Polymer Synthesis via Intermolecular Carbonyl-Olefin Metathesis Polymerization

Intermolecular carbonyl-olefin metathesis polymerization (ICOMP) catalyzed by Lewis acids has been developed as an efficient method for synthesizing functional polymeric materials. The reactivities and polymerization kinetics of various aldehyde and olefin monomers were systematically investigated. Readily accessible iron- and boron-based Lewis acids exhibited high catalytic efficiency even at low loadings. Aromatic aldehydes demonstrated superior reactivity compared to aliphatic analogs, while 1,1-disubstituted olefins and conjugated dienes showed enhanced metathesis efficiency over conventional olefins or 2-methyl-substituted derivatives. Mechanistic studies revealed that ICOMP proceeds through step-growth polycondensation when combining aldehydes with acyclic dienes, whereas a chain-growth mechanism predominates in reactions involving cyclic dienes. Notably, the compatibility of ICOMP with numerous potentially bioderived aldehydes and olefins underscores its broad substrate scope and sustainability.