Sulfonated poly synthesis

Robeson and Matzner were the first to report the synthesis of the sulfonation of DCDPS.205 This work makes it possible to synthesize sulfonated poly(arylene ether sulfone) with well-controlled structures. Ueda et al. used this monomer (Scheme 6.27) as a comonomer of DCDPS to react with bisphenol A and high-molecular-weight bisphenol-A-based copolymers with up to 30 mol % sulfonation achieved.206 Biphenol-based copolymers with up to 100 mol % sulfonation were recently reported by Wang et al.207... 

Polyether-PA segmented copolymers, synthesizing, 191-192 Polyether polyols, 200, 205, 211-212 synthesis of, 223, 224 Poly(ether sulfone) (PES), 327. See also Poly(arylene ether sulfone)s Poly(phenylene ether sulfone) chains Sulfonated poly (ary lene ether sulfone)... 

An example for the synthesis of poly(2,6-dimethyl-l,4-phenylene oxide) - aromatic poly(ether-sulfone) - poly(2,6-dimethyl-1,4-pheny-lene oxide) ABA triblock copolymer is presented in Scheme 6. Quantitative etherification of the two polymer chain ends has been accomplished under mild reaction conditions detailed elsewhere(11). Figure 4 presents the 200 MHz Ir-NMR spectra of the co-(2,6-dimethyl-phenol) poly(2,6-dimethyl-l,4-phenylene oxide), of the 01, w-di(chloroally) aromatic polyether sulfone and of the obtained ABA triblock copolymers as convincing evidence for the quantitative reaction of the parent pol3rmers chain ends. Additional evidence for the very clean synthetic procedure comes from the gel permeation chromatograms of the two starting oligomers and of the obtained ABA triblock copolymer presented in Figure 5. 

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. 

Shi, Z. Q., and Holdcroft, S. 2005. Synthesis and proton conductivity of partially sulfonated poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) block copolymers. Macromolecules 38 4193-4201. 

Figure 15. Synthesis of directly copolymerized wholly aromatic sulfonated poly(arylene ether sulfone), BPSH-ax, where XX is the ratio of sulfonated/unsulfonated activated halide.

Shobha et al. employed a novel sulfonated diamine containing a phosphine oxide moiety in the synthesis of a five—membered ring sulfonated poly-imide. The synthesis is shown in Figure 24. 

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

Figure 34. Synthetic scheme for the direct synthesis of sulfonated poly(benzthiazole)s.

Figure 35. Synthesis of sulfonated poly (benzimidazole) and poly(benzoxazole).

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. 

Novel approaches in PEM synthesis focusing on cheaper, usually fluorine-free PEMs and membranes capable of sustained fuel cell operation at elevated temperatures, have been reviewed in Ref. 75. Mature fuel cell membranes have been casted from sulfonated poly(arylene ether sulfone) (BPSH) random (statistical) copolymers [76]. 

K. Miyatake, H. Iyotani, K. Yamamoto, E. Tsuchda, Synthesis of poly(phenylene sulfite sulfonic acid) via poly(sulfonium cation) as a thermostable proton-conducting polymer, Macmmolecules, 1996, 29, 6969 K. Miyatake, K. Shouji, K. Yamamoto, E. Tsuchda, Synthesis and proton conductivity of highly sulfonated poly(thiopheny-lene), Macmmolecules, 1997, 30, 2941 K. Miyatake, K. Fukushima, S. Takeoka and... 

Figure 1. Schematic illustration of hollow polyelectrolyte capsule formation (a-c) followed by the selective inorganic synthesis inside (d-e). a-b layer-by-layer precipitation of poly(styrene sulfonate), poly(allylamine hydrochloride) monolayers b-c dissolution of template core c-d loading of polyelectrolyte capsules with corresponding anions d-e precipitation of inorganic material from... 

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). 

C. Zhao, X. Li, Z. Wang, Z. Dou, S. Zhong, and H. Na. Synthesis of the block sulfonated poly(ether ether ketone)s (S-PEEKs) materials for proton exchange membrane. J. Membr. ScL, 28(Xl-2) 643-650, September 2006. 

H. Weisse, H. Keul, and H. Hdcker. A new route to carboxylated poly-(ether sulfone)s Synthesis and characterization. Polymer, 42(14) 5973-5978, June 2001. 

