Synthesis of a high‐trans 1,4‐butadiene/isoprene copolymers with supported titanium catalysts

The copolymerization of butadiene (Bd) and isoprene (Ip) with a supported titanium‐triisobutyl aluminum catalyst system was studied. An analysis using differential scanning calorimetry, X‐ray diffraction, and13C‐NMR spectra indicated that products with 25–60 mol % Bd units were random copolymers and that the melting temperatures and glass‐transition temperatures (Tg) were 30–40 and −74°C (or thereabout), respectively, which were very similar to those of natural rubber. The chemical structure of these copolymers was characterized by a high‐trans 1,4‐configuration: the trans 1,4‐content of Ip units was greater than 98%, and the trans 1,4‐content of Bd units was greater than 90%. The reactivity ratio of Bd was greater than that of Ip (rBd= 5.7 andrIp= 0.17). The sequence distribution of the monomer units of the copolymers followed a first‐order Markov statistical model.