2 REACTION ROUTES FOR THE PREPARATION OF AROMATIC POLYOXADIAZOLES AND POLYTRIAZOLES - SYNTHESES AND PROPERTIES

Two reaction routes for the preparation of aromatic poly-1,3,4-oxadiazoles and poly-1,2,4-triazoles are studied and their influence on the physical properties, i.e., inherent viscosity, glass transition, degradation temperature, and film integrity of the final products are discussed. Aromatic poly-1,3,4-oxadiazoles are prepared by means of a polycondensation reaction of terephthaloyl chloride and isophthalic dihydrazide yielding a precursor polymer, poly (p,m-phenylene) hydrazide, which is converted into the corresponding poly- 1,3,4-oxadiazole by means of a cyclodehydration reaction. Poly-1,3,4-oxadiazoles are also prepared by means of a polycondensation reaction between terephthalic and isophthalic acid and hydrazine yielding poly-1,3,4-oxadiazoles with higher inherent viscosities. Flexible poly-1,3,4-oxadiazole films are obtained only if the inherent viscosities of the polymers used are higher than 2.7 dL/g. The thermal stability is found to increase with increasing content of p-phenylene groups in the polymer backbone. Aromatic poly-1,2,4-triazoles are prepared using polyhydrazides with alternating para- and meta-phenylene groups and poly-1,3,4-oxadiazoles with a random incorporation of para- and meta-phenylene groups in the main chain as precursor polymers. The glass transition temperatures are found to increase with increasing content of p-phenylene groups in the main chain of these polymers. Cold crystallization is observed only for the alternating polymer. (C) 1994 John Wiley & Sons, Inc.