Controlled polymerization of levoglucosenone-derived enynes to give bio-based polymers with tunable degradation rates and high glass transition temperatures

In recent years, pollution from plastic waste has intensified the demand for sustainable polymers. Hence, biomass-derived degradable polymers offer a promising solution. For example, levoglucosenone, a readily available biomass product from cellulose pyrolysis, is an attractive building block for polymer synthesis. However, the metathesis polymerization of levoglucosenone-derived monomers has been difficult to control due to poor monomer reactivity, requiring an unstable but reactive ruthenium catalyst (C793). To facilitate the polymerization, we introduced a cascade motif to successfully demonstrate controlled polymerization of levoglucosenone-derived enynes using a commercially available 3rd-generation Grubbs catalyst. This living polymerization also enabled block copolymer synthesis. Furthermore, the degradation rates of these polymers can be adjusted over 2 orders of magnitude through monomer structural modifications. Notably, we observed higher glass transition temperatures of 152-198 °C by varying structural parameters.