Copolymerization of styrene and conjugated dienes with half‐sandwich titanium(IV) catalysts: The effect of the ligand structure on the monomer reactivity, monomer sequence distribution, and insertion mode of dienes

The copolymerization of styrene and 1,3‐butadiene (Bd) or isoprene (Ip) was carried out with half‐sandwich titanium(IV) Cp′TiCl3 catalysts (where Cp′ is cyclopentadienyl 1, indenyl 2, or pentamethylcyclopentadienyl 3) with methylaluminoxane as a cocatalyst. For the copolymerization with Bd, catalyst 3 gave the copolymers containing the highest amount of Bd among the catalysts used. The resulting copolymers were composed of a styrene–Bd multiblock sequence. High melting points were observed in the copolymers prepared with catalyst 1. The structures of hydrogenated poly(styrene‐co‐Bd) were studied by 13C NMR spectroscopy, and the long styrene sequence length was detected in the copolymers prepared with catalyst 1. For styrene/Ip copolymerization, random copolymers were obtained. Among the used catalysts, catalyst 1 gave the copolymers containing the highest amount of Ip. The copolymers prepared with catalyst 1 showed a steep melting point depression with increasing Ip content because of the high ratio of 1,4‐inserted Ip units and/or the low molecular weights of the copolymers.