Sulfonated poly phthalazinone ether

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. ... 

Gao, Y., Robertson, G. R, Guiver, M. D., Jian, X. G., Mikhailenko, S. D. and Kaliaguine, S. 2005. Proton exchange membranes based on sulfonated poly(phthalazinone ether ketone)s/aminated polymer blends. Solid State Ionics 176 409-415. 

Figure 31. Synthesis of directly polymerized sulfonated poly(phthalazinone ether sulfone) ...

Su et al. [138] prepared composite PEMs from sulfonated poly(phthalazinone ether ketone) (sPPEK) and various amounts of sulfonated silica nanoparticles (silica-SO3H). The use of silica-SO H was seen to compensate for the reduction in the lEC of the membrane, while the strong -SO3H/-SO3H interaction between sPPEK chains and silica-SO3H particles led to ionic crosslinking in the membrane structure, which improved not only the thermal stability but also the methanol resistance. 

Y. Dai, X. Jian, S. Zhang, and M. D. Guiver. Thermostable ultrafiltration and nanoflltration membranes from sulfonated poly(phthalazinone ether sulfone ketone). J. Membr. ScL, 188(2) 195-203, July 2001. 

Sulfonated poly(phthalazinone ether ketone nitrile) (SPPEKN) copolymers prepared by the copolymerization of disodium 3,3 -disulfonate-4,4 -difluorobenzophenone, 2,6-difluorobenzonitrile, and 4-(4-hydroxy-phenyl)-l(2H)-phthalazinone exhibit a tensile strength higher than that of Nafion 117. The proton conductivities of the acid form of SPPEKN copolymers, with a feed ratio or sulfonated to unsulfonated monomer above 0.35, are around lO Scm at 80°C, which is close to that of Nafion 117.39... 

Sulfonated poly(phthalazinone ether ketone nitrile), 295 TAZ... 

Dai, Y, Jian, X., Zhang, S., and Guiver, M. D. 2002. Thin film composite (TFC) membranes with improved thermal stability from sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK). Journal of Membrane Science 207 189-197. 

Sulfonated poly(phthalazinone ether ketones) were synthesized directly by aromatic nucleophilic polycondensation of 4-(4-hydroxyphenyl)phthalazino-ne with various ratios of 5,5 -carbonylbis-(2-fluorobenzenesulfonate) or 4,4 -difluorobenzophenone [109]. 

Sulfonated poly(phthalazinone ether sulfones) were directly prepared by polycondensation of 4-(4-hydroxyphenyl)phthalazinone with various rations of disodium salt of 5,5 -sulfonylbis-(2-fluorobenzenesulfonate) to 4-lluorophenylsulfone [117]. 

Kim DS, Shin KH, Park HB, Lee YM (2004) Preparation and characterization of sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK)/silica hybrid membranes for direct methanol fuel cell applications. Macromol Res 12 413-421... 

Nafion (Fu et al. 2008). However, the corresponding proton conductivity value is lower. The methanol crossover, however, is only one-third of that found in Nafion 115, compared at the same thickness. Although the PSf membrane has lower proton conductivity than Nafion, the lower production cost and methanol crossover make it a promising alternative for DMFC. Sulfonated poly(phthalazinone ether ketone) (SPPEK) has been discovered as a new kind of PEM for DMFC due to its superior performance in terms of chemical and oxidative resistances, mechanical strength, and thermal stability (Gao et al. 2003). Tian et al. reported that SPPEK prepared from direct polymerization of presulfonated monomer has better performance than that of postsulfonation (Tian et al. 2005). Unfortunately, with direct polymerization it was hard to control the DS and location of sulfonation. 

Tian, S.H., Shua, D., Chen, Y.L., Xiao, M. and Meng, Y.Z. 2005. Preparation and properties of novel sulfonated poly(phthalazinone ether ketone) based PEM for PEM fuel cell application. J. Power Sour. 158 88-93. 

Wu, X., He, G., Gu, S., Hu, Z., Yao, P. Novel interpenetrating polymer network sulfonated poly(phthalazinone ether sulfone ketone)/polyaciylic acid proton exchange membranes for fuel cell. J. Membr. Scl. 295, 80-87 (2007)... 

Proton exchange membranes (PEM) were also prepared by solution blending of sulfonated poly(phthalazinone ether ketone) (sPPEK) and various amotmts of sulfonated silica nanoparticles (silica-SOsH) [58]. The solution blending techiuque was also used in combination with compression molding thus, poly(ether ether ketone) (PEEK)-based nanohybrids were fabricated by means of compression molding at 400°C under a pressure of 60 MPa using silica surface-modified with stearic acid and PEEK [59]. 

Su Y-H, Liu Y-L, Sun Y-M, Lai J-Y, GuiverMD, Gao Y (2006) Using silica nanoparticles for modifying sulfonated poly(phthalazinone ether ketone) membrane for direct methanol fuel cell a significant improvement on cell performance. J Power Sourc 155(2) 111-117... 

Scheme 2.30 Structure of sulfonated poly(phthalazinone ether ketone)s. Taken from Ref. [141],...

H. Pan, X. Zhu, J. Chen, X. Jian, Synthesis of fluoro-containing sulfonated poly(phthalazinone ether ketone ketone)s and their properties as PEM in PEMFC and DMFC, J. Memb. Sci. 326 (2) (2009) 453 59. 

YX. Zhang, Synthesis and Modification of Sulfonated Poly(Phthalazinone Ether)s for Proton Exchange Membranes (Master s degree dissertation), Dalian University of Technology, China, 2007. 

In the case of sulfonated poly(phthalazinone ether ketone)s being used as a matrix, composite membranes showed less swelling in water and methanol, better mechanical and thermal stability, but lower proton conductivity [94, 95]. The results suggest that the amount of inorganic additives have to be optimized for each ionomer material and fuel cell operation conditions. Addition of 5 wt% of... 

Xiao GY, Sun GM, Yan DY, Zhu PF, Tao P (2002) Synthesis of sulfonated poly (phthalazinone ether sulfones) by direct polymerization. Polym Prepr 43(19) 5335-5339... 

Sulfonated poly(phthalazinone ether ketone) [91], Data from [73],... 

Y. Gao, G. P. Robertson, M. D. Guiver, X. Jian, Synthesis and characterization of sulfonated poly(phthalazinone ether ketone) for proton exchange membrane materials. J. Polym. Sci. A 41, 497-507 (2003). 

Y. L. Chen, Y. Z. Meng, A. S. Hay, Direct synthesis of sulfonated poly(phthalazinone ether) for proton exchange membrane via N-C coupling reaction. Polymer 46, 11125-11132 (2005). 

Sulfonated poly(phthalazinone ether sulfone ketone) (sPPESK) (Eig. 1.10) was prepared by sulfonation of PPESK with faming H2SO4. The proton conductivity of sPPESK (DS of 81%) was 0.013 at 80 °C (not much lower than that of Nafion 15). On the other hand, its permeability to methanol at 15 °C was apparently nearly 40 times less than that of Nafion 115. These results seem to indicate that the Faraday efficiency of DMFCs may be good, if sPPESK membranes are used as PEMs [168]. 

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