The Synthesis and Thermal Degradation of Some Ferrocene - Containing Polyazines and Poly-Schiff Bases.

A series of ferrocene-containing polymeric azines and polymeric Schiff bases were synthesized by means of acid-catalyzed solutions poly-condensations. The molecular structures of the polymers synthesized have been determined and information concerning their thermal behavior has been obtained. Comparative thermal stabilities of the products of polymerization of aliphatic and aromatic diamines with 1,1-diformylferrocene and 1,1-diacetylferrocene were investigated by thermogravimetric analysis both in air and in an inert atmosphere. In the inert atmosphere, initial weight loss due to thermal stress did not occur below 300C in all cases and in many cases 50-70 residue of polymer sample remained at 700C. The use of a fluorinated diamine led to the synthesis of a polymer which did not exhibit any significant enhancement of thermal properties. Investigation of the polymer products by direct inlet mass spectroscopy led to the observation that several of the systems contained significant amounts of cyclic dimers, although linear polymers were the major products in most cases. Extraction of the cyclic dimers followed by molecular weight determinations by vapor phase osmometry confirmed their molecular structures. Author