A New Strategy for the Synthesis of Hydroxyl Terminated Polystyrene-b-Polybutadiene-b-Polystyrene Triblock Copolymer with High Cis-1, 4 Content.

This work reports the preparation of a hydroxyl terminated polystyrene-b-polybutadiene-b-polystyrene triblock copolymer (SBS) with high cis-1, 4 content via a novel nickel catalyst, [η³-Ni(CH₂CHCHCH₂OOCH₃)][BPhF₄]. FT-IR, ¹H-NMR, and 13C NMR indicated that the polybutadiene segment of the copolymer contains greater than 90% cis-1, 4 structure, indicating achievement of the objective. Toward the functionalization goal, a hydroxyl group was successfully introduced at the end of the triblock copolymer (HO⁻SBS⁻OH). The results of gel permeation chromatography (GPC) revealed that the polymer is indeed a triblock copolymer, with no traces of homopolymer. Differential scanning calorimetry (DSC) showed that HO⁻SBS⁻OH synthesized using the novel catalyst had a lower glass transition temperature (Tg) than HO⁻SBS⁻OH synthesized with an alkyl lithium catalyst. Therefore, the polymer synthesized via the novel catalyst contains high cis-1,4 content and displays excellent low-temperature mechanical properties.