Cyclopolymerization of ( E,E ) - [6.2]paracyclophane-1,5-diene

Abstract

Polymerization of ( E , E )-[6.2]paracyclophane-1,5-diene proceeds by an intra–intermolecular mechanism to give a polymer containing a [3.2]paracyclophane in the repeat unit. Polymerization occurs with either free radical or cationic initiation; anionic initiation was unsuccessful. Cationic polymerization is favored and appears to proceed through a stabilized carbonium ion intermediate. Spectroscopic and model compound studies are consistent with the proposed polymer structure. Thermal analyses of the polymer indicate a complex thermooxidative behavior in the presence of oxygen, while depolymerization occurs above about 400°C in an inert atmosphere.