Structure of cyclopentene unit in the copolymer with propylene obtained by stereospecific zirconocene catalysts

Copolymerization of propylene and cyclopentene (CPE) was carried out using as a catalyst isospecific rac-ethylenebis(indenyl)zirconium dichloride (1), rac-dimethylsilylenebis(indenyl)zirconium dichloride (2), rac-dimethylsilylenebis(2-methylindenyl)zirconium dichloride (3), or syndiospecific diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (4) with methylaluminoxane as a cocatalyst. Isospecific zirconocene catalysts 1-3 produced copolymers having narrow molecular weight distribution, while syndiospecific catalyst 4 effected propylene homopolymerization. Microstructures of the copolymers were studied by ¹³C NMR and distortionless enhancement of polarization transfer (DEPT) spectroscopy. CPE was found to be incorporated in the copolymer preferentially via 1,2-insertion mechanism in the copolymerization with the catalyst 3. The catalyst 1 and 2 gave copolymers containing CPE units formed by either 1,2-insertion or 1,3-insertion mechanism. The proportion of 1,3-insertion units increased with increasing CPE content in the copolymers. The isomerization reaction from 1,2-insertion to 1,3-insertion CPE units was discussed on the basis of kinetic parameters.