Ring-opening metathesis polymerization (ROMP) has become a versatile technique to synthesize well-defined polymers due to its high functional group tolerance and reliability in complex settings, though controlling the chain-end functionality and recycling the metal initiators still remain challenges.This presentation will explore the application of functional enyne reagents to overcome these challenges in ROMP. The key to all of these methods is a terminal alkyne that rapidly reacts with the ruthenium alkylidene and serves as a directing group to promote otherwise inefficient transfer reactions intramolecularly. Using this general relay strategy, different enyne molecules can be designed to give direct polymer-polymer coupling or to generate functional initiators, enabling the functionalization of both ends of the metathesis-derived polymer chain. The enyne derivatives are also capable of recycling the ruthenium catalyst in pulsed-addition ring-opening metathesis polymerization (PA-ROMP) to produce multiple functional chains from single ruthenium initiator with low dispersities. The utility of ROMP for macromolecular construction are widely expanded through these enyne reagent designs and could find broad application in the design of functional materials.

Functional enyne reagents for modifying metathesis-derived polymers

ACS Fall 2020 Virtual Meeting

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