Syndiotactic styrene‐butadiene block copolymers synthesized with CpTiX3/MAO (Cp = C5H5, X = Cl,F; Cp = C5Me5, X = Me) and TiXn/MAO (n = 3, X = acac; n = 4, X = O‐tert‐Bu)

Copolymers sPS‐B consisting of blocks of syndiotactic polystyrene (sPS) and polybutadiene (B) have been prepared using CpTiX₃ (Cp = C₅H₅, X = Cl, F; Cp = C₅Me₅, X = Me) and TiX_n (n = 3, X = acetylacetonate (acac); n = 4, X = O‐tert‐Bu) activated with methylaluminoxane (MAO). If proper conditions are used, copolymers containing a range of styrene and butadiene molar fractions can be prepared. Structural analysis of these copolymers by means of ¹³C NMR spectroscopy allowed the assignment of different monomer diads (SS, SB, BB; S = styrene, B = butadiene) and the calculation of reactivity ratio products r₁·r₂. Differential scanning calorimetry (DSC) analysis further confirmed the block‐like structure of these copolymers. The melting points (T_m) of syndiotactic styrene sequences decrease as the styrene molar fraction decreases, whereas the glass transition temperature (Tg) increases with decreasing butadiene molar fraction in the copolymer. The polydispersity values (M_w/M_n) determined by GPC suggest that these copolymers are produced by a single site catalyst.