Synthesis and characterization of some new aromatic polytriazoles as proton conductive membranes

A series of new poly(1,2,4-triazole)s (PTAs) containing pyridine heterocyclic ring, bearing bulky aromatic pendent groups, were synthesized from the reaction of the corresponding polyhydrazides with aniline or 4-aminobenzenesulfonic acid in polyphosphoric acid (PPA) at 175 °C. The non-sulfonated PTAs showed glass transition temperatures (T _gs) of 220–250 °C and inherent viscosities (η _inh) equal to 0.48–0.78 dL/g, and the sulfonated poly(1,2,4-triazole)s (S-PTAs) exhibited T _gs of 235–265 °C and inherent viscosities equal to 0.50–0.83 dL/g. The former polymers were soluble in conc. H₂SO₄ and partially soluble in hot N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), and 1-methyl-2-pyrrolidone (NMP), and the latter were soluble in DMF, NMP, DMSO and DMAc at room temperature. All polymers had useful levels of thermal stability and were stable up to 450 °C in nitrogen. The proton conductivities of undoped sulfonated polytriazole membranes and the acid-doped sulfonated polytriazole membranes lie in the range of 5 × 10^?4–8.1 × 10^?3 and 5 × 10^?3–2.3 × 10^?2 S/cm, respectively, at 90 °C and 100 % relative humidity.