CpTiCl3/MAO-catalyzed polymerization and copolymerization with isoprene and [3]dendralene derivatives

Coordination polymerization of a series of 2-substituted-[3]dendralenes, i.e., phenyl- (P3D), hexyl- (H3D), and trimethylsilyl-substituted [3]dendralenes (TMS3D), was investigated. No polymerization was observed for TMS3D, whereas P3D polymerized by CpTiCl3 as a catalyst and modified methylaluminoxane as an auxiliary catalyst to generate polymers that became insoluble in the process of isolation. Additionally, the coordination polymerization of H3D was conducted using a CpTiCl3/modified methylaluminoxane catalyst to produce polyH3D with mainly a trans-4,6 structure, which differs from that of the polymer obtained via anionic polymerization. The copolymerization of isoprene with H3D was also examined, and it was found that the reaction proceeded in a random fashion.