Sulfonated poly properties

Properties Unfilled 20% glass-fiber- reinforced Unfilled 20% glass-fiber- reinforced Poly(ether sulfone) Poly(phenyl sulfone)... 

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. 

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. 

Hietala, S., Skou, E. and Sundhokn, F. 1999. Gas permeation properties of radiation-grafted and sulfonated poly-(vinylidene fluoride) membranes. Polymer 40 5567-5573. 

Zhang, L., Ma, C. and Mukerjee, S. 2005. Effect of copolymer composition on the oxygen transport properties of sulfonated poly(arylene ether sulfone) and sulfonated poly(sulfide sulfone) PEMs. Journal of the Electrochemical Society 152 A1208-A1216. 

Tang, H., Pintauro, P. N., Guo, Q. and O Connor, S. 1999. Polyphosphazene membranes. ni. Solid-state characterization and properties of sulfonated poly[bis(3-methylphenoxy)phosphazene]. Journal of Applied Polymer Science 71 387-399. 

Elabd, Y. A., Napadensky, E., Walker, C. W. and Winey, K. 1. 2006. Transport properties of sulfonated poly(styrene-b-isobutylene-b-sytrene) triblock copolymers at high ion-exchange capacities. Macromolecules 39 399-407. 

Postsulfonation of polymers to form PEMs can lead to undesirable side reactions and may be hard to control on a repeatable basis. Synthesis of sulfonated macromolecules for use in PEMs by the direct reaction of sulfonated comonomers has gained attention as a rigorous method of controlling the chemical structure, acid content, and even molecular weight of these materials. While more challenging synthetically than postsulfonation, the control of the chemical nature of the polymer afforded by direct copolymerization of sulfonated monomers and the repeatability of the reactions allows researchers to gain a more systematic understanding of these materials properties. Sulfonated poly(arylene ether)s, sulfonated poly-(imide)s, and sulfonated poly(styrene) derivatives have been the most prevalent of the directly copolymerized materials. 

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 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...

A large number of macromolecules possess a pronounced amphiphilicity in every repeat unit. Typical examples are synthetic polymers like poly(l-vinylimidazole), poly(JV-isopropylacrylamide), poly(2-ethyl acrylic acid), poly(styrene sulfonate), poly(4-vinylpyridine), methylcellulose, etc. Some of them are shown in Fig. 23. In each repeat unit of such polymers there are hydrophilic (polar) and hydrophobic (nonpolar) atomic groups, which have different affinity to water or other polar solvents. Also, many of the important biopolymers (proteins, polysaccharides, phospholipids) are typical amphiphiles. Moreover, among the synthetic polymers, polyamphiphiles are very close to biological macromolecules in nature and behavior. In principle, they may provide useful analogs of proteins and are important for modeling some fundamental properties and sophisticated functions of biopolymers such as protein folding and enzymatic activity. 

Table 12. Mechanical properties of the complexes of aminoacetalized poly(vinyl alcohol) (PC)-carboxymethylated poly(vinyl alcohol) (PA) and sulfonated poly(vinyl alcohol) (PSA)-poly(vinyl alcohol) acetalized with 2,2-diethoxyethyltrimethylammonium (PTC)4415... 

Hung [3] incorporated benzimidazole derivatives, (II), into sulfonated poly-ethersulfones as a method for preventing filler leaching, improving mechanical properties, and decreasing methanol permeability. 

Furthermore, in 2001, Ballard entered an alliance with Victrex to produce two new membrane alternatives. One membrane is based on sulfonated poly(arylether) ketone (a variant of PEEK) supplied by Victrex, which may be better suited to PEMFC fabrication applications. In March 2002, U.S. Patent 6,359,019 was issued to Ballard Power for a graft-polymeric membrane in which one or more trifluorovinylaromatic monomers are radiation graft polymerized to a preformed polymeric base. The strucmres of BAM membranes have been studied by way of small-angle neutron scattering (SANS) [97]. The study of the ionomer peak position suggests the existence of relatively small ionic domains compared to Nalion, despite large water content. Phase separation in the polymer matrix is possibly crucial for the membrane s mechanical and transport properties. 

H. Tang, P.N. Pintauro, Q. Guo and S. O Connor, Polyphosphazene membranes. III. Solid-state characterization and properties of sulfonated poly[bis(methylphenoxy)-phosphazene], J. Appl. Polym. Sci., 1999, 71, 389-399. 

In this chapter, we describe the synthesis, kinetics, and solution properties of poly(N-vinylpyrrolidone-co-sodium styrenesulfonate) [poly(NVP-co-NaSS)], poly(N-vinylpyrrolidone-co-sodium acrylamido-2-methylpropane-sulfonate [poly(NVP-co-NaAMPS)], poly(N-vinylpyrrolidone-co-N,N-di-methyl-N-methacroyloxyethylammoniopropanesulfonate [poly(NVP-co-SPE)], poly(N-vinylpyrrolidone-co-N,N-dimethyhN-methacroylamidopropylam-moniopropanesulfonate [poly(NVP-co-SPP)], and poly(N-vinylpyrrolidone-co-2-vinylpyridiniopropanesulfonate [poly(NVP-co-SPV)]. Radical copolymerizations were carried out in water solutions with AIBN initiator at elevated temperature (e.g., 60 °C), (see reactions 1-5). 

M. Yoshimune, 1. Fujiwara, H. Suda, and K. Haraya. Gas transport properties of carbon molecular sieve membranes derived from metal containing sulfonated poly(phenylene oxide). Desalination, 193(l-3) 66-72, May 2006. 

Y. S. Kim, B. Einsla, M. Sankir, W. Harrison, and B. S. Pivovar. Stracture-property-performance relationships of sulfonated poly(arylene ether sulf-one)s as a polymer electrolyte for fuel cell applications. Polymer, 47(11) 4026 035, May 2006. 

Mauritz, K. A., Blackwell, R. L, and Beyer, F. L., Viscoelastic properties and morphology of sulfonated poly(styrene-i -ethylene/butylenes-i>-styrene) block copolymers (sBCP), and sBCP/[silicate] nanostructured materials. Polymer, 45, 3001-3016 (2004). 

B. Bae, K. Miyatake, M. Watanabe, Sulfonated poly(arylene ether sulfone ketone) multiblock copolymers with highly sulfonated block. Synthesis and properties. Macromolecules 2010,43(6), 2684-2691. 

---