Monocyclopentadienyltitanium trichloride (CpTiCl3)/modified methylaluminoxane-catalyzed polymerization of 2-phenyl[3]dendralene: Homopolymerization and copolymerization of 2-phenyl[3]dendralene with isoprene or styrene

The control of the microstructures of polymer materials derived from diene-based monomers is crucial, and various synthetic methods, including anionic, radical, and coordination polymerization reactions, have been extensively explored. Here, we demonstrated the coordination polymerization of 2-phenyl[3]dendralenes (P3D) as a diene monomer. The polymerization process using monocyclopentadienyltitanium trichloride (CpTiCl₃) as a catalyst and modified methylaluminoxane (MMAO) as a cocatalyst (CpTiCl₃/MMAO) yielded polymers with an exclusive 4,6-structure that is distinct from those produced by anionic polymerization. Furthermore, the copolymerization of P3D with isoprene and styrene proceeded randomly.