Ring-Opening Metathesis Polymerization in Miniemulsion Using a TEGylated Ruthenium-Based Metathesis Catalyst

Ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) in miniemulsion was conducted utilizing a water-soluble TEGylated ruthenium alkylidene catalyst that was designed to undergo phase transfer from the aqueous phase to the monomer droplets or polymer particles following activation. The catalyst yielded colloidally stable latexes with ∼100% conversion, often in less than 1 h. Kinetic studies revealed first-order kinetics with good livingness as confirmed by the shift of gel permeation chromatography (GPC) traces. Depending on the surfactants used, the particle sizes ranged from 100 to 300 nm with monomodal distributions. The more strained cyclic olefin norbornene (NB) could also be efficiently polymerized in miniemulsion with full conversion and without coagulum formation.