Novel Sulfonated Co-poly(ether imide)s Containing Trifluoromethyl, Fluorenyl and Hydroxyl Groups for Enhanced Proton...

A hydroxyl group containing new cardo diamine monomer was synthesized, namely 9,9-bis (hydroxy- (4'-amino(3-trifluoromethyl)biphenyl-4-oxy)-phenyl)-9H-fluorene (mixture of isomers, HAPHPF). HAPHPF, along with a sulfonated diamine monomer, 4,4'-diaminostilbene-2,2'-disulfonic acid (DSDSA), was used to prepare a series of new sulfonated copolyimides by polycondensation with 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA). The degree of sulfonation (DS < 1) was adjusted by the feed ratio of DSDSA/HAPHPF and the copolymers were named as DHN-XX, where XX denotes the mole percentage of DSDSA (XX = 50, 60, and 70). The copolymers showed high molecular weights. The copolymer structure and composition were confirmed by FTIR and NMR techniques. Copolymer membranes were prepared through solution cast route by using dimethyl sulfoxide as a solvent. The membranes showed high thermal, mechanical, hydrolytic and peroxide radical stability, and low water uptake and low swelling ratios. Well-separated hydrophilic and hydrophobic phase morphology was observed in TEM and AFM images of the copolymer membranes and was further supported by the SAXS studies. The proton conductivity of the DHN-70 was as high as 97 mS cm^-1 at 80 °C and the value is significantly higher than that of the nonhydroxylated analogue. The membranes also showed superior microbial fuel cell (MFC) performance, similar like Nafion 117 under similar test conditions. The chemical oxygen demand removal values provide substantial evidence that the fabricated membranes can be utilized in bioelectrochemical systems.