Polymerization of Quinodimethane and Related Compounds.

Abstract

Polymerizations of unsubstituted quinodimethane which is too reactive to be obtainable as condense state, were described in the flash pyrolysis and vapor-coating methods. Chlorine-substituted quinodimethanes were compared with the number of chlorine-substituents. Electron-accepting, substituted quinodimethanes like TCNQ, obtainable as stable crystalline compounds, are not homopolymerizable but copolymerizable with donor monomers like styrene in an alternating fashion. Tetrakis (methoxycabonyl) - and tetrakis (ethoxycarbonyl) -quinodimethane exhibit amphoteric behavior in their alternating copolymerizations. Some quinodimethanes with different two substituents at 7 and 8 positions are homopolymerizable, for instance, anionic polymerization of BCQ occured in living type and gave the polymer with molecular weight above million. Their homopolymerizations also showed an equilibrium behavior which allowed us to determine thermodynamic data for polymerization of those monomers. Their copolymerizations with styrene occurs in random fashion The cross propagation step was studied in detail by means of linear free energy relationship.