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Updated: Sep 21, 2025

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life
Ian D Robertson1, Leon M Dean2, Gabriel E Rudebusch3
1Departments of Chemistry, ‡Materials Science and Engineering, §Aerospace Engineering, and the ⊥Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States.
Abstract:
Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.
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