Bulk Synthesis and Modeling of Living ROMP of 1,5‐Cyclooctadiene for Narrowly Distributed Low Molecular Weight Linear Polyethylenes

The bulk ring‐opening metathesis polymerization (ROMP) of 1,5‐cyclooctadiene is carried out with a commercially available Grubbs' catalyst, bis(tricyclohexylphosphine)benzylidine ruthenium(IV) dichloride, with and without triphenylphosphine. Bulk ROMP exhibits living polymerization features and yields polyethylene mimics with comparable or improved molecular weight distribution control and similar conversions as solution ROMP. The reaction kinetics and polymer molecular weight development are well‐described by a mathematical model developed using the method of moments. The success of bulk ROMP and the development of the kinetic model show that bulk ROMP can be a viable polymerization pathway for the synthesis of low molecular weight linear polymers with well‐controlled structures.