In order to improve the synthetic route for diazonium perfluoroalkyl benzenesulfonylimide (PFSI) zwitterionic monomers, N-deacetylation of the coupling product was proposed to replace the reduction of aromatic amine intermediates. A series of hydrolysis methods, such as acid and base catalyzed refluxing, were explored for the N-deacetylation to obtain the PFSI aromatic amine. Factors such as temperature, concentration of acid/base and the time needed for the reaction to take place were investigated in an attempt to optimize the reaction condition. The basic hydrolysis was preferred since it was expected to carry out the N-deacetylation and debromination in one batch reaction. N-deacetylation in base at high concentrations was successful, however, side reaction of the perfluorovinyl ether occurred. It was discovered that the best N-deacetylation method is to reflux/sonicate the coupling product with acid in methanol for six hours. The intermediates and purified products were characterized with 1HNMR, 19FNMR, GC-MS and IR.

In order to achieve a more stable and highly proton conducting membrane that is also cost effective, the perfluoroalkyl benzenesulfonylimides (PFSI) polymers are proposed as electrolyte for Proton Exchange Membrane Fuel Cells. 4-(trifluoromethyl)-2-diazonium perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide (I) is synthesized from Nafion monomer via a 5-step schematic reaction at optimal reaction conditions. This diazonium PFSI zwitterionic monomer can be further subjected to polymerization. The loss of the diazonium N2+ functional group in the monomer is believed to form the covalent bond between the PFSI polymer electrolyte and carbon electrodes support. All the intermediates and final products were characterized using 1H NMR, 19F NMR and IR spectrometry.

It is very promising to introduce diazonium moiety into Nafion monomer based Diazonium (Perfluoroalkyl) Arylsufonylimide (PFSI) monomers for further polymerization and chemical grafting onto carbon electrodes as innovative electrolyte materials in the Proton Exchange Membrane (PEM) fuel cells. The PFSI polymers, more proton conductive and stable at high temperatures, can dramatically increase the stability and lifetime of the PEM fuel cells, compared to widely used perfluorosulfuric acid (PFSA) polymers. This paper presents such a straightforward methodology to optimally construct a new nafion based diazonium PFSI monomer analogue, 2-diazonium 4-(trifluoromethyl) perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonylimide II. New approaches have been investigated to dramatically increase the percent yield for another monomer I, 4-diazonium perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonylimide. The thermal stability of the two monomer analogues then have been measured and compared. Another monomer analogue, 4-diazonium-3-fluoro perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonylimide III, has been attempted and discussed.

Two new bis(perfluoroalkyl)arylsulfonyl imide monomers, which contain the aryl diazonium moiety and intramolecular zwitterionic fragment, have been designed and prepared for the first time from perfluoro(3-oxa-4-pentene)sulfonyl fluoride. As promising monomer candidates for high-performance proton exchange membrane fuel cell electrolytes, these two monomers have furnished perfluorinated electrolytes that include the polymers from perfluorinated sulfonic acid or perfluorinated sulfonimide monomers. The synthesis strategies and NMR analysis are summarized and discussed in details.

The overall goal of this research is to synthesize two different monomers for proton exchange membrane (PEM) Fuel Cells. Such monomers are proposed to be polymerized to improve the efficiency and compatibility of electrodes and electrolytes in PEM fuel cells. The first target is to synthesize 4-diazonium-3-fluoro PFSI zwitterionic monomer. Three steps were carried out in the lab. First one was the ammonolysis of 3-fluoro-4-nitrobenzenesulfonyl chloride. Second reaction was the bromination of Nafion monomer. The next coupling reaction, between brominated Nafion monomer and the 3-fluoro-4-nitrobenzenesulfonamide, was failed. The obstacles involve the harsh reaction condition and troublesome purification procedure. The second target is to synthesize 5-nitro-1, 3-benzenedisulfonamide. According to the literature, this synthesis was also designed as three steps: 1)nitration of sodium 1, 3-benzenedisulfonate salt; 2)chlorination of sodium 5-nitro-1, 3-benzenedisulfonate salt; and 3)ammonolysis of 5- nitro-1, 3- benzenedisulfonyl chloride. This monomer is expected to be copolymerized for membrane electrolyte in PEM fuel cells.

Two diazonium perfluoroalkyl arylsulfonimide (PFSI) zwitterionic monomers, 4-diazonium perfluoro(3-oxapent-4-ene)benzenesulfonimide (I) and 4-(trifluoromethyl)-2-diazonium perfluoro(3-oxapent-4-ene)benzenesulfonimide (II) have been synthesized from perfluoro(3-oxapent-4-ene) sulfonyl fluoride (POPF) for proton exchange membrane fuel cells. PFSI polymers are proposed as new electrolytes due to their better thermal stability, inertness to electrochemical conditions, and lower susceptibility to oxidative degradation and dehydration. For a better integration between the electrode and the electrolyte, the PFSI polymers are expected to be grafted onto the carbon electrode via the diazonium moiety. All the reaction intermediates and the final product were characterized with 1H NMR, 19F NMR and IR spectroscopies.

3-Diazonium- 4-(trifluorovinyloxy) - perfluorobutanesulfonyl benzenesulfonimide zwitterionic monomer (see figure 1) is proposed to be polymerized and further act as a new electrolyte for Polymer exchange membrane fuel cells (PEMFCs). One reason is that, the aromatic trifluorovinyl aryl ether (TFVE) group can easily be homopolymerized to aromatic perfluorocyclobutane (PFCB) polymer. Furthermore, the diazonium moiety in the monomer is expected to covalently attach the electrolyte to the carbon electrodes support. The perfluoroalkyl(aryl) sulfonimide (PFSI) pendant provides good chemical and mechanical stability as well as better proton conductivity. Several multi-step synthetic schemes are designed to obtain such monomer from perfluoroalkyl(aryl) sulfonimide (PFSI). Among them, the purified coupling product 4-OCF2CF2Br-3-NO2-PhSO2(M) SO2C4F9 from the first approach was successfully completed. The next stages of the work will involve dehalogenation, reduction, and diazotization to achieve the targeting monomer. All the intermediates were characterized by 1H and 19F NMR and FT-IR spectroscopy.

The objective of the research is to synthesize the diazonium N-(perfluoroalkyl) benzenesulfonimide (PFSI)zwitterionicpolymers as electrolytes in polymerelectrolyte membrane (PEM) fuel cells. The proposed diazoniumPFSI zwitterionic polymer (I) is expected to enhance the thermal and chemical stability, increase the proton conductivity of electrolytes, and improve the catalyst efficiency for PEM fuel cells. Synthesis of the perfluorobenzoyl peroxide initiator, homopolymerization of perfluoro (3-oxapent-4-ene) sulfonyl fluoride,coupling reaction with4-sulfamonylacetanilide, couplingreaction with 4-nitrobenzene sulfonyl amide, n-deacetylation reaction, and diazotization reactionhave been carried outsuccessfully in the lab. The intermediate chemicals are characterized by GC-MS, IR, NMR, and GPC spectroscopies.