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 < Mn < 4,500,000 g mol−1) 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.