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

Abstract

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 (Tg) 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 Tgs 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.