The Structure of Polyfulvenes

Cationic polymerisation of 6,6-disubstituted pentafulvenes yields highly unsaturated, reactive macromolecules of high mo- . lecular weight. The mechanistic pathways leading to the polymers are discussed, and the structure XIV of the polymers has been elucidated by a combination of spectroscopic methods as well as by comparison with model compounds. In contrast to reports in the literature, the main process in thermal oligomerisation of simple pentafulvenes at 20 °c is a Diels-Alder reaction giving products of type XXI. Anionic polymerisation of pentafulvenes is initiated by traces of sodium cyclopentadienide or phenylsodium respectively. The reaction products consist of a mixture of oligomers of the series (fulvene)n. This surprising result can be explained by structure elucidation of the fulvene dimers, which gives formula XX. The mechanistic aspects of the reaction are discussed