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 {Me2Si(C13H8)2Nd(BH4)2Li(THF)}2 complex in combination with n-butyl,n-octyl magnesium (BOMAG) used as both alkylating and chain transfer agent (CTA). Triblock and multiblock copolymers featuring highly semi-crystalline PE hard segments and soft EBR segments were further obtained via 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.