Multiblock Copolymers Based on Highly Crystalline Polyethylene and Soft Poly(ethylene‐co‐butadiene) Segments: Towards Polyolefin Thermoplastic Elastomers

Block copolymers based on polyethylene (PE) and ethylene butadiene rubber (EBR) were obtained by successive controlled coordinative chain transfer polymerization (CCTP) of a mixture of ethylene and butadiene (80/20) and pure ethylene. EBR-b-PE diblock copolymers were synthesized using the {Me2 Si(C13 H8 )2 Nd(BH4 )2 Li(THF)}2 complex in combination with n-butyl,n-octyl magnesium (BOMAG) used as both the alkylating and chain transfer agent (CTA). Triblock and multiblock copolymers featuring highly semi-crystalline PE hard segments and soft EBR segments were further obtained by the development of a bimetallic CTA, the pentanediyl-1,5-di(magnesium bromide) (PDMB). These new block copolymers undergo crystallization-driven organization into lamellar structures and exhibit a variety of mechanical properties, including excellent extensibility and elastic recovery in the case of triblock and multiblock copolymers.