Both the vinyl insertion polymerization (VIP) of olefins and the ring-opening metathesis polymerization (ROMP) of cyclic olefins are well-established polymerization techniques and are based on the insertion of a monomer between a transition metal (ion) and the growing polymer chain. In fact, they are related to each other, since a cationic, VIP-active catalyst may be converted into a ROMP-active one by a simple α-H elimination process. The occurrence of both VIP- and ROMP-derived structures in poly(norborn-2-ene) was observed for the first time some 60 years ago and in fact paved the way for identifying and understanding metathesis-based processes. However, the controlled synthesis of cyclic olefin copolymers of ethylene with, e.g., norborn-2-ene or cis-cyclooctene containing both VIP- and ROMP-derived structures is unprecedented. Here, we describe our approach to such copolymers having high molecular weights (Mn≤1,500,000 g/mol), low polydispersity indexes (1.02&lt;PDI&lt;2.0) and a tailored content of double bonds. These unsaturated groups can be used for grafting as well as for hydrophilization and derivatization reactions and thus provide access to functional polyolefins.

Tandem ring-opening metathesis/vinyl insertion copolymerization of ethylene with cyclic olefins: Access to functional polyolefin block-copolymers

253rd National Meeting (2017)

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