Y. Li, F. Wang, J. Yang, D. Liu, A. Roy, S. Case, J. Lesko, and J. E. McGrath. Synthesis and characterization of controlled molecular weight di-sulfonated poly(arylene ether sulfone) copolymers and their applications to proton exchange membranes. Polymer, 47(11) 4210-4217, May 2006. 

Z. Wang, X. Li, C. Zhao, H. Ni, and H. Na. Synthesis and characterization of sulfonated poly(arylene ether ketone ketone sulfone) membranes for application in proton exchange membrane fuel cells. J. Power Sources, 160 (2) 969-976, October 2006. 

S. Vetter and S. P. Nunes. Synthesis and characterization of new sulfonated poly(arylene ether l,3,4-oxadiazole)s. React. Funct Polym., 61(2) 171-182, September 2004. 

Sulfonated poly(arylene ether phosphine oxide)s with fluorenyl groups were synthesized to establish proton exchange membranes (Scheme 42). Triphenylphosphine oxide-based diamino (arylene ethers) were made available (Scheme 43) that were utilized in the synthesis of polyimides. ... 

Bowen, W. R., Doneva, T. A., and Yin, H. B. 2001. Polysulfone—Sulfonated poly(ether ether)ketone blend membranes Systematic synthesis and characterisation. Journal of Membrane Science 181 253-263. 

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. 

Bisphenol Structure on the Direct Synthesis of Sulfonated Poly(arylene ether) Copolymers. 1. Journal ofPdymer Science Part A Polymer Chemistry 41 (2003) 2264-2276. 

B. ViSHNUPRIYA, K. Ramya, K. S. Dhathathreyan. Synthesis and characterization of sulfonated poly(phenyl-ene oxides) as membranes for polymer electrolyte membrane fuel cells. Journal of Applied Polymer Science 83 (2002) 1792-1798. 

P. Xing, G.P. Robertson, M.D. Guiver, S. D. Mikhailenko, K. Wang, S. Kaliaguine, Synthesis and characterization of sulfonated poly(ether ether ketone) for proton exchange membranes. Journal of Membrane Science 229 (2004) 95 106. 

Tsuchida et al. [95,96] reported the synthesis of poly(thiophenylene sulfonic acid) containing up to two sulfonic acid groups per repeating unit. Polymerisation of 4-(methylsulfinyl)diphenyl sulfide in sulfuric add upon heating or in the presence of SO3 resulted in sulfonated poly(sulfonium cation), which was then converted into the corresponding sulfonated poly(phenylene sulfide). 

Sulfonated ACPs are prepared both by direct sulfonation and by polycondensation and polycyclocondensation of sulfonated compounds. Synthesis of the first sulfonated poly(p-phenylene) was reported by Wegner and co-workers [103]. The Suzuki coupling of diboronic ethers with dibromo-aromatic monomers furnished poly(p-phenylene) with 95% yield. 

Sulfonated monomers were also used for the synthesis of sulfonated poly-imides [123,124]. hi particular, sodium salt of the sulfonated bis-4-[(3-aminophenoxy)phenyl]phenylphosphine oxide was used for the preparation of sulfonated polyimides [123]. 

Zhao Qiuxia, Hanson James, E. (2006). Direct Synthesis of Poly(arylmethyl sulfone) Monodendrons. Synthesis, (3), 397-399. 

Liu B, Kim DS, Guiver MD, Kim YS, Pivovar BS (2008) Sulfonated poly(aryl ether)-type polymers as proton exchange membranes synthesis and performance. In Peinemann KV, Pereira Nunes S (eds) Membranes for energy conversion, vol 2. Wiley-VCH, Weinheim, pp... 

Li X, Zhao C, Lu H, Wang Z, Na H (2005) Direct synthesis of sulfonated poly(ethCT ether ketone ketone)s (SPEEKKs) proton exchange membranes for fuel cells applications. Polymer 46 5820-5827... 

Crosslinked sulfonated poly(phenylene sulfide sulfone nitrile) has been prepared for its potential use for direct methanol fuel cell membrane applications [91]. The monomers and the synthesis are shown in Figure 5.9. 

Phu DS, Lee CH, Park CH, Lee SY, Lee YM. Synthesis of crosslinked sulfonated poly(phenylene sulfide sulfone nitrile) for direct methanol fuel cell applications. Macro-mol Rap Commun 2009 30(l) 64—8. 

Feng S, Shang Y, Xie X, Wang Y, Xu J. Synthesis and characterization of crosslinked sulfonated poly(arylene ether sulfone) membranes for DMFC applications. J Membr Sci 2009 335(l-2) 13-20. 

---