A novel synthetic strategy for styrene–butadiene–styrene tri-block copolymer with high cis-1,4 units via changing catalytic active centres

A styrene–butadiene–styrene tri-block copolymer (SBS) with a high cis-1,4 unit content (greater than 97%) was synthesized by a novel synthetic strategy based on changing the catalytic active centres using n-butyllithium and a nickel-based catalyst. Firstly, styrene was polymerized via anionic polymerization using butyllithium as the initiator (Li, activity centre Li) at 50°C. The obtained alkylated macroinitiator (PSLi) was aged with nickel naphthenate (Ni) and boron trifluoride etherate (B) to prepare a second reactive centre (Ni-F), which was used to initiate the polymerization of butadiene (Bd). Finally, triphenyl phosphine (PPh(3)) was added to adjust the electron density of the third active centre (P-Ni-F), and styrene monomer was added again to synthesize the second polystyrene block to obtain SBS. The polymerization technique presented here is simple and has an efficient initiation effect due to the high initiation activities for the different monomers. It also exhibits excellent control over the stereo-structure of the butadiene segments in the prepared copolymers, and the SBS polymers with high cis-1,4 unit content were easily achieved.