Synthesis and characterization of some new aromatic polyoxadiazoles through cyclodehydration of polyhydrazides

A series of new polyhydrazides containing pyridine heterocyclic ring, bearing bulky aromatic pendent groups, were synthesized from the reaction of diacid chlorides with dihydrazides via low-temperature solution polycondensation. All the polymers were readily soluble in polar solvents such as N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), and 1-methyl-2-pyrrolidone (NMP) and showed inherent viscosities equal to 0.38–0.68 dL/g. They indicated glass transition temperatures (T _g) ranging from 190 to 220 °C. Polyhydrazides were subjected to cyclodehydration to prepare poly(1,3,4-oxadiazole)s either by thermally or chemically cyclodehydration approximately in the region of 150–320 °C. The poly(1,3,4-oxadiazole)s, made by chemically cyclodehydration exhibited T _gs of 220–250 °C and inherent viscosities equal to 0.38–0.62 dL/g, while the PODs made via thermally cyclodehydration of polyhydrazides did not show any glass transition and exhibited inherent viscosities equal to 0.39–0.66 dL/g. The former polymers were soluble in conc. H₂SO₄ and partially soluble in hot DMF, NMP, DMSO, and DMAc, and the latter were only soluble in conc. H₂SO₄. They had useful levels of thermal stability and were stable up to 450 °C in nitrogen. The structure of polymers was fully characterized by IR and NMR spectroscopies.