Enol Ethers Are Effective Monomers for Ring-Opening Metathesis Polymerization: Synthesis of Degradable and Depolymerizable Poly(2,3-dihydrofuran).

Abstract

Enol ethers are widely used as quenching reagents for Grubbs catalysts. However, we report the surprisingly effective ring-opening metathesis polymerization (ROMP) of cyclic enol ethers, because the resulting electron-rich ruthenium alkylidene complex remains active toward metathesis of electron-rich olefins, despite its deactivation toward hydrocarbon olefins. We demonstrate the first example of ROMP of cyclic enol ethers, using 2,3-dihydrofuran as the monomer, producing a new type of degradable and depolymerizable poly(enol ether). The polymers exhibited perfect regioregularity, and their molecular weights can be regulated by the loading of Grubbs initiators or by the use of a linear vinyl ether as the chain transfer agent. We also developed protocols to deactivate the catalyst following metathesis of enol ethers and cleave the catalyst off the resulting polymers using H2O2 oxidation. The resulting poly(dihydrofuran) can be recycled to monomer via depolymerization with Grubbs catalyst or degraded to small molecules by hydrolysis under acidic conditions. This work opens exciting opportunities for a new class of ROMP monomers that lead to degradable polymers.