (water and/or methanol) volume fraction Xy. (a) the internal hydrophobic/hydrophilic interface, and (b) the average hydrophobic/hydrophilic separation and the diameter of the solvated hydrophilic channels (pores).

Figure 14. Solvent (water, methanol) diffusion coefficients of (a) Nafion 117 (EW =1100 g/equiv) and (b) sulfonated poly(arylene ether ketone)s, as a function of the solvent volume fraction. Self-diffusion data (AiaO. T eOi-i) are taken from refs 197, 224, 226, 255—263 and unpublished data from the laboratory of one of the authors) chemical diffusion coefficients (Z>h2o) are calculated from self-diffu-sion coefficients (see text), and permeation diffusion coefficients are determined from permeation coefficients. ...

Figure 17. Room-temperature proton conductivity of two Dow membranes of different EW values, Nation, two varieties of sulfonated poly (ary lene ether ketone) s (S— PEK and S—PEEKK, unpublished data from the laboratory of one of the authors), and sulfonated poly(phenoxyphos-phazene)s (S—POPs °9 of different equivalent weights (685 and 833 g/equiv), as a function of the degree of hydration n = [H20]/I—SO3H] (number below the compound acronym/ name indicates the EW value).

Figure 18. Proton conductivity of (a) Nation 117 (EW = 1100 g/equiv) and (b) a sulfonated poly(arylene ether ketone), as a function of temperature and degree of hydration [n = [H20]/[-S03H]). ...

Figure 18 shows the temperature dependence of the proton conductivity of Nafion and one variety of a sulfonated poly(arylene ether ketone) (unpublished data from the laboratory of one of the authors). The transport properties of the two materials are typical for these classes of membrane materials, based on perfluorinated and hydrocarbon polymers. This is clear from a compilation of Do, Ch 20, and q data for a variety of membrane materials, including Dow membranes of different equivalent weights, Nafion/Si02 composites ° ° (including unpublished data from the laboratory of one of the authors), cross-linked poly ary lenes, and sulfonated poly-(phenoxyphosphazenes) (Figure 19). The data points all center around the curves for Nafion and S—PEK, indicating essentially universal transport behavior for the two classes of membrane materials (only for S—POP are the transport coefficients somewhat lower, suggesting a more reduced percolation in this particular material). This correlation is also true for the electro-osmotic drag coefficients 7 20 and Amcoh...

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