Tandem Ring-Opening Metathesis - Vinyl Insertion Polymerization: Fundamentals and Application to Functional Polyolefins.

The accomplishments in the copolymerization of ethylene with cyclic olefins such as norborn-2-ene or cis-cyclooctene via tandem ring-opening metathesis polymerization (ROMP) - vinyl insertion polymerization (VIP) are outlined. This approach provides polyolefins with high molecular weight (600,000 < M < 4,500,000 g mol ) and substantial amounts of double bonds along the polymer main chain. Olefinic moieties in ROMP-derived polymers can be converted into hydroxyl, amino, silyl, ester, or carboxylate groups by different means including controlled radical polymerization-based grafting. The underlying concept for the switch in polymerization mechanism, the resulting pre-catalyst requirements, limitations and challenges and the chemistry developed for functionalizing unsaturated polymers are outlined in detail.