Biaxial Chain Growth of Polyolefin and Polystyrene from 1,6-Hexanediylzinc Species for Triblock Copolymers

Abstract

Synthesis of polyolefin (PO)-based block copolymers is of immense research interest. In this work, we report a strategy for the construction of polystyrene (PS)-block-PO-block-PS, a useful thermoplastic elastomer, directly from olefin and styrene monomers. Multinuclear zinc species Et[Zn(CH2)6]aZnEt were prepared through successive additions of BH3 and Et2Zn to 1,5-hexadiene. Poly(ethylene-co-propylene) chains were biaxially grown from the −(CH2)6– units in Et[Zn(CH2)6]aZnEt via “coordinative chain transfer polymerization (CCTP)” using the pyridylaminohafnium catalyst. PS chains were subsequently grown in one pot from the generated polymeryl–Zn sites by subsequent introduction of the anionic initiator Me3SiCH2Li·(pmdeta) (pmdeta, pentamethyldiethylenetriamine) and styrene monomers. The fraction of the extracted PS homopolymer grown from the Me3SiCH2 sites was low (homo-PS (g)/total PS (g), 15–22%). The gel permeation chromatography (GPC) curves shifted evidently after styrene polymerization, and change in...