Polyisobutylene-Based Thermoplastic Elastomers. I. Synthesis and Characterization of Polystyrene-Polyisobutylene-Polystyrene Triblock Copolymers

Abstract Polystyrene-polyisobutylene-polystyrene triblock copolymer thermoplastic elastomers have been synthesized by living carbocationic sequential copolymerization using the tert-butyl dicumyl chloride/TiCl4/methylcyclohexane:methyl chloride (60:40 v:v)/ −80°C system in the presence of the proton trap 2,6-di-tert-butylpyridine. Structure-property relationships have been examined by varying the Mn of the PIB middle block (39,000 to 156,000) and that of the PSt end-segment (1,000 to 19,000). The tensile strength is controlled by the molecular weight of the PSt segment and independent of the PIB middle block length in the studied range. Phase separation starts when the Mn of the PSt segment reaches ∼ 5,000, and it is complete when the Mn reaches ∼ 15,000. These triblocks exhibited 23-25 MPa tensile strength, similar to that of styrenic thermoplastic elastomers obtained by anionic polymerization.