Unveiling the molecular structure of ethylene/1-octene multi-block copolymers from chain shuttling technology

A method for assessing the puzzling molecular architecture of ethylene/1-octene multi-block copolymers, synthesized via chain-shuttling technology, is proposed. They are commercial elastomers characterized by alternating segments with low (hard blocks) and high (soft blocks) octene concentration. Our molecular assessment allows determining plausible value for the average length of blocks and number of blocks/chain, setting the basis for a definitive elucidation of structure-properties relationships of these elusive systems. Namely, the molecular basis which explains the similar crystallization properties, and the large difference in mechanical properties of this class of copolymers is unveiled thanks to our approach. We demonstrate that at 25 °C we have similar values of Young modulus and deformation at break higher than 1400%, but large strain hardening before breaking or flat mechanical behavior up to the break, depending on the short or long average block length of the multiblock copolymers, respectively, coupled with a high or low number of blocks/chain, respectively. At 60 °C these differences are amplified entailing no strain hardening but preservation of high ductility for copolymers with short average block length and high number of blocks/chain, remarkable decrease of strain at break of about two orders of magnitude (from ≈2000 to ≈90%) for copolymers with long average block length and lower number of blocks/chain.