Transition metal catalyzed polymerisation of norbornene

Metallocene/methylaluminoxane and single component Pd(II)-catalysts are compared to methylaluminoxane activated Ni and Pd-catalysts for the vinylpolymerisation of norbornene. Ni(II), Ni(0) and Pd(II)-compounds were found to be orders of magnitude more active than metallocenes and produce polymers of much higher molecular weights. Polymerisation kinetics for these systems have been studied in detail and reflected high initial activity followed by significant catalyst deactivation. Based on NMR-spectroscopy and WAXS five types of polynorbornenes have been identified and structures are proposed.