AbstractRing-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) of an unsaturated ε-caprolactone, 6,7-dihydro-2(3H)-oxepinone (DHO2), are alternative routes to produce unsaturated aliphatic polyesters with the same molecular structure. Polymerization of DHO2 initiated by Al isopropoxide in toluene at room temperature or at 0°C proceeds by a coordination-insertion mechanism, although intramolecular transesterification takes place beyond complete monomer conversion. The molecular weight distribution is narrow as long as monomer conversion does not exceed 90%. Ring-opening metathesis polymerization of DHO2 initiated by Schrock’s Mo-based catalyst, 1, at 60°C allows higher molecular weight unsaturated polyester to be prepared, even though an intramolecular side reaction also operates. The structure of poly(DHO2) synthesized by ROP and ROMP is the same, as confirmed by 1H, 13C NMR, and FT-IR spectra. Copolymers of DHO2 with norbornene, cis-cyclooctene, and 1,5-cyclooctadiene have been successfully prepared.
Molecular Weight Control via Cross Metathesis in Photo‐Redox Mediated Ring‐Opening Metathesis Polymerization
