SYNTHESIS OF POLYMERS CONTAINING N-N LINKAGES

The N-N linkage in hydrazine is thermally stable when it is tetrasubstituted and there are electron-withdrawing groups attached to the nitrogen atoms. Our research on the synthesis of polymers containing N-N linkages is reviewed. The N,N-bisimide structure has been introduced in the backbone of polymers as well as a pendant group in poly(aryl ether)s to give very thermoxidatively stable polymers with very high glass transition temperatures. Most of the polymers form tough,flexible films. N-Aminotriazoles also form stable imides by reaction with anhydrides and these N-imidotriazole groups have been introduced as pendent groups on poly(aryl ether)s. The polymers are highly fluorescent materials. Three methods for the synthesis of polymers containing the tetrasubstituted-azine structure will be discussed: (1) oxidative coupling of bisimines;(2) condensation of bishydrazones with diketones; (3) poly(aryl ether azines) from the azine formed from 4-fluorobenzophenone by reaction with salts of bisphenols.