| Ionomers for polymer electrolyte membranes in fuel cell applications were developed utilizing the acidic bis(perfluoromethyl sulfonyl) imide functional group. Perfluorinated vinyl ether sulfonimide monomers CF2=CFOCF 2CF(CF3)O(CF2)2SO2N(Na)SO 2CF3 (1), CF2=CFOCF2CF(CF 3)O(CF2)2SO2N(Na)SO2(CF 2)4SO2N(Na)CF3 (2), CF 2=CFOCF2CF(CF3)O(CF2)2SO 2N(Na)SO2(CF2)6SO2N(Na)CF 3 (3) and CF2=CFOCF2CF(CF3)O(CF2) 2SO2N(Na)SO2(CF2)2O(CF 2)2SO2N(Na)CF3 (4) were synthesized through multiple steps.; The complete coupling reaction between the water sensitive CF3SO 2N(Na)Si(CH3)3 and the bromine-protected Dupont monomer BrCF2CFBrOCF2CF(CF3)O(CF2) 2SO2F is an important step to incorporate the sulfonimide group into the monomer 1. Bis(fluorosulfonyl) perfluoroalkanes FSO2RfSO2F (Rf = −(CF 2)4−, −(CF2)6− and −(CF 2)2O(CF2)2−) were used to introduce multifunctional sulfonimides into monomers 2, 3 and 4. Disulfonyl fluoride compounds were reacted with CF 3SO2N(Na)SiMe3 affording the unsymmetrical sulfonyl fluoride intermediates CF3SO2N(Na)SO2R fSO2F. After the transformation of −SO2F into −SO2N(Na)Si(CH3), the coupling reaction of the silyl compounds with BrCF2CFBrOCF2CF(CF3)O(CF 2)2SO2F followed by debromination gave the final products 2, 3 and 4.; Copolymers of the sulfonimide monomers with tetrafluoroethylene (TFE) were produced by semi-batch free-radical emulsion copolymerizations. The perflurinated vinyl ether sulfonimide, TFE, the redox initiator pair (NH4) 2S2O8/NaHSO3, the emulsifier C 7F15COONH4 and the buffer NaH2PO 4/Na2HPO4 were mixed in a stirred Parr autoclave at 10°C. During the copolymerization, TFE pressure and the sulfonimide monomer concentration were kept nearly constant in the reaction system to generate copolymers with acidic groups randomly distributed in the polymer chains. Copolymerization conditions were optimized through variations of some important reaction parameters such as the initiator concentration, TFE pressure, the sulfonimide monomer concentration and the surfactant concentration. Self-emulsifying copolymerizations of 2, 3 and 4 with TFE were also investigated. Among them, only monomer 4 can be copolymerized with TFE in the absence of the emulsifier C7F 15COONH4. Perfluorinated sulfonimide copolymers were characterized using the functional analysis, NMR and thermal analyses. The membranes and solutions produced from these sulfonimide copolymers exhibited excellent performance when incorporated into membrane electrode assemblies for fuel cell testing. |
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