Ethylene-co-norbornene Copolymerization Using a Dual Catalyst System in the Presence of a Chain Transfer Agent

Ethylene-co-norbornene copolymers were synthesized by a dual catalyst system at three concentrations of norbornene in the feed and variable amounts of ZnEt2, as a possible chain transfer agent. The dual catalyst system consists of two ansa-metallocenes, isopropyliden(η5-cyclopentadienyl)(η5-indenyl)zirconium dichloride (1) and isopropyliden(η5-3-methylcyclopentadienyl)(η5-fluorenyl)zirconium dichloride (2), activated with dimethylanilinium tetrakis(pentafluorophenyl)borate, in presence of TIBA. Values of norbornene content, molecular mass, glass transition temperature, and reactivity ratios r11 and r21 of copolymers prepared in the presence of 1+2 are intermediate between those of reference copolymers. The study of tensile and elastic properties of ethylene-co-norbornene copolymers (poly(E-co-N)s) gave evidence that copolymers were obtained in part through transfer of polymer chains between different transition metal sites. Mechanical properties are clearly different from those expected from a blend of the parent samples and reveal that copolymers obtained in the presence of 1+2 and ZnEt2 consist of a reactor blend of segmented chains produced by exchange from 2 to 1 and 1 to 2 acting as the ideal compatibilizer of chains produced by the chain transfer from 1 to 1, and from 2 to 2.