Preparation and Characterization of Soft-Hard Block Copolymer of 3,4-IP-b-s-1,2-PBD Using a Robust Iron-Based Catalyst System

A series of well-defined diblock copolymers, namely, 3,4-polyisoprene-block-syndiotactic-1,2-polybutadiene (3,4-PI-b-s-1,2-PBD), with a soft–hard block sequence were synthesized via an in situ sequential polymerization process using a robust iron-based catalytic system Fe(acac)3/(isocyanoimino) triptenylphosphorane (IITP)/AliBu3. This catalyst exhibits vigorous activity and temperature tolerance, achieving a polymerization activity of 5.41 × 106 g mol(Fe)−1 h−1 at 70 °C with a [IP]/[Fe] ratio of 15,000. Moreover, the quasi-living polymerization characteristics of the catalyst were verified through kinetic experiments. The first-stage polymerization of isoprene (IP) is performed at 30 °C to give a soft 3,4-PI block, and then a quantitative amount of 1,3-butadiene was added in situ to the quasi-living polymerization system to produce a second hard s-1,2-PBD. The s-1,2-PBD segments in block copolymers display a rodlike morphology contrasting with the spherulitic morphology characteristic of s-1,2-PBD homopolymers. The precise tunability of the length of the soft and hard chain segments of these novel elastic materials with the feed ratio of IP and BD, endowing them with outstanding mechanical properties and excellent dynamic mechanical properties, which are expected to be promising high-performance rubber materials.