Norbornene polymerization and ethylene/norbornene copolymerization catalyzed by constrained geometry cyclopentadienyl-phenoxytitanium catalysts

Norbornene polymerization and ethylene/norbornene copolymerization were studied using constrained geometry complexes 2-(tetramethylcyclopentadienyl)-4,6-di-tert-butylphenoxytitanium dichloride (1), 2-(tetramethylcyclopentadienyl)-6-tert-butylphenoxytitanium dichloride (2), and 2-(tetramethylcyclopentadienyl)-6-phenylphenoxytitanium dichloride (3) as catalysts with AliBu3 and Ph3CB(C6F5)4 as cocatalysts. Polymerization results indicate that these catalyst systems are highly active for both the homopolymerization of norbornene and the copolymerization of ethylene with norbornene. The norbornene homopolymerization is vinyl addition polymerization. Ethylene/norbornene copolymers with high norbornene incorporation (>50%) were easily obtained with these catalyst systems by increasing the norbornene feed concentration. The produced polymers were characterized by 13C NMR, IR, DSC and GPC